inkjet ink, inkjet engraving method, and inkjet engraving device

专利摘要:
INK JET INK, INK JET RECORDING METHOD, AND INK JET RECORDING DEVICE. An inkjet ink, which contains water, organic solvent, a surfactant, and a colorant, in which the organic solvent contains at least one polyhydric alcohol having an equilibrium moisture content of 30% by weight or more at a temperature of 23 ° C and humidity of 80% RH, at least one amide compound represented by the general formula (I), and at least one selected from the group consisting of compounds represented by the following general formula (II) to (IV): general formula (I ) general formula (II) general formula (III) general formula (IV)
公开号:BR112013023754B1
申请号:R112013023754-6
申请日:2012-03-09
公开日:2020-12-01
发明作者:Hiroshi Goto；Akihiko Gotoh；Kiyofumi Nagai；Yuuki Yokohama；Hidetoshi Fujii
申请人:Ricoh Company, Ltd.；
IPC主号:

专利说明:

TECHNICAL FIELD
The present invention relates to an inkjet ink, an inkjet engraving method and an inkjet engraving device. BACKGROUND OF THE TECHNIQUE
An inkjet ink containing an aqueous pigment as a colorant has several advantages when it is used for printing on flat paper, such as less scattering occurrences, high image density, and less passing orientation occurrences. In the event that a large amount of ink is deposited, such as when printing photographs or diagrams, on flat paper, however, printed flat paper tends to cause backsliding. Backfeeding is a phenomenon in which the paper is bent away from the side of the printed surface. If flat paper backfeed occurs right after printing, a paper transfer failure occurs in the inkjet printer (inside the device) during the paper transport process. Transporting the paper is very difficult especially when the paper is backfired right after high speed printing or double sided printing.
Therefore, it is desired to develop an inkjet ink that does not give any or less feedback when it is used with a large amount of its deposition on flat paper, such as when printing photographs and drawings on flat paper. Especially a high-speed inkjet printer equipped with an inline head has a greater need for such ink compared to a serial printer.
As the known technique for suppressing paper curl, there is a method for applying an alcohol solution to the paper before embossing with an ink, allowing the paper to be substantially dry in a recording position, and performing the embossing with the ink ( see PTL1). PTL1 teaches that the hydroxy groups in the alcohol solution are linked to hydroxyl groups present at the hydrogen bonding points between the cellulose fibers of paper to block water molecules in the ink with hydrophobic groups in the alcohol solution. However, this method does not work when a large amount of aqueous ink is ejected during high speed printing and is therefore not able to prevent the paper from curing immediately after printing.
Furthermore, there is a recording method for ejecting an ink and a reaction solution that reacts with the ink, and in this method the reaction solution is ejected to land on an opposite surface of a recording medium to the surface where the ink is recorded, corresponding to the data identical to the data to record the ink (see PTL2). According to this method, however, the configuration of a recording device for use is complex, and the curl of the printed paper cannot be prevented unless a reaction liquid formed from substantially the same formulation for that ink is ejected in the same or in an amount similar to that of the ink. Therefore, the method is economically disadvantageous. Since the large amount of water is contained on both sides of the paper when a solid image is printed on almost the entire area of the paper, the paper loses its stiffness, making it difficult to transport the paper.
In addition, PLT3 discloses an inkjet ink composition containing diglycerin or polyglycerin in combination with polyethylene glycol monoalkyl ether, and PTL4 discloses an inkjet ink composition containing polyethylene glycol monomethyl ether. This inkjet ink composition, however, does not demonstrate any paper curl prevention effect when the aqueous ink is ejected in large quantities with high speed printing. Therefore, the proposed inkjet ink composition does not meet the demands to prevent paper curl right after it is printed. Since the organic solvent contained in the inkjet ink composition has a low equilibrium moisture content, moreover, the ink composition cannot ensure ejection stability. LIST OF CITATIONS Patent Literature PTL1: JP Patent Application Open to the Public (JP-A) no 2004-136458 PTL2: JP-A no 2008-18711 PTL3: JP-A no 2009-52018 PTL4: JP-A no 2009- 287014 SUMMARY OF THE INVENTION Technical problem
The present invention aims to provide an inkjet ink capable of suppressing the curl of flat paper right after it is printed with the ink, and having excellent ejection stability, and to provide an inkjet engraving method and a printing device. inkjet recording. Solution to the Problem
The means to solve the problems mentioned above are as follows: An inkjet ink that contains: water; 5 an organic solvent; a surfactant; and a colorant, in which the organic solvent contains at least one polyhydric alcohol having an equilibrium moisture content of 30% by mass or more at a temperature of 23oC and humidity of 80% RH, at least one amide compound represented by the formula general (I), and at least one selected from the group consisting of 15 compounds represented by the following general formulas (II) to (IV):
General Formula (I) where R is a C4-C6 alkyl group
where R1 is a hydrogen atom or a C1-C2 alkyl group, and R2 is a C1-C4 alkyl group,
a C1-C2 alkyl group, and R3 is an atom of
the present invention contains at least one polyhydric alcohol having an equilibrium moisture content of 30% by weight or more at a temperature of 23oC and humidity of 80% RH, at least one amide compound represented by the general formula (I), and at least one selected from the group consisting of compounds represented by the following general formulas (II) to (IV), irregularity and curl just after printing the ink can be reduced, which provides excellent image quality image formation on flat paper, excellent correspondence with high speed printing and excellent ejection stability.
Furthermore, using, as the colorant for use in the inkjet ink of the present invention, a self-dispersing pigment on a surface from which a functional group is provided, preferably the functional group which is at least one selected from the group consisting of - COOM, -SO3M, -PO3HM, -PO3M2, -CONM2, -SO3NM2, -NH-C6H4-COOM, - NH-C6H4-SO3M, -NH-C6H4-PO3HM, -NH-C6H4-PO3M2, -NH-C6H4 -CONM2, and -NH-C6H4-SO3NM2, (M is a quaternary ammonium ion), an inkjet ink having particularly high storage stability over time, and capable of suppressing the increase in ink viscosity can be provided when the moisture is evaporated. It is assumed that the use of the functional group that uses quaternary ammonium as a counterion in the inkjet ink makes it possible to stably maintain the dispersion state of the water-dispersible pigment ether in water-rich ink or in ink rich in organic solvent.
In addition, when using a modified pigment as the colorant, preferably a modified pigment that is modified with a geminal bisphosphonic acid group or a geminal bisphosphonate group, an inkjet ink having particularly high storage stability over time, and capable to suppress the increase in ink viscosity when moisture is evaporated. It is assumed that modifying the pigment surface with the geminal bisphosphonic acid group or geminal bisphosphonate group makes it possible to stably maintain the dispersion state of the water-dispersible pigment ether in water-rich paint, or in paint rich in organic solvent.
When an ordinary printing sheet is used for printing, high quality images having less dripping (irregularities in the image density), having excellent drying properties can be formed for the printed images. Note that the common printing sheet mentioned above is a recording medium that contains a support and a coating layer formed on at least one surface of the support, and has low ink absorption, that is, an amount of pure water transferred to the recording medium as measured by a dynamic scanning absorptometer being 1 ml / m2 to 35 ml / m2 with a contact duration of 100 ms, with 3 ml / m2 to 4 ml / m2 with a contact duration of 400 ms.
The ink means fixed for use in the present invention contain the ink jet ink of the present invention and embossing means. The recording medium contains a support, and a coating layer coated on at least one surface of the support, and an amount transferred from pure water to the recording medium as measured by a dynamic scanning absorptometer is 1 ml / m2 to 35 ml / m2 with contact duration of 100 ms, and is 3 ml / m2 to 40 ml / m2 with contact duration of 400 ms. As a result of this configuration of the recording medium in combination with the ink, it is possible to image high-quality images to print images, with excellent drying properties, without causing dripping (density inequalities).
The ink cartridge for use in the present invention contains a container, and the inkjet ink of the present invention housed in the container. The ink cartridge is preferably used in inkjet engraving system printers. The use of the ink housed in the ink cartridge makes it possible to reduce the degree of curl of flat paper right after printing, and to provide excellent image quality images on flat paper corresponding to high speed printing. Furthermore, it can reduce the dripping (irregularities in image density) of an image formed on a glossy printing paper, and the ink has excellent drying properties as well as excellent ejection stability from a nozzle, to this how to conceive image recording of similar quality to that of vivid prints.
The inkjet engraving method of the present invention contains at least one inkjet step, where the inkjet step is applying stimulation to the inkjet ink of the present invention to make the inkjet jet ink, in this way, forming an image on a recording medium. According to the inkjet engraving method, stimulus (energy) is applied to the inkjet ink of the present invention, in the inkjet stage, to make the inkjet inkjet form an image on the recording medium. Therefore, the inkjet engraving method produces significantly improved color saturation images, and excellent colorability even when images are formed on flat paper. Furthermore, the inkjet engraving method of the invention can provide vivid images close to images of industrial prints, with less dripping (unevenness in image density) on glossy printing paper, excellent drying properties, speed of drying, and correspondence to high speed printing, and desirable stability in ink ejection from the nozzles.
The ink jet recording device of the present invention contains at least one ink jet unit configured to apply stimulus (energy) to the ink jet ink of the present invention to make the ink jet form an image on a recording medium. . In the inkjet recording device, the inkjet unit applies stimulus (energy) to the inkjet ink of the present invention to make the inkjet form an image on a recording medium. As a result, the formed image has significantly improved color saturation, and excellent coloring ability when the image is formed on flat paper. In addition, the inkjet engraving device can form vivid images close to industrial print images, with less dripping (unevenness in image density) on glossy printing paper, excellent drying properties, drying speed, and correspondence with high speed printing, and desirable stability in ink ejection from nozzles. ADVANTAGE EFFECTS OF THE INVENTION
As will become clear from the descriptions below, the present invention can solve the various problems in the technique, and provide an inkjet ink capable of suppressing the curl of flat paper right after it is printed with the ink, yielding excellent quality images and having excellent response to high speed printing, excellent ejection stability, and drying properties on printing sheets in general, as well as providing an inkjet engraving method, and an inkjet engraving device. BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a schematic diagram illustrating an example of an ink cartridge for use in the present invention.
Figure 2 is a schematic diagram illustrating an example of a modification of the ink cartridge of figure 1.
Figure 3 is a perspective diagram illustrating an example of the state in which the cover of the ink cartridge loading section is open.
Figure 4 is a cross-sectional view to explain an example of the entire body structure of the inkjet recording device of Figure 3.
Figure 5 is an enlarged schematic diagram to illustrate an example of an inkjet head for use in the present invention.
Figures 6A to 6C are diagrams to explain an example of a difference in an effect of the interaction between cellulose molecules between water and a water-soluble organic material containing a hydroxy group, and Figure 6A is a schematic diagram of an elementary fibril, figure 6B is a schematic diagram of a cellulose molecule, and figure 6C is a diagram illustrating hydrogen bonds (α), (β) and (Y) formed between two cellulose molecules.
Figure 7 is a schematic diagram illustrating an example of an internal structure of a printing device prototype with in-line head used in the evaluation of ripple. DESCRIPTION OF THE MODALITIES (Inkjet Ink)
The present invention will be specifically explained below.
The inkjet ink of the present invention contains at least water, an organic solvent, a surfactant, and a colorant, and can also contain a penetrating agent, a water-dispersible resin, and other substances, if necessary. <Organic Solvent>
The inkjet ink contains, as the organic solvent, at least one polyhydric alcohol having an equilibrium moisture content of 30% by weight or more at a temperature of 23oC and humidity of 80% RH, at least one amide compound represented by the general formula (I), and at least one selected from the group consisting of compounds represented by the following general formulas (II) to (IV). The use of these compounds as the organic solvent for inkjet ink can suppress paper curl right after printing, in order to design an inkjet ink capable of providing high quality images. This is because the organic solvent (for example, the amide compound represented by the general formula (I) and the compounds represented by the general formulas (II) to (IV) are unlikely to cleave the hydrogen bonds between the cellulose molecules of the paper when the organic solvent penetrates the space between the cellulose molecules.
General formula (I) In general formula (I), R is a C4-C6 alkyl group.
Examples of the C4-C6 alkyl group include a butyl group, an isobutyl group, a tertiary butyl group, a pentyl group, an isopentyl group, a hexyl group and an isohexyl group.

In the general formula (II), R1 is a hydrogen atom or a C1-C2 alkyl group, and R2 is a C1-C4 alkyl group. Examples of the C1-C4 alkyl group include a methyl group and an ethyl group. Examples of the C1-C4 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and a tertiary butyl group.
General formula (III) In the general formula (III), R 'is a C1-C2 alkyl group, and R3 is a hydrogen atom, a C1-C8 alkyl group, a cyclic alkyl group, or an aromatic group. Examples of the C1-C2 alkyl group represented by R 'include a methyl group and an ethyl group. Examples of the C1-C8 alkyl group represented by R3 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tertiary butyl group, a pentyl group, an isopentyl group, a group hexyl, an isohexyl group, a heptyl group, an isoeptyl group, an octyl group and an isooctyl group. Examples of the cyclic alkyl group represented by R3 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloeptyl group and a cyclooctyl group. Examples of the aromatic group represented by R3 include a phenyl group, a tolyl group and a xylyl group.
General formula (IV) In the general formula (IV), R4 and R5 are both a C1-C8 alkyl group. 5 Examples of the C1-C8 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tertiary butyl group, a pentyl group, an isopentyl group, a hexyl group, an isohexyl group, a heptyl group, an isoeptyl group, an octyl group and an isooctyl group. Specific examples of the compounds represented by the general formulas (I) to (IV) are listed below, but are not limited to these examples. << Amide Compound of Formula (1) >>
15 << Amide Compound of Formula (2) >>
<< Amide Compound of Formula (3) >>
<< Compound of Formula (4) >>
<< Compound of Formula (5) >>
<< Compound of Formula (6) >>
<< Compound of Formula (7) >>
<< Compound of Formula (8) >>
<< Compound of Formula (9) >>
<< Compound of Formula (10) >>
<< Compound of Formula (11) >>
<< Compound of Formula 12) >>
<< Compound of Formula 13) >>
<< Compound of Formula (14) >>
<< Compound of Formula (15) >>
In the formula above, Et indicates an ethyl group. << Compound of Formula (16) >>
In the above formula, n-Bu indicates an n-butyl group. 5 << Compound of Formula (17) >>
In the above formula, n-Oc indicates an n-octyl group. << Compound of Formula (18) >>
It is preferred in the present invention that as the organic solvent, at least one polyhydric alcohol having an equilibrium moisture content of 30% by mass or more at a temperature of 23oC and a humidity of 80% RH, at least the amide compound represented by formula (1) above, and at least one selected from the compounds represented by formulas (4), (8) and (18) is used in the mixture. With respect to a balance between hydrophilicity and hydrophobicity, the amide compound represented by formula (1) and the compounds represented by formulas (4), (8) and (18) are on the hydrophobic side compared to the conventional organic solvent (for example, glycerin and butanediol), and have a low proportion of a hydrophilic group capable of forming a hydrogen bond (for example, a hydroxyl group) within a molecule. Furthermore, these solvents do not easily cleave a hydrogen bond between cellulose molecules even when they are penetrated into the space between cellulose molecules. This model can simply be referred to as "low aggressiveness to a hydrogen bond between cellulose molecules".
As the organic solvent on the hydrophobic side mentioned above has a low surface tension, it first penetrates between the cellulose molecules. The amide compound represented by formula (1) is, as illustrated with the hydrogen bond (y) of figure 6C mentioned below, in the form of a hydrogen bond between the amide group of the same and a hydroxyl group of a cellulose molecule to remain with the cellulose molecule part, it covers the hydrogen bond of the cellulose molecule with a hydrophilic group on the alkyl group part of the amide compound, to thereby inhibit a contact of the cellulose with water which is a rich solvent of the volatile hydrophilic. Thus, the amide compound represented by formula (1) makes the cleavage of hydrogen bonds between cellulose molecules difficult. Similarly, a hydroxyl group, carbonyl group or other bond of the compounds represented by formulas (4), (8) and (18) has the same effect for those of the amide group of the amide compound represented by formula (1). This model can simply be referred to as "properties to cover hydrogen bonds of cellulose molecules".
The solvents that cover the hydrogen bonds of cellulose molecules and inhibit any contact with a continuous aqueous phase (for example, alcohol and water) are the amide compounds represented by formula (1) and the compounds represented by formulas (4), ( 8) and (18). The organic solvent which is an auxiliary solvent to demonstrate the effect mentioned above is, for example, alkane diol alkyl, or a glycolic ether compound. Therefore, the ink containing these solvents as the organic solvents do not easily cause the precipitation of their solid contents, solidification of them and reduction in their fluidity (that is, the ink can maintain the ejection stability) even if the water in the ink is evaporated.
In this document, the difference in an effect of the interaction between cellulose molecules between water and a water-soluble organic material is explained with reference to figures 6A to 6C. Figure 6A is a schematic diagram illustrating an elementary fibril. A plant fiber is formed of a fiber structure called a fibril, the fibril is formed of microfibrils each having a diameter of several nanometers at 20 nm, and a length of 1 μm to several micrometers, and each microfibril is formed from a few to several dozen elementary fibrils. Figure 6B is a schematic diagram illustrating a cellulose molecule. Elementary fibril is formed from several dozen lines in each of which the cellulose molecules are aligned. In the present document, hydrogen bonds are formed between adjacent cellulose molecules to form a package having a diameter of about 3 nm to about 4 nm. Figure 6C is a model diagram illustrating the modalities of the hydrogen bonds (α), (β) and (Y) formed between two cellulose molecules. The dotted line represents a hydrogen bond, and R represents a lipophilic group. The hydrogen bond (α) illustrates a normal state of a hydrogen bond between cellulose molecules. The hydrogen bond (β) illustrates the state where a water molecule is present in the hydrogen bond between the cellulose molecules, and the position of the hydrogen bond is shifted as the moisture evaporates. This phenomenon will be more specifically explained from now on. Since the bond between the cellulose molecules is cleaved as illustrated in the drawing when water permeates the paper, the paper fibers loosen and are stretched (back-curling phenomenon). So, if the water disappears due to drying or movement from there, the fibers shrink and the hydrogen bonds once cleaved are rewired. In the course of rewiring the hydrogen bonds, however, pressure is not naturally applied to the paper other than the time when the paper is produced, and the hydrogen bonds are formed in the free and loose state of the fibers in the drying process. Therefore, the paper forms a different shape to the original shape, that is, causing the paper face to curl (face curl is a phenomenon in which the paper curls towards the surface on which images are formed or printed with the water ink ). The hydrogen bond (y) illustrates a state where a hydrophobic group (amide group) of the amide compound represented by formula (1) and a hydrophilic group (hydroxyl group, carbonyl group, or ether bond) of the compounds represented by formulas (4) , (8) and (18) are present in the hydroxyl groups of cellulose molecules where no hydrogen bond is formed to thereby inhibit the approach of water molecules between cellulose molecules.
As mentioned above, the amide compound represented by formula (1) and the compounds represented by formulas (4), (8) and (18) are hydrophobic groups rich in terms of a balance between hydrophilic groups and hydrophobic groups, and have within molecule a low proportion of hydroxyl groups, which are hydrophilic groups, capable of forming hydrogen bonds. Therefore, these compounds do not easily cleave hydrogen bonds between cellulose molecules even when they permeate between cellulose molecules.
An amount of the amide compound represented by the general formula (I) in the inkjet ink is preferably 1 wt% to 50 wt%, more preferably 2 wt% to 40 wt%. When the amount is less than 1% by mass, the resulting ink does not have an effect of suppressing paper curl, an effect of improving image quality, and an effect of improving drying properties on the sheets of paper. overall impression. When the amount is greater than 50% by mass, the resulting ink increases its viscosity, resulting in stability in undesirable ejection of the ink.
Furthermore, the amount of the compounds represented by the general formulas (II) to (IV) used in combination with the amide compound represented by the general formula (I) is preferably 1% by weight to 50% by weight, more preferably 2% by mass to 40% by mass. When their quantity is less than 1% by mass, the resulting ink has no effect of suppressing paper curl, an effect of improving image quality and an effect of improving drying properties on printing sheets generally. When their quantity is greater than 50% by mass, the resulting ink increases its viscosity, resulting in stability in undesirable ejection of the ink.
In addition, as for the organic solvent to demonstrate an auxiliary ripple suppression effect, there is an alkyl alkane diol. As long as the alkane diol alkyl has a C3-C6 alkane diol backbone and a branched C1-C2 alkyl chain, the balance between hydrophilic groups and hydrophobic groups is on the side rich in hydrophobic groups, as well as the alkane diol alkyl being soluble in water, and thus it desirably demonstrates the aforementioned models of "low aggressiveness for a hydrogen bond between cellulose molecules" and "properties for covering hydrogen bonds of cellulose molecules". Among them, 2-methyl-1,3-propanediol (boiling point: 214oC), 3-methyl-1,3-butanediol (boiling point: 203oC), 3-methyl-1,5-pentanediol (boiling point : 250oC), and 2-ethyl-1,3-hexanediol (boiling point: 243.2oC) are preferable.
An amount of the alkane diol alkyl in the inkjet ink is preferably 2 wt% to 40 wt%, more preferably 5 wt% to 30 wt%. When the amount of the same is less than 2% by mass, the resulting ink has no effect of suppressing paper curl, an effect of improving image quality, and an effect of improving drying properties on printing sheets. generally. When the amount is greater than 40% by mass, the resulting ink increases its viscosity, resulting in stability in undesirable ejection of the ink.
The organic solvent used when mixing with the wave suppression solvents (for example, the amide compound represented by the general formula (I), the compounds represented by the general formulas (II) to (IV), and the alkane diol alkyl) include a amide compound represented by the structural formula (V).
Structural Formula (V)
The amide compound represented by the structural formula (V) has a high boiling point (pe), that is, 216oC, a high equilibrium moisture content (EMC) at a temperature of 23oC and a relative humidity of 80%, that is, 39, 2% by mass, and very low fluid viscosity at 25oC, that is, 1.48 mPa.s. Since the amide compound represented by the structural formula (V) is very easily dissolved in the organic solvent (for example, the amide compound represented by the general formula (I), compounds represented by the general formulas (II) to (IV), and alkane diol alkyl) and water, the resulting inkjet ink may result in low viscosity. Therefore, the amide compound represented by structural formula (V) is most preferable as an organic solvent for use in inkjet ink. The inkjet ink containing the amide compound represented by the structural formula (V) has a high equilibrium moisture content, and thus desirably has stability in storage and stability in ejection, as well as a suitable ink used with a maintenance device of an inkjet device.
An amount of the amide compound represented by the structural formula (V) in the inkjet ink is preferably 1 wt% to 50 wt%, more preferably 2 wt% to 40 wt%. When the amount of the same is less than 1% by mass, the amide compound represented by the structural formula (V) does not demonstrate a sufficient effect to reduce the viscosity of the resulting paint, resulting in low stability in paint ejection. When the amount of the same is greater than 50% by mass, the drying properties of the resulting ink on the paper are not sufficient, which can cause deformation of the low character quality of a resulting image on flat paper.
Furthermore, the organic solvent used together with the amide compound represented by the structural formula (V) is preferably a water-soluble organic solvent. Such organic solvent includes at least one polyhydric alcohol having an equilibrium moisture content of 30% by mass or more at a temperature of 23oC, humidity of 80% RH. Examples of organic solvent preferably include the high equilibrium moisture content and high boiling wetting agent A (wetting agent A is a wetting agent having an equilibrium moisture content of 30% by weight or more at 23oC, and humidity of 80% RH and a boiling point of 250oC or more, and the equilibrium moisture content of wetting agent A is preferably 40% by mass or more), and a high equilibrium moisture content, but the wetting agent Low boiling point B (wetting agent B is a wetting agent having an equilibrium moisture content of 30% by weight or more at 23oC, 80% RH, and a boiling point of 140oC to 250oC).
Among polyhydric alcohols, examples of wetting agent A having a boiling point greater than 250oC under normal pressure include 1,2,3-butanotriol (eg 175oC / 33hPa, EMC: 38% by mass), 1,2,4 -butanotriol (eg: 190-191oC / 24hPa, EMC: 41% by weight), glycerin (eg: 290oC, EMC: 49% by weight), diglycerin (eg: 270oC / 20hPa, EMC: 38% by weight), triethylene glycol (eg: 285oC, EMC: 391% by weight), and tetraethylene glycol (eg: 324oC-330oC / 24hPa, EMC: 37% by weight). Examples of wetting agent B having a boiling point of 140oC to 250oC include diethylene glycol (eg: 245oC, EMC: 43% by weight) and 1,3-butanediol (eg: 203- 204oC / 24hPa, EMC: 35% by weight) ).
These wetting agent A and wetting agent B are both highly hygroscopic materials, each having an equilibrium moisture content of 30% by weight or more at a temperature of 23oC, relative humidity of 80%. However, it is also true that wetting agent B has a relatively higher vaporization capacity than wetting agent A.
Polyhydric alcohol is particularly preferably selected from the group consisting of glycerin, and 1,3-butanediol.
When wetting agent A and wetting agent B are used in combination, a ratio (mass ratio) B / A of wetting agent B to wetting agent A cannot be determined unconditionally because it depends more or less on an amount of another agent humectant C, which will be described later, or other additives for use (for example, a penetrating agent) and amounts thereof. For example, the B / A ratio is preferably in the range of 10/90 to 90/10. The equilibrium moisture content described in this document is an equilibrium moisture content measured using a saturated aqueous solution of potassium chloride and a dissector as follows. The internal temperature of the dissector is maintained at 23 ° C ± 1oC and its internal humidity is maintained at 80 RH ± 3% RH. Then, each sample of organic solvents is weighed by 1 g and placed in a dish, and the dish is placed in the desiccator and stored until there is no further change in the sample mass, and an equilibrium moisture content of the sample can be determined by following equation.
Equilibrium moisture content (%) = Amount of water absorbed in the organic solvent / (Amount of organic solvent + Amount of water absorbed in the organic solvent) x 100
The use of polyhydric alcohol in an amount of 50% by mass or higher with respect to the total amount of the organic solvent is preferable as the resulting ink has desirable ejection stability, and is excellent at suppressing waste ink depositions on a device maintenance of an inkjet device.
In the inkjet ink of the present invention, except wetting agent A and wetting agent B, other wetting agents C (for example, wetting agent C is typically a wetting agent having an equilibrium moisture content of less than 30 % by mass at 23oC, 80% RH) can be used to partially replace with wetting agents A and B, or in combination with wetting agents A and B.
Examples of wetting agent C include polyhydric alcohols, polyhydric alcohol alkyl ethers, polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, sulfur-containing compounds, propylene carbonate, ethylene carbonate, and other wetting agents.
Examples of polyhydric alcohols include dipropylene glycol (eg: 232oC), 1,5-pentanediol (eg: 242oC), propylene glycol (eg: 187oC), 2-methyl-1,2-pentanediol (eg: 197oC), ethylene glycol ( eg: 196oC-198oC), tripropylene glycol (eg: 267oC), hexylene glycol (eg: 197oC), polyethylene glycol (viscous to solid liquid), polypropylene glycol (eg: 187oC), 1,6-hexanediol (eg: 253oC- 260oC), 1,2,6-hexanotriol (eg 178oC), trimethylol ethane (solid, mp: 199oC-201oC), and trimethylol propane (solid, PF: 61oC).
Examples of polyhydric alcohol alkyl ethers include ethylene glycol monoethyl ether (eg 135oC), ethylene glycol monobutyl ether (eg 171oC), diethylene glycol monomethyl ether (eg 194oC), diethylene glycol monoethyl ether (eg 197oC ), diethylene glycol monobutyl ether (eg: 231oC), ethylene glycol mono-2-ethylexyl ether (eg: 229oC) and propylene glycol monoethyl ether (eg: 132oC).
Examples of polyhydric alcohol aryl ethers include ethylene glycol monophenyl ether (eg 237oC), and ethylene glycol monobenzyl ether.
Examples of nitrogen-containing heterocyclic compounds include 2-pyrrolidone (eg: 250oC, PF: 25.5oC, EMC: 47% by mass to 48% by mass), N-methyl-2-pyrrolidone (eg: 202oC), 1.3 -dimethyl-2-imidazolidinone (eg: 226oC), ε-caprolactam (eg: 270oC), and Y-buritolactone (eg: 204oC-205oC).
Examples of amides include formamide (eg: 210oC), N-methylformamide (eg: 199oC-201oC), N, N-dimethylformamide (eg: 153oC) and N, N-diethylformamide (eg: 176oC-177oC).
Examples of amines include monoethanolamine (eg: 170oC), diethanolamine (eg: 268oC), triethanolamine (eg: 360oC), N, N-dimethylmonoethanolamine (eg: 139oC), N-methyldiethanolamine (eg: 243oC), N-methylethanolamine (eg : 159oC), N-phenylethanolamine (eg: 282oC-287oC), and 3-aminopropylethyl amine (eg: 169oC).
Examples of sulfur-containing compounds include dimethyl sulfoxide (eg: 139oC), sulfolane) (eg: 285oC) and thiodiglycol (eg: 282oC).
As with other wetting agents, saccharides are preferable.
Examples of saccharides include monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides), and polysaccharides. Specific examples thereof include glucose, mannose, fructose, ribose, xylose, arabinose, galactose, maltose, cellobiose, lactose, sucrose, trehalose and maltotriose. In the present document, the polysaccharides mentioned above mean saccharides in a broad sense, which may include materials widely existing in nature, such as α-cyclodextrin and cellulose. In addition, other examples include saccharide derivatives such as saccharide reducing sugars (for example, sugar alcohol, which is represented by the general formula: HOCH2 (CHOH) nCH2OH, where n is an integer from 2 to 5) , oxidized sugars (for example, aldonic acids and uronic acids), amino acids and thio acids. Among these, sugar alcohol is preferable. Specific examples of sugar alcohol include maltitol and sorbitol.
A mass relationship between the pigment and the wetting agent greatly affects the ink ejection stability from a head, and also affects the prevention of waste ink depositions in an inkjet device maintenance device. When the solids content of the pigment is large considering a small amount of the wetting agent, the evaporation of the moisture from the ink near the ink meniscus of the nozzles continues, and as a result ejection defects can be caused.
As the organic solvents used in combination with the amide compound represented by the general formula (I), the compounds represented by the general formulas (II) to (IV), the alkane diol alkyl, and the amide compound represented by the structural formula (V), there is an organic solvent including wetting agents A, B and C. An amount of the organic solvent including wetting agents A, B and C in the inkjet ink is preferably 20% and mass to 80% by weight, more preferably 30% by mass to 70% by mass.
When the amount of the same is less than 20% by mass, the effect of suppressing the ripple cannot be demonstrated, and can adversely affect the ejection stability, and the prevention of waste ink depositions in a maintenance device.
When the amount of them is greater than 80% by mass, the viscosity of the resulting inkjet ink is too high, which can make it difficult to eject the ink from an inkjet device. In addition, the drying properties of the resulting ink on the paper can be impaired, which can degrade the qualities of the characters printed on the paper. <<Coloring>>
Preferred embodiments where the dye is a pigment include the following first to third embodiments. (1) In the first embodiment, the colorant contains a dispersion liquid containing a pigment (it can also be referred to as “self-dispersing pigment” from now on), which has at least one hydrophilic group on a surface of the same, and demonstrates the ability to dispersion in water without a dispersant. (2) In the second embodiment, the dye contains a polymeric emulsion (polymeric particles containing aqueous dispersion liquid each including a pigment) in which an insoluble or sparingly soluble pigment is contained in each polymeric particle.
Like the pigment, an organic pigment or an inorganic pigment can be used. Note that the dye may contain a dye in combination with the pigment in order to adjust the color tone, as long as the dye does not degrade the weather resistance of the resulting paint.
Examples of inorganic pigment include titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow and carbon black. Among them, carbon black is particularly preferable. Examples of carbon black include those produced by conventional methods such as a contact method, oven method and thermal method.
Examples of organic pigment include an azo pigment, polycyclic pigment, chelate dye, nitro pigment, nitrous pigment and black aniline. Among them, the azo pigment and the polycyclic pigment are more preferable. Examples of azo pigment include azo lake, an insoluble azo pigment, a condensed azo pigment and an azo chelated pigment. Examples of polycyclic pigment include a phthalocyanine pigment, a perylene pigment, a perinone pigment, anthraquinone pigment, a quinacridone pigment, a dioxazine pigment, an indigo pigment, a thioindigo pigment, an isoindolinone pigment and a quinophthalone pigment. Examples of dye chelate include a basic dye chelate and an acidic dye chelate.
A color of the colorant is appropriately selected depending on the intended purpose without any restrictions, and examples of the same include a colorant for black and a colorant for colors. These can be used independently or in combination.
Examples of colorant for black include: carbon blacks (C.I. Pigment Black 7) such as oven black, lamp black, acetylene black, and channel black; metals such as copper, iron (C.I. Pigmento Preto 11) and titanium oxide; and organic pigments such as black aniline (C.I. Black Pigment 1).
Examples of commercial carbon black products include carbon black obtained from Cabot Corporation under the trademarks Regal®, Black Pearls®, Elftex®, Monarch®, Mogul® and Volcan®.
Examples of colorant for colors include CI Pigment Yellow 1, 3, 12, 13, 14, 17, 24, 34, 35, 37, 42 (yellow iron oxides), 53, 55, 74, 81, 83, 95, 97 , 98, 100, 101, 104, 408, 109, 110, 117, 120, 128, 138, 150, 151, 153, 155, 183, 213; C.I. Orange Pigment 5, 13, 16, 17, 36, 43, 51; CI Pigment Red 1, 2, 3, 5, 17, 22, 23, 31, 38, 48: 2, 48: 2 (Permanent Red 2B (Ca)), 48: 3, 48: 4, 49: 1, 52 : 2, 53: 1, 57: 1 (Brilliant Carmine 6B), 60 = 1, 63: 1, 63: 2, 64: 1, 81, 83, 88, 101 (colcothar), 104, 105, 106, 108 (Red Cadmium), 112, 114, 122 (quinacridone magenta), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 185, 190, 193, 209, 219; C.I. Pigment Violet 1 (Rhodamine Lake), 3, 5: 1, 16, 19, 23, 38; C.I. Blue Pigment 1, 2, 15 (phthalocyanine blue), 15: 1, 15: 2, 15: 3 (phthalocyanine blue), 15: 4 (phthalocyanine blue), 16, 17: 1, 56, 60, 63; C.I.Green Pigment 1, 4, 7, 8, 10, 17, 18, 36. Other soluble pigments for use are disclosed in The Color Index, 3rd Ed. (The Society of Dyers and Colourists, 1982). -Coloring of the first modality-
The self-dispersing pigment of the first embodiment is a pigment whose surface is modified so that at least one hydrophilic group is, directly or through another group of atoms, combined with the surface of the pigment. To obtain the surface modification, for example, the following methods are employed: a method in which a specific functional group (functional group such as a sulfone group and a carboxyl group) is chemically combined with the surface of a pigment, or a method wherein the surface of a pigment is subjected to oxidation treatment with moisture using at least one hypoal acid or a salt thereof. Among these, the modality where a carboxyl group is attached to a pigment surface, which is dispersed in water, is particularly preferable. Since the self-dispersing pigment of the first embodiment has a surface modified in the manner mentioned above, and a carboxyl group attached to its surface, not only the highest impression can be obtained and the water resistance of the recording medium after printing is further improved.
An ink containing the self-dispersing pigment of the first modality is excellent in the redispersion capacity after being dried, and thus excellent printing can be performed easily with a simple cleaning operation without causing clogging, even when the printing operation is interrupted for a long period , and the moisture in the ink displayed near the nozzle of the inkjet head is evaporated. The volume-average particle diameter (D50) of the self-dispersing pigment in the paint is preferably 0.01 μm to 0.16 μm.
As the self-dispersing carbon black, for example, a self-dispersing carbon black having ionicity is preferred, and a cationically charged self-dispersing carbon black is used appropriately.
Examples of the anionic hydrophilic group include -COOM, -SO3M, -PO3HM, -PO3HM2, —PO3M2, -CONM2, -SO3NM2, -NH-C6H4-COOM, -NH-C6H4-SO3M, -NH-C6H4-PO3HM, -NHH —C6H4-PO3M2, —NH — C6H4 - CONM2, and -NH-C6H4-SO3NM2 (where M is a hydrogen atom, an alkali metal, quaternary ammonium or organic ammonium, preferably quaternary ammonium). Among these, -COOM, - colored pigments on the surfaces to which -COOM and -SO3M are bonded are particularly preferable.
Examples of alkali metal indicated by M include lithium, sodium and potassium. Examples of organic ammonium 5 indicated by M include monomethyl to trimethyl ammonium, monoethyl to triethyl ammonium, and monomethanol to trimethanol ammonium. As a method of obtaining the anionically charged color pigment, examples of the method for introducing -COONa to a surface of a color pigment include a method for oxidizing a color pigment with sodium hypochlorite, a method for sulfonating a color pigment, and a method in which a colored pigment is reacted with the diazonium salt.
As for the cationic hydrophilic group, a 15 quaternary ammonium group is preferable, and the quaternary ammonium groups represented by the following formulas are more preferable.

Specific examples of quaternary ammonium ion include tetramethyl ammonium ion, tetraethyl ammonium ion, tetrapropyl ammonium ion, tetrabutyl ammonium ion, tetrapentyl ammonium ion, benzyltrimethyl ammonium ion, benzyltriethyl ammonium ion and tetanyl ammonium ion. Among these, tetraethyl ammonium ion, tetrabutyl ammonium ion and benzyltrimethyl ammonium ion are preferable, and tetrabutyl ammonium ion 10 is particularly preferable.
Examples of the anionic functional group include polar anionic groups such as a carboxylic acid group, a sulfonic acid group, a phosphate group, an amide group and a sulfonamide group. Preferable examples thereof are carboxylic acid and p-aminobenzoic acid.
Anionic functional groups can be attached to pigment particle surfaces according to the methods disclosed in Patent JP (JP-B) No. 4697757, JP-A No. 2003-513137, International Application Publication No. WO97 / 48769 and JP-A nos 10-110129, 11-246807, 11-57458, 11-189739, 11-323232 and 2000-265094.
The use of water-dispersible pigment having the anionic functional group and quaternary ammonium ion makes it possible to maintain the stable dispersion state of the dispersible pigment either in a water-rich paint, or in a paint rich in organic solvent from which the moisture has been evaporated, such as the anionic functional group and quaternary ammonium ion demonstrate affinity.
A method for producing the cationic self-dispersing carbon black to which the hydrophilic group is attached is appropriately selected depending on the intended end without any restriction, and examples of this include a method for linking the N-ethyl pyridyl group represented by the following structural formula to the black carbon, and a method for processing carbon black with 3-amino-N-ethylpyridinium bromide.

The hydrophilic group can be attached to a carbon black surface through another atom group.
Examples of another atom group include a C1C12 alkyl group, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted naphthyl group. Specific examples where the hydrophilic group is attached to the carbon black surface through another atom group include —C2H4COOM (where M is an alkali metal or a quaternary ammonium), -PhSO3M (where Ph is a phenyl group, and M is a alkali metal or a quaternary ammonium), and —C5H10NH3 +.
As another embodiment within the first embodiment, the colorant is preferably a modified pigment, which has been modified with a geminal bisphosphonic acid group, or a geminal bisphosphonate group.
Examples of such a modified pigment include modified pigments, which have been modified with any of the groups represented by the following structural formulas (1), (2), (3) and (4):

Structural Formula (3)
N (CH3) 4 +, N (C2H5) 4+ or N (C4H9) 4+. Structural Formula (4)
In structural formula (4), X + is Li +, K +, Na +, NH4 +. N (CH3) 4 +, N (C3H5) 4 +, N (C3H7) 4 +, or N (C4H9) 4+.
The surface modification will be specifically explained below.
A liquid dispersion containing the modified pigment is prepared by one of the general methods. As the method, it is preferred that the pigment is allowed to react with the compounds represented by the following formulas (VI) and (VII), and the phosphonic acid group is replaced with alkali metal or organic ammonium to disperse the pigment in water.
[Compound of Formula (VII)]
<Surface Modification Process> [Method A] 5 In space at room temperature, 20 g of carbon black, 20 mmol of the compound of formula (VI) or the compound of formula (VII), and 200 ml of highly pure water ion exchange are mixed by Silverson Mixer (6,000 rpm). When the obtained suspension has a pH value higher than 10 than 4.20 mmol of nitric acid are added to the suspension. Thirty minutes later, sodium nitrite (20 mmol) dissolved in a small amount of highly pure ion exchange water is gradually added to the suspension. The resultant is heated to 60oC with stirring 15 to thus react for 1 hour. As a result, a modified pigment in which the compound of the formula (VI) or the compound of the formula (VII) was added to the carbon black is generated. Subsequently, the pH of the resultant or adjusted to 10 with an aqueous solution of NaOH, to thereby obtain a modified dispersion liquid in 30 minutes. The dispersion liquid containing the pigment bound to at least one group of geminal bisphosphonic acid or to a group of geminal bisphosphonate and highly pure ion exchange water is used and subjected to ultrafiltration with a permeable membrane, and the resultant is further subjected to ultrasonic dispersion in order to obtain a modified pigment dispersion liquid whose sodium content has been concentrated. [Method B]
The ProcessAll 4HV Mixer (4L) is loaded with 500 g of dry carbon black, 1 L of highly pure ion exchange water and 1 mol of the compound of formula (VI) or the compound of formula (VII). Subsequently, the resulting mixture is mixed strongly at 300 rpm for 10 minutes, with heating at 60 ° C. For this, 20% by weight of an aqueous solution of sodium nitrite [1 mol equivalent to the compound of the formula (VI) or the compound of the formula (VII)] is added over 15 minutes. The resulting mixture is mixed and stirred for 3 hours with heating at 60 ° C. The reagent is absorbed while diluting with 750 ml of highly pure ion exchange water. The obtained pigment dispersion liquid and highly pure ion exchange water are used, and subjected to ultrafiltration with a permeable membrane, and the resultant is further subjected to ultrasonic dispersion to thereby obtain a modified pigment dispersion liquid whose solids content was concentrated. In the case where coarse particles are contained in a large amount, the coarse particles are preferably removed, for example, by a centrifugal separator.
A sodium ion content of each of the modified pigment dispersion liquids is measured by an ion meter. A total amount of phosphorus is measured by an elementary analysis. In addition, the volume-average particle diameter (D50) of the modified pigment in the dispersion liquid is measured using a Microtrac® particle size distribution measuring device.
The volume average particle diameter (D50) of the dispersed elements of the modified pigment in the ink is preferably 0.01 μm to 0.16 μm.
Furthermore, dispersed elements containing ink from a surface-treated pigment bonded to at least one group of bisphosphonic acid geminal and group or sodium salt of bisphosphonic acid geminal have excellent redispersion capacity even after the moisture in the paint has evaporated. Therefore, the use of such ink provides excellent clogging, when the printing operation rests for a long period and the humidity of the ink adjacent to the nozzles of an inkjet head. In addition, the ink has high stability during storage, which is a paint capable of suppressing the increase in viscosity as moisture is evaporated, and having excellent properties in terms of ejection reliability, and preventing ink deposition in the head maintenance device. -Color of the Second Mode-
As for the dye of the second embodiment, in addition to the pigment mentioned above, a polymeric emulsion in which a pigment is contained in each of the polymeric particles is preferably used. The polymeric emulsion in which the pigment is contained in each of the polymeric particles means a polymeric emulsion in which the pigment is encapsulated in each of the polymeric particles, or the pigment is absorbed on each surface of the polymeric particles. In the polymeric emulsion, all pigment particles do not need to be encapsulated or adsorbed, and part of the pigment particles can be dispersed in the emulsion with the proviso that they do not adversely affect the achievable effect of the present invention. Examples of the polymer to form the polymeric emulsion (the polymer of the polymeric particles) include a vinyl polymer, a polyester polymer, and a polyurethane polymer. The polymers particularly preferably used are the vinyl polymer and the polyester polymer. For example, the polymers disclosed in the JP Open Patent Application (JP-A) No. 200053897 and 2001-139849 can be used.
In the second embodiment, moreover, a composite pigment, in which particles of known organic or inorganic pigment are each coated with an organic pigment or carbon black, can be used appropriately as the colorant. The composite pigment can be obtained by a method to precipitate an organic pigment in the presence of inorganic pigment particles, and a mechanical-chemical method in which an inorganic pigment and an organic pigment are mechanically mixed and ground. In this case, a layer of an organosiloxane compound formed from polysiloxane or alkyl silane can optionally be provided between the inorganic pigment and the organic pigment to improve the adhesion between the layers of these pigments.
The organic pigment and the inorganic pigment are appropriately selected from those listed above.
A mass ratio of the inorganic pigment particles to the organic or carbon black pigment as the colorant is preferably 3/1 to 1/3, more preferably 3/2 to 1/2. When the amount of the colorant is small, the coloring capacity and the dyeing capacity may be low. When the amount of the colorant is large, a transparency or color tone of the resulting ink may not be desirable.
Like the coloring particles where the particles of inorganic pigment with organic pigment or carbon black. A carbon black silica composite material, a PB 15: 3 silica-phthalocyanine composite material, a yellow silica-diazo composite material, and a PR122 silica-quinacridone composite material, which are manufactured by TODA KOGYO CORPORATION, are used appropriately because this material has small primary particle diameters.
For example, if inorganic pigments that have a primary particle diameter of 20 nm are coated with an equivalent amount of an organic pigment, the coated particles have a primary diameter of approximately 25 nm. Therefore, with the proviso that these particles are dispersed maintaining the primary particle state using finely dispersed having a dispersed particle diameter of 25 nm can be obtained. Note that not only does the organic pigment present on the surface of the composite pigment contribute to its dispersion state, but also the characteristics of the inorganic pigment present in the center of the composite pigment affect the state of dispersion through the thick layer of about 2 , 5 nm of the organic pigment. Therefore, it is also important that a pigment dispersant that can stabilize both the organic pigment and the inorganic pigment in the composite pigment in the dispersion is selected. << Coloring of Other Modalities >>
In another embodiment, the colorant is a pigment dispersion liquid containing a pigment, a pigment dispersant and a polymer dispersion stabilizer, where the polymer dispersion stabilizer is at least one selected from the group consisting of an α-olefin copolymer. maleic anhydride represented by the following general formula (A), a styrene-methacryl copolymer, a water-soluble polyurethane resin and a water-soluble polyester resin.
General Formula (A)
In the general formula (A) above, R is a C6-C30 alkyl group, preferably C12-C22, more preferably C18-C22, 5 and n is an integer of 1 or more, preferably 20 to 100. The α-olefin copolymer - maleic anhydride represented by the general formula (A) can be synthesized using a mixture of olefins including olefins that have 10 different numbers of carbon atoms, as a starting material. In this case, the resulting copolymer is a copolymer in which the alkyl groups having different numbers of carbon atoms are randomly introduced into a polymer chain. In the present invention, not only the α-olefin-maleic anhydride copolymer in which the alkyl groups having the same numbers of carbon atoms are introduced in a polymer chain like R, but also the α-olefin-maleic anhydride copolymer in that the alkyl groups, each having different numbers of carbon atoms, are randomly introduced into the polymer chain as R can be used as the α-olefin-maleic anhydride copolymer represented by the general formula (A).
The weight average molecular weight of the α-olefin-maleic anhydride copolymer represented by the general formula (A) is preferably 5,000 to 20,000.
In this document, the average molecular weight of the α-olefin-maleic anhydride copolymer can be measured by the following method. [Measurement of Ponderal Average Molecular Weight]
The weight molecular weight of the copolymer can be measured using a gel permeation chromatography (GPC) analysis system.
First, the copolymer is dissolved in tetrahydrofuran, which is the same as an eluent, and KF806L (for THF) is prepared as a GPC column. As standard molecular weight materials, three types of polystyrene whose molecular weights are known, and each having different molecular weights (from 1,000, 2,400 and 8,500) are measured to form a calibration curve.
Then, the copolymer is subjected to GPC analysis. From the SC chromatography obtained, and a graph reflecting the molecular weight distribution curve for standard molecular weight materials, a weight average molecular weight of the copolymer is calculated.
The α-olefin-maleic anhydride copolymer represented by the general formula (A), the styrene-methacryl copolymer, the water-soluble polyurethane resin, and the water-soluble polyester resin are solid at normal temperature, and are hardly soluble in cold water. However, these copolymers and resins demonstrate an effect as a dispersion stabilizer when they are used by being dissolved in an equivalent amount or more (preferably 1.0 times 1.5 times the acid value) of an alkaline solution or aqueous alkaline solution acid values of copolymers and resins.
The dissolution of the polymer or resin in the alkaline solution or aqueous alkaline solution can be easily accomplished by heating and stirring. However, in the case where an olefin chain in the α-olefin-maleic anhydride copolymer is long, it is relatively difficult to dissolve the α-olefin-maleic anhydride copolymer in the alkaline solution or aqueous alkaline solution, and is sometimes the case in that insoluble products remain. That said, the α-olefin-maleic anhydride copolymer dissolved in the alkaline solution or aqueous alkaline solution does not lose its effect as the dispersion stabilizer as long as these insoluble products are removed using an appropriate filter.
Examples of the base used in the alkaline solution or aqueous alkaline solution include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide: basic materials such as ammonium, triethyl amine and morpholine; amine alcohol such as triethanol amine, diethanol amine, N-methyldiethanol amine, 2-amino-2-ethyl-1,3-propanediol and choline.
The α-olefin-maleic anhydride copolymer represented by the general formula (A) can be synthesized appropriately for use, or selected from commercial products. Examples of commercial product include T-YP112, T-YP115, T-YP114 and T-YP116 (all manufactured by SEIKO PMC CORPORATION).
The styrene-methacryl copolymer can be synthesized appropriately for use, or selected from commercial products. Examples of commercial product include: JC-05 (manufactured by SEIKO PMC CORPORATION and ARUFON UC-3900, ARUFON UC-3910 and ARUFON UC-3920 (all manufactured by TOAGOSEI CO., LTD.).
The water-soluble polyurethane resin can be synthesized appropriately for use, or selected from commercial products. Examples of the commercial product thereof include TAKELAC W-5025, TAKELAC W-6010 and TAKELAC W-5661 (manufactured by Mitsui Chemicals, Inc.). The water-soluble polyester resin can be synthesized appropriately for use, or selected from commercial products. Examples of such a commercial product include: NICHIGO POLYESTER W-0030, NICHIGO POLYESTER W-0005S30WO and NICHIGO POLYESTER WR-961 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.); and PESRESIN A-210, and PESRESIN A-520 (manufactured by TAKAMATSU OIL & FAT CO., LTD.).
The acid value of the polymeric dispersion stabilizer is preferably 400 mgKOH / g to 400 mgKOH / g, more preferably 60 mgKOH / g to 350 mgKOH / g. When its acid value is lower than 40 mgKOH / g, the polymeric dispersion stabilizer may have poor solubility in an alkaline solution. When its acid value is greater than 400 mgKOH / g, the viscosity of the pigment dispersing element increases, which can lead to the poor ejection capacity of the resulting ink, or the dispersion stability of the pigment dispersing elements can increase.
The mass average molecular weight of the polymeric dispersion stabilizer is preferably 20,000 or less, more preferably in the range of 5,000 to 20,000. When the mass average molecular weight of the same is less than the dispersion stability of the pigment dispersion elements it can decrease. When the mass average molecular weight thereof is greater than 20,000, the polymeric dispersion stabilizer may have poor solubility in an alkaline solution, or the viscosity of the pigment dispersion elements may increase.
An amount of the polymeric dispersion stabilizer is preferably 1 part by weight to 100 parts by weight, more preferably 5 parts by weight to 50 parts by weight on solid basis, with respect to 100 parts by weight of the pigment. When the amount thereof is less than 1 part by mass, the polymeric dispersion stabilizer may not be able to demonstrate an effect of stabilizing a dispersion state. When the amount of the same is greater than 10 parts by mass, the viscosity of the resulting ink increases, which can degrade the ejection capacity of the ink from a nozzle, or its use is not economical.
In the embodiment, the colorant preferably contains the pigment dispersant. As for the pigment dispersant, either an anionic surfactant or a nonionic surfactant having an HLB value of 10 to 20 is preferable.
Examples of anionic surfactant include polyoxyethylene alkyl ether acetic acid salts, benzene alkyl sulfonic acid salts (for example, NH4, Na or Ca), alkyldiphenyl ether disulfonic acid salts (for example, NH4, Na or Ca ), sodium dialkyl succinate sulfonate (Na salt), a condensate of sodium formalin naphthalene sulfonate (Na salt), polyoxyethylene polycyclic phenyl ether sulfuric acid ester salt (for example, NH4 or Na) , lauric acid salts, polyoxyethylene alkyl ether sulfate salt and oleic acid salts. Among these, sodium dioctylsulfosuccinate (Na salt), and polyoxyethylene phenyl styrene ammonium sulfonate (NH4 salt) are particularly preferable.
Examples of nonionic surfactant having an HLB value of 10 to 20 include polyoxyethylene alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene polycyclic ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylphenyl ether, alkyl polyoxyethylene amine, polyoxyethylene alkyl amide and acetylene glycol. Among these, polyoxyethylene lauryl ether, polyoxyethylene e-naphthyl ether, polyoxyethylene sorbitan monooleate and polyoxyethylene styrenophenyl ether are particularly preferable. preferably 1 part by weight to 100 parts by weight, more preferably 10 parts by weight to 50 parts by weight with respect to 100 parts by weight of the pigment. When the amount of dispersant for use is small, the pigment cannot be sufficiently finely dispersed. When the amount of the product is excessively large, an excessive portion of the product that is not adsorbed on the pigment influences the physical properties of the resulting paint, which can cause image stains, low water resistance and low abrasion resistance.
The pigment dispersion elements dispersed evenly and finely in water by the pigment dispersant can be prepared by the method which includes dissolving, dispersing the pigment in an aqueous medium, adding the pigment to the solution to sufficiently wet the pigment, and dispersing the mixture high speed by means of a homogenizer, a disperser using balls (for example, a ball mill and a ball mill), a dispersing kneading using shear force (for example, roller mill), or an ultrasonic disperser.
In many cases, coarse particles are contained in the dispersion after the kneading and dispersion step mentioned above, which causes clogging of the inkjet nozzles or supply channels. Therefore, it is necessary to remove particles that have diameters of 1 μm or larger by means of a filter or a centrifuge.
The average particle diameter (D50) of the pigment dispersing elements is preferably 150 nm or less, more preferably 100 nm or less in the ink. When their average particle diameter (D50) is greater than 150 nm, the ejection stability of the resulting paint is significantly decreased, which can cause the nozzles to clog or bend a track of the blasted paint. Furthermore, when their average particle diameter (D50) is 100 nm or less, the blasting stability of the resulting ink improves and, moreover, the saturation of images formed with the resulting ink improves.
An amount of the dye in the inkjet ink is preferably 2 wt% to 15 wt%, more preferably 3 wt% to 12 wt% on solid base. When the amount of the same is less than 2% by mass, the coloring capacity of the resulting ink and the image density of the resulting image may be low. When the amount of the same is greater than 15% by mass, the resulting ink increases its viscosity, which can result in undesirable ejection properties, and is also not economically desirable. <Surfactant>
The surfactant is preferably selected from those that have low surface tension, high penetration capacity and high leveling capacity that do not impair dispersion stability depending on a combination with the colorant for use, or the wetting agent for use. The surfactant is preferably at least one selected from the group consisting of an anionic surfactant, a nonionic surfactant, a silicone surfactant, and a fluoroturfactant. Among these, the silicone surfactant, the fluoroturfactant, an acetylene glycol or acetylene alcohol surfactant are particularly preferable. These surfactants can be used independently, or in combination.
As for the fluorotensive, a fluorotensive where 2 to 16 carbon atoms are replaced with fluorine atoms is preferable, and a fluorotensive where 4 to 16 carbon atoms are replaced with fluorine atoms is more preferable. When the number of carbon atoms replaced with fluorine atoms is less than 2, an effect of fluorine cannot be obtained. When their number is more than 16, the resulting ink may have a storage stability problem.
Examples of fluorotensive agents include a perfluoroalkyl sulfonic acid compound, a perfluoroalkyl carboxylic acid compound, a perfluoroalkyl phosphate compound, a perfluoroalkyl ethyl oxide adduct, and a polyoxyethylene ether polymer compound having a perfluoroalkyl ether group. in a side chain of it. Among these, the polyoxyethylene ether polymer compound having a perfluoroalkyl ether group on a side chain thereof is particularly preferable because it has a low foaming capacity. More preferably, the fluorosurfactant is a fluorosurfactant represented by the following general formula (VII) or (VIIa): CF3CF2 (CF3CF2) m-CH2CH2O (CH2CH2O) aH General Formula (VII) In the general formula (VII), m is an integer of 0 to 10, and n is an integer from 1 to 40. CnF2n + 1-CH2CH (OH) CH2-O- (CH2CH2O) a-Y 'General Formula (VIIa) In the general formula (VIIa), n is an integer from 2 to 6, a is an integer from 15 to 50, and Y 'is -ChH2b + 1 (b is an integer from 11 to 19) or —CH2CH (OH) CH2-CdF2d + 1 (d is a number 2 to 6). Examples of the perfluoroalkyl sulfonic acid compound, and perfluoroalkyl sulfonic acid salt.
Examples of the perfluoroalkyl carboxylic acid compound include perfluoroalkyl carboxylic acid, and perfluoroalkyl carboxylic acid salt.
Examples of the perfluoroalkyl phosphate compound include perfluoroalkyl phosphate, and perfluoroalkyl phosphoric acid ester salt.
Examples of the polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group on a side chain thereof include polyoxyalkylene ether polymer having a perfluoroalkyl ether group on a side chain thereof, a sulfuric acid ester salt of polymer polyoxyalkylene ether having a perfluoroalkyl ether on a side chain thereof, and a polyoxyalkylene ether polymer salt having a perfluoroalkyl ether group on a side chain thereof.
Examples of the salt counterion of these fluorotensive agents include Li, Na, K, NH4, NH3CH2CH2OH, NH2 (CH2CH2OH) 2 and NH (CH2CH2OH) 3.
Fluorotensive can be synthesized appropriately for use or selected from commercial products. Examples of commercial products include SURFLON S-111, S-112, S-113, S-121, S-131, S-132, S-141, S-146 (all manufactured by AGC SEIMI CHEMICAL CO., LTD.) ; FLOURAD FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431 (all manufactured by Sumitomo 3M Limited); MEGAFACE F-470, F-1405, F-474 (all manufactured by DIC Corporation); Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, UR (all manufactured by DuPont Kabushiki Kaisha); FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW (all manufactured by NEOS COMPANY LIMITED); and PolyFox PF-151N (manufactured by Omnova Solutions, Inc.). Among them, FS-300 manufactured by DuPont Kabushiki Kaisha, FT-110, FT-250, FT-251, FT- 400S, FT-150 and FT-400SW manufactured by NEOS COMPANY LIMITED, and PolyFox PF-151N manufactured by Omnova Solutions , Inc. are particularly preferable because they can achieve the desirable print quality, particularly the coloring ability, and can significantly improve uniform dye affinity. Specific examples of fluorotensive agents preferably include those represented by the following general formula (VIII): (1) Anionic fluoride agents
General Formula (VIII) In the general formula (VIII), Rf represents a mixture of hydrophobic groups containing fluorine represented by the following structural formulas (IX) to (X); and A is -SO3X, - COOX or -PO3X (where X is a specific counterion, examples of which include a hydrogen atom, Li, Na, K, NH4, NH3CH2CH2OH, NH2 (CH2CH2OH) 2 and NH (CH2CH2OH) 3) ;
Structural Formula (IX)
: Structural Formula (X)
General Formula (XI) In the general formula (XI), Rf 'is the group containing fluorine represented by the following general formula (XII), X represents the same as described above, n is an integer of 1 or 2, in is 2- n.
General Formula (XIII) In the general formula (XII), n is an integer from 3 to Rf'-S-CH2CH2-COO'X General Formula (XIII) In the general formula (XIII), Rf 'and X, respectively, represent the same as described above. Rf'-SO3'X General Formula (XIV) In the general formula (XIV), Rf 'and X, respectively, represent the same as described above. (2) Non-ionic fluorotensive
General Formula (XV) In the general formula (XV), Rf represents the same as described above, and n is an integer from 5 to 20.
General Formula (XVI) In the general formula (XVI), Rf 'represents the same as described above, and n is an integer from 1 to 40.
(3) Fluorotensoativo Amfoterico General Formula (XVII) In the general formula (VII), Rf represents the same as described above. (4) Oligomeric Fluototensive
General Formula (XVIII) 5 In the general formula (XVIII), Rf 'represents the group containing fluorine represented for the following general formula (XIX), n is an integer from 0 to 10, and X represents the same as described above,
10 General Formula (XIX) In the general formula (XIX), n is an integer from 1 to 4.
General Formula (XX) 15 In the general formula (XX), Rf 'represents the same as described above, l is an integer from a 10, m is an integer from 0 to 0 and n is an integer from 1 to 10. Furthermore, the compound represented by the general formula (VII) preferably satisfies the ratio of MWEO / MWF = 2.2 to 10, where MWEO is a molecular weight of the polyoxyethylene group [the (CH2CH2O) a site] and MWF is a molecular weight of the fluoroalkyl group (the CnF2n + 1 side and the CmF2m + 1 side) in view of the functions as a surfactant and the water solubility balance. Preferable examples of the compound represented by the general formula (VIIa) include compounds represented by the following formulas (a) to (v), which are desirable because they have high performance in reducing surface tension and have high permeability. (a) C4F9-CH2CH (OH) CH2OHCH2CH2O) 21-C12H25 (b) C4F9-CH2CH (OH) CH2OHCH2CH2O) 25-C12H25 (c) C4F9-CH2CH (OH) CH2OHCH2CH2O) 30-C12H25 (d) C4F9 -2 ) CH2OHCH2CH2O) 20-C12H29 (e) C4F9-CH2CH (OH) CH2OHCH2CH2O) 30-C12H29 (f) C4F9-CH2CH (OH) CH2OHCH2CH2O) 20-C16H33 (g) C4F9-CH2CH (OH) CH2OHCH2CH2O) ) C4F9-CH2CH (OH) CH2OHCH2CH2O) 25-C16H33 (i) C4F9-CH2CH (OH) CH2OHCH2CH2O) 30-C16H33 (j) C4F9-CH2CH (OH) CH2OHCH2CH2O) 40-C16H33 (k) C4F9-CH2CH2CH2OH ) 20-C18H37 l) C4F9-CH2CH (OH) CH2OHCH2CH2O) 30-C18H37 (m) C4F9-CH2CH (OH) CH2OHCH2CH2O) 40-C18H37 (n) C4F9-CH2CH (OH) CH2O- (CH2CH2O) 23-CH2CH (OH) ) CH2-C4F9 (o) C4F9-CH2CH (OH) CH2OHCH2CH2O) 35-CH2CH (OH) CH2-C4F9 (p) C4F9-CH2CH (OH) CH2OHCH2CH2O) 45-CH2CH (OH) CH2-C4F9 (q) C6F13-CH2CH (OH) CH2OHCH2CH2O) 21-C12H25 (r) C6F13-CH2CH (OH) CH2OHCH2CH2O) 25-C12H25 (S) C6F13 - CH2CH (OH) CH2OHCH2CH2O) 30-C12H25 (t) C6F13-CH2CH (OH) CH2OH2 CH2CH2 (OH) CH2-C6F13 (u) C6F13-CH2CH (OH) CH2OHCH2CH2O) 35-CH2CH (OH) CH2-C6F13 (v) C6F13-CH2CH (OH) CH2O HCH2CH2O) 45-CH2CH (OH) CH2-C6F13
Among these, the compounds of (a) to (c) and (n) to (v) are particularly preferable because they have desirable affinity for the organic solvent.
The silicone surfactant is appropriately selected depending on the intended purpose without any restrictions, but it is preferably selected from those that are not decomposed in a high pH condition. Examples of silicone surfactant include modified polydimethylsiloxane in the side chain, a modified polydimethylsiloxane in the terminal, and modified polydimethylsiloxane in both the side and the terminals.
The silicone surfactant having, as a modified group, a polyoxyethylene group, or a polyoxyethylene polyoxypropylene group is particularly preferable because it has excellent properties as an aqueous surfactant.
These surfactants can be synthesized appropriately for use, or selected from commercial products. Commercial products thereof may be readily available from BYK Japan KK, Shin-Etu Chemical Co., Ltd., Dow Corning Toray Co., Ltd. The polyether modified silicone surfactant is selected appropriately depending on the intended purpose without any restrictions , and examples thereof include a compound in which the polyalkylene oxide structure represented by the following general formula is introduced into a dimethyl polysiloxane Si side chain.
alkylene. As for the polyether modified surfactant commercial products of the same can be used, and examples of commercial products include KF-618, KF-462 and KF-643 (all manufactured by Shin-Etsu Chemical Co., Ltd.). The acetylene glycol or acetylene alcohol surfactant is preferably a compound represented by the following formula (16) or (17). Specific examples thereof include the compound represented by the following formula (20). <Formula (16)>
In the general formula (16), integer of 1 or more. 10 <General Formula (17)>
In the general formula (17), alkyl. <Formula (20)>
15 OH men are each a number As for the acetylene glycol surfactant or acetylene alcohol surfactant, commercial products of the same can be used. Examples of these include: Dynol® 607 (manufactured by Air Products and Chemicals Inc.); Surfynol® 104, Surfynol® 420, Surfynol® 440 and Surfynol® SE (available from Nissin Chemical Industry Co., Ltd.): OLFINE E1004, OLFINE E1010, OLFINE EXP.4001, OLFINE EXP.4200, OLFINE EXP.4051F and OLFINE EXP.4123 (manufactured by Nissin Chemical Industry Co., Ltd.).
Examples of anionic surfactant include a polyoxyethylene alkyl ether acetic acid salt, dodecylbenzene sulfonic acid salt, lauric acid salt and polyoxyethylene alkyl ether sulfate salt. Examples of anionic surfactant include polyoxyethylene alkyl ether, polyoxypropylene polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylphenyl ether, polyoxyethylene alkylamine, and polyoxyethylene alkylamide.
An amount of surfactant in the inkjet is preferably 0.01 mass% to 3.0 mass%, more preferably 0.5 mass% to 2.0 mass%.
When the amount of the product is less than 0.01% by mass, an effect of the surfactant cannot be sufficiently demonstrated. When the amount of the same is greater than 3.0% by mass, the penetration capacity of the resulting ink into the recording medium is higher than necessary, which can cause a reduction in the image density of the resulting image, or eliminate it. <Penetrating Agent>
The inkjet ink of the present invention preferably contains, as the penetrating agent, at least one selected from the group consisting of a C8-C11 polyol compound and a glycol ether compound. The penetrating agents are preferably those that have a solubility of 0.2 mass% to 5.0 mass%, in water of 25oC. Among them, 2-ethyl-1,3-hexanediol [solubility: 4.2% (25o)] and 2,2,4-trimethyl-1,3-pentanediol [solubility: 2.0% (25oC)] are particularly preferred. Examples of other compounds include: aliphatic diol such as 2-ethyl-2-methyl-1,3-propanediol, 3,3-dimethyl-1,2-butanediol, 2,2-diethyl-1,3-propanediol, 2-methyl -2-propyl-1,3-propanediol, 2,4-dimethyl-2,4-pentanediol, 2,5-dimethyl-2,5-hexanediol and 5-hexane-1,2-diol. Other penetrating agents used in combination with the above are appropriately selected depending on the intended purpose without any restriction, with the proviso that they dissolve in the paint to adjust the paint to have desirable properties, and examples of which include: alkyl or aryl alcohol ethers polyhydric such as diethylene glycol monophenyl ether, ethylene glycol monophenyl ether, ethylene glycol monoalyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether and tetraethylene glycol chlorophenyl ether; and lower alcohols such as ethanol.
An amount of the inkjet penetrating agent is preferably 0.1% by mass to 4.0% by mass. When the amount of it is less than 0.1% by mass, the resulting ink cannot have quick drying properties, which can cause the formation of a blurred image. When the amount of the same is greater than 4.0% by mass, the dispersion stability of the colorant is impaired to cause the nozzle to clog, or the penetration capacity of the resulting ink into the recording medium is higher than necessary , which can cause reduced image density of the resulting image, or eliminate. <Water Dispersible Resin>
As for water-dispersible resin for use in ink, a water-dispersible resin having excellent film-forming ability (image-forming ability) and having high water repellency, high water resistance is effective for image recording.
Examples of water-dispersible resin include synthetic resin, such as synthetic addition resin and a natural polymeric compound.
Examples of condensed synthetic resin include a polyester resin, a polyurethane resin, a polyepoxy resin, a polyamide resin, a polyether resin, a poly (meth) acrylic resin, an acrylic silicone resin and a fluororesin. Examples of addition synthetic resin include a polyolefin resin, a polystyrene resin, a polyvinyl alcohol resin, a polyvinyl resin, a polyacrylic acid resin and an unsaturated carboxylic acid resin.
Examples of natural polymeric compound include cellulose, rosin and natural rubbers.
Among these, polyurethane resin particles, acrylic silicone resin particles and fluororesin particles are particularly preferable. Two or more of these water-dispersible resins can be used in combination, without any particular problems.
As for the fluororesin particles, fluororesin particles having fluoroolefin unit are preferable. Among these, fluorine-containing vinyl ether resin particles containing a fluoroolefin unit and a vinyl ether unit are particularly preferable.
The fluoroolefin unit is appropriately selected depending on the intended purpose without any restrictions, and examples of it include -CF2CF2-, - CF2CF (CF3) - and —CF2CFCl-. 5 The vinyl ether unit is appropriately selected depending on the intended purpose without restriction, and examples of it include the units represented by the following structural formulas.
fluorine each containing a fluoroolefin unit and a vinyl ether unit, an alternating copolymer, in which the fluoroolefin unit and the vinyl ether are alternatively copolymerized, is preferable.
These fluoresine particles can be synthesized appropriately or selected from commercial products. Examples of such commercial products include: FLUONATE FEM-500 and FEM-600, DICGUARD F-52S, F-90, F-90M, F- 90N and AQUAFURFURAN TE-5A manufactured by Dainippon Ink Chemical Industries Co., Ltd .; and LUMIFLON FE4300, FE4500, FE4400, ASAHI GUARD AG-7105, AG-950, AG-7600, AG-7000 and AG-1100 manufactured by AGC SEIMI CHEMICAL CO., LTD.
As for the water dispersible resin, a homopolymer can be used, or a copolymer can be used as a composite resin. In addition, the water-dispersible resin for use can have a single-phase or core-wrap structure, or it can be prepared by a power supply emulsion.
As for the water-dispersible resin, it is possible to use a resin itself having a hydrophilic group and self-dispersion, and a resin itself having no dispersivity, but in which dispersivity is impaired with the use of a surfactant and another resin having a hydrophilic group. Among these resins, an ionomer of a polyester resin or a polyurethane resin, or a fine particle resin emulsion obtained by emulsification polymerization or suspension polymerization of an unsaturated monomer is mostly appropriately used. In the case of emulsification polymerization of the unsaturated monomer, a resin emulsion is obtained by reacting the water in which an unsaturated monomer, a polymerization initiator, a surfactant, a resin transfer agent, a chelating agent and a pH adjuster are added . Thus, a water-dispersible resin can be easily obtained, and the desired properties are easily obtained because the components of the resin can be exchanged.
Examples of unsaturated monomer include unsaturated carboxylic acids, monofunctional or polyfunctional methacrylic acid ester monomers, methacrylic acid amide monomers, cyano vinyl compound monomers, vinyl monomers, allyl compounds monomers, olefin monomers, diomers, and monomers oligomers having unsaturated carbons. These can be used independently or in combination. By combining these monomers, the resulting resin properties can be modified flexibly. The properties of the resulting resin can also be modified with the use of an oligomer-type polymerization initiator, through a polymerization reaction or graft reaction.
Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, fumaric acid and maleic acid.
Examples of monofunctional methacrylic acid ester monomers include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, methacrylate, hexacrylate 2-ethylexyl, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, glycidyl methacrylate, 2-hydroxy methacrylate, hydroxy methacrylate 2-hydroxy ethyl amino dimethyl, methacryloxyethyltrimethylammonium salt, 3- methacryloxypropyltrimethoxysilane, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-amine acrylate, hexyl acrylate, isoamyl acrylate 2-ethylhexyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate, octadecyl acrylate, cyclohexyl acrylate, f acrylate enyl, benzyl acrylate, glycyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, ethyl dimethyl ethyl acrylate, and acryloxyethyltrimethyl ammonium salt.
Examples of polyfunctional methacrylic acid ester monomers include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene dimethacrylate 1,6-hexanediol, neopentyl glycol dimethacrylate, dipropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, polybutylene glycol dimethacrylate, 2,2'-bis (4-methacryloxydiethoxyphenyl) propane, trimethyl acrylate propane, trimethyl acrylate, propane polyethylene glycol, triethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, 1,9-nonanediol diacrylate, diacrylate polypropylene glycol, 2,2'-bis (4-acryloxypropyloxyphenyl) propane, 2,2'-bis (4-acryloxydiethoxyphenyl) trimethylol propane, tetramethyl triacrylate ol methane, ditrimethylol tetraacrylate, tetramethylol methane tetraacrylate, pentaerythritol tetraacrylate and dipentaerythritol hexacrylate.
Examples of methacrylic acid amide monomers, methacryl amide, N, N-dimethyl acrylamide, methylene bisacryl amide, and 2-acrylamide-2-methylpropane sulfonic acid.
Examples of aromatic vinyl monomers include styrene, α-methylstyrene, toluene vinyl, 4-t-butylstyrene, chloro-styrene, vinyl anisole, naphthalene vinyl and divinyl benzene.
Examples of cyano vinyl compound monomers include acetonitrile and methacrylonitrile.
Examples of vinyl monomer include vinyl acetate, vinylidene chloride, vinyl chloride, vinyl ether, vinyl ketone, vinyl pyrrolidone, vinyl sulfonic acid or salts thereof, vinyl trimethyloxysilane, and vinyl triethoxysilane.
Examples of the allyl compound monomer include allyl sulfonic acids or salts thereof, allyl amine, allyl chloride, diallyl amine and diallylmethyl ammonium.
Examples of olefin monomers include ethylene and propylene.
Examples of diene monomers include butadiene and chloroprene.
Examples of oligomers that have unsaturated carbon atoms include styrene oligomer having a methacryloyl group, styrene-acrylonitrile oligomer having a methacryloyl group, methyl methacrylate oligomer having a methacryloyl group, dimethyl siloxyl oligomer having a methylacrylyl oligomer having a group having an acryloyl group.
The water-dispersible resin experiences the disruption of molecular chains, such as dispersion and hydrolysis disruption, in the presence of a strong alkali or strong acid, and thus the pH of the water-dispersible resin is preferably 4 to 12 and, particularly, of the from the point of view of the ability to mix with water-dispersible dyes, it is more preferably 6 to 11, and even more preferably 7 to 9.
The average particle diameter (D50) of the water-dispersible resin is relevant to the viscosity of the dispersion liquid. In the case of water-dispersible resins that have the same composition, the smaller the particle diameter becomes, the higher the viscosity at the same solids content. The average particle diameter (D50) of the water-dispersible resin is preferably 50 nm or greater to prevent the resulting paint from having excessively high viscosity. When the average particle diameter is several tens of micrometers, the water-dispersible resin cannot be used because the diameter of the water-dispersible resin is larger than that of the nozzle holes in the inkjet head. When the diameter of the water-dispersible resin is smaller than that of the nozzle holes, but particles having large particle diameters are present in an ink, the ink's ejection stability degrades. In order not to impair the dispersion stability of the paint, the average particle diameter (D50) of the water-dispersible resin is preferably 200 nm or less, and more preferably 150 nm or less.
The water-dispersible resin preferably has a function of fixing the water-dispersible dye on the surface of the paper, to form a coating at normal temperature and to improve the ability to fix the dye. Therefore, the minimum film-forming temperature (MFT) of the water-dispersible resin is preferably 30oC or lower. In addition, when the glass transition temperature of the water-dispersible resin is -40oC or lower, folds occur in the printed matter due to the increased viscosity of the resin coating. Thus, the water-dispersible resin preferably has a glass transition temperature of -30oC or higher.
An amount of the water-dispersible resin in the inkjet ink is preferably 2 wt% to 30 wt%, plus PV, 5 wt% to 25 wt% on solid basis.
In this document, the solids content of the colorant, the pigment contained in the colorant, and the water-dispersible resin can be determined by a method of separating only the colorant and the components of the water-dispersible resin from the paint. When the pigment is used as the colorant, a mass reduction ratio of the paint is evaluated through a thermal mass analysis, thus making it possible to measure a mass ratio between the colorant and the water-dispersible resin. When the molecular structure of the dye is apparently known, in the case where the dye is a pigment or dye, it is possible to determine the solids content of the dye using NMR; in the case where the dye is an inorganic pigment contained in metal atoms and in the molecular skeleton, or an organic pigment containing metal or dye containing metal, the solids content of the dye can be determined using fluorescent X-ray analysis. <Other Components>
The other components mentioned above are appropriately selected depending on the intended purpose without any restriction, and examples of them include a foam inhibitor (a defoaming agent), a pH regulator, an antiseptic antifungal agent, a chelating agent, a rust-preventing agent , an antioxidant, an ultraviolet absorber, an oxygen absorber and a photostabilizer. -Foam Inhibitor- The foam inhibitor is used by adding a small amount of it to an inkjet ink to thereby inhibit foaming. In the present document, "foaming" means that the air is encapsulated with thin films of liquid. Foaming is related to inkjet ink properties such as surface tension and viscosity. Namely, with a liquid having a high surface tension, such as water, a force to minimize the surface area of the liquid as little as possible works and, therefore, such a liquid is difficult to foam. In contrast, inkjet ink having high viscosity and high permeability has low surface tension. Therefore, t forms easily, and the bubbles produced tend to remain due to the viscosity of the ink, therefore the inkjet ink is difficult to defoam. The foam inhibitor typically destroys the bubbles by partially reducing the surface tension of the bubble film, or by spreading the foam insoluble foam inhibitor in the foaming liquid over the surface of the foaming liquid. In the case where a fluorotensive which has a very strong effect of reducing the surface tension, is used as a surfactant in the inkjet ink, the foam inhibitor of the first mechanism cannot partially reduce the surface tension of the bubble film. Therefore, it is not generally used. Consequently, the last foam inhibitor that is insoluble in the foaming liquid (for example, the paint) is used. In this case, inkjet ink stability is reduced due to the ink-soluble foam inhibitor.
Contrary to these, the foam inhibitor represented by the general formula (19) has a high affinity for fluorotensive, although it has no high effect of reducing surface tension compared to fluorotensive. Therefore, the foam inhibitor is effectively included in the bubble film, and the surface of the bubble film becomes partially unbalanced due to the difference in surface tension between the fluorotensive and the foam inhibitor, which destroys the bubbles.
As for the foam inhibitor, a compound represented by the following formula (19) is used.
<General Formula (19)>

In the general formula (19), R1 and R2 are each independently a C3-C6 alkyl group; R3 and R4 are each independently a C1-C2 alkyl group; and n is an integer and 1 to 6.
Preferable examples of the compound represented by the general formula (19) include 2,4,7,9-tetramethyldecane-4,7-diol and 2,5,8,11-tetramethyldodecane-5,8-diol. Among these, 2,5,8,11-tetramethyldodecane-5,8-diol is particularly preferable because it has a high foam inhibiting effect and a high affinity for the paint.
An amount of the foam inhibitor in the inkjet ink is preferably 0.01 wt% to 10 wt%, more preferably 0.1 wt% to 5 wt%. When the amount of the foam inhibitor is less than 0.01% by mass, the defoaming effect may not be obtained. When the amount of the same is greater than 10% by mass, the effect of inhibiting foaming reaches its peak, and the excessive amount of the same can adversely affect the physical properties of the paint such as viscosity and particle diameters. - pH regulator The pH regulator is selected appropriately depending on the intended purpose, without any restriction, with the proviso that it does not adversely affect an ink to be prepared, and can adjust the pH of the ink in 7 to 11. Examples of pH regulator pH include alcohol amines, hydroxides of alkali metal elements, ammonium hydroxides, phosphonium hydroxides, and alkali metal carbonates. When the pH of the inkjet ink is lower than 7 or higher than 11, problems such as degeneration and ink leakage and ejection defects can occur due to the large amount of ink dissolving in the inkjet head and of a used ink supply unit.
Examples of alcohol amines include diethyl amine, triethanol amine and 2-amino-2-ethyl-1,3-propanediol.
Examples of hydroxides of alkali elements include lithium hydroxide, sodium hydroxide and potassium hydroxide.
Examples of ammonium hydroxides include ammonium hydroxide and quaternary ammonium hydroxide.
Examples of phosphonium hydroxides include quaternary phosphonium hydroxide.
Examples of alkali metal carbonates include lithium carbonate, sodium carbonate and potassium carbonate. -Antiseptic Antifungal Agent-
Examples of antiseptic antifungal agent include sodium dehydroacetate, sodium sorbate, sodium 2-pyridinethiol-1-oxide, sodium benzoate and sodium pentachlorophenol. -Chelating Agent-
Examples of a chelating agent include sodium ethylenediamine tetraacetate, sodium nitrileacetate, sodium hydroxyethylethylenediamine triacetate, sodium diethylene triamine pentaacetate and sodium uramyl diacetate. -Rustproof Agent-
Examples of antirust agent include acid sulfite, acid thiosulfate, thioglycolic acid ammonium, ammonium diisopropyl nitrate, pentaerythritol tetranitrate and ammonium dicyclohexyl nitrate. -Antioxidant-
Examples of antioxidants include a phenolic antioxidant (including hindered phenolic antioxidant), an amine antioxidant, a sulfuric antioxidant and a phosphoric antioxidant.
Examples of phenolic antioxidant (including hindered phenolic antioxidant) include butylated hydroxyanisol, 2,6-di-tert-butyl-4-ethyl phenol, stearyl-β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenobis (4-methyl-6-tert-butylphenol), 2,2'-methylenobis (4-ethyl-6-butylphenyl), 3,9-bis (1,1-dimethyl-2- [β - (3-tert-butyl-4-hyroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5.5] undecane, 1,1,3-tris (2-methyl-4- hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, and tetracis [methylene-3- ( 3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane.
Examples of amine antioxidant include phenyl-β-naphthyl amine, α-naphthyl amine, N, N'-di-sec-butyl-p-phenylene diamine, phenothiazine, N, N'-diphenyl-p-phenylene diamine, 2, 6- di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butyl-phenol, hhydroxyanisol, 2,2'-methylenebis- (4-methyl- 6-ter-butylphenol), 4,4'-butylenobis (3-methyl-6-tert-butylphenol), 4,4'-thiobis (3-methyl-6-tert-butylphenol), tetracis [methylene-3 (3 , 5-di-tert-butyl-4-dihydroxyphenyl) propionate] methane, and 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane.
Examples of the sulfuric antioxidant include dilauryl-3,3'-thiodipropionate, distearyliodipropionate, laurylstearltiodipropionate, dimiristyl-3,3'-thiodipropionate, diesterathyl-β-β'-thiodipropionate, 2-mrcaptobenzoimidyluryl and dulfide. Examples of phosphoric antioxidant include triphenyl phosphate, octadecyl phosphate, triisodecyl phosphate, trilauryltrithium phosphate and trinonylphenyl phosphate. -Ultraviolet absorber-
Examples of an ultraviolet absorber include a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, a salicylate ultraviolet absorber, a cyanoacrylate ultraviolet absorber and a nickel complex salt ultraviolet absorber.
Examples of the benzophenone ultraviolet absorber include 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone and 2,2 ', 4,4 '-tetrahydroxybenzophenone.
Examples of benzotriazole ultraviolet absorber include 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-4 ' - octoxyphenyl) benzotriazole and 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole.
Examples of the salicylate ultraviolet absorber include phenyl salicylate, p-tert-butylphenyl salicylate and p-octylphenyl salicylate.
Examples of cyanoacrylate ultraviolet absorber include ethyl-2-cyano-3,3'-methoxyphenyl acrylate) and butyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate.
Examples of nickelbis (octylphenyl) complete salt ultraviolet absorber, 2,2'-thiobis (4-tert-octylferrate) -n-butyl nickel (II), 2,2'-thiobis (4-tert-octyferrate) ) -2-ethylexyl amine nickel (II), and 2,2'-thiobis (4-tert-octylferrate) -triethanol amine nickel (II).
The inkjet ink of the present invention can be prepared by dispersing or dissolving, in an aqueous medium, water, the organic solvent (wetting agent), the colorant, the surfactant, optionally the penetrating agent, the water-dispersible resin, and another component, and optionally and stirring and mixing the mixture. The dispersant can be carried out, for example, by a sand mill, a homogenizer, a ball mill, an ink stirrer or an ultrasonic disperser, and the stirring and mixing can be carried out by a stirrer using a stirring paddle, a magnetic stirrer or high speed disperser.
The physical properties of the inkjet ink of the present invention are selected appropriately depending on the intended purpose, without any restriction. For example, viscosity and surface tension are preferably within the following ranges.
The viscosity of the inkjet ink is preferably 5 mPa.s to 25 mPa.s, more preferably 7.0 mPa.s to 20 mPa.s at 25 ° C. When the ink viscosity is 5 mPa.s or more, the print density and character qualities of images formed with the resulting ink can be improved. When the ink viscosity is 25 mPa.s or lower, the ejection capacity of the resulting ink can be ensured.
Viscosity can be measured, for example, using a viscometer (RL-550, manufactured by Toki Sangyo Co., Ltd.) at 25oC.
The dynamic surface tension of the inkjet ink is preferably 35 mN / m or lower, more preferably 32 mN / m or lower at 25oC with the bubble run time on the surface of 15 ms in the bubble pressure method maximum. When its surface tension is greater than 35 mN / m, the resulting ink is not easily leveled in the recording medium, which can prolong the time required for drying.
The coloring of the inkjet ink of the present invention is appropriately selected depending on the intended purpose, without any restriction, and examples thereof include yellow, magenta, cyan and black. Engraving using an ink set containing two or more of these paint colors in combination makes it possible to form multicolored images, and engraving using an ink set containing all these paint colors makes it possible to form fully colored images.
The inkjet ink of the present invention can be used appropriately with a printer equipped with either a piezo inkjet head, a thermal inkjet head, an electrostatic inkjet head, where the jet head piezo ink is configured to eject ink droplets by deforming a vibrating plate constituting a wall surface of an ink flow channel to change the volume within the ink flow channel using a piezoelectric element as a pressure generating unit for compress the ink into the ink (see JP-A no 02-51734), the thermal inkjet head is configured to generate air bubbles by heating an ink within an ink flow channel using a thermal element (see JP- No. 61-59911), and the electrostatic inkjet heat is configured to eject ink droplets by deforming a vibration plate with electrostatic force generated between the vibration plate and an electrode provided with a wall surface of an ink flow channel to confront the vibration plate, to thereby change the volume within the ink flow channel (see JP-A no 06-71882).
The inkjet ink of the present invention is used appropriately in a number of fields such as inkjet inks, fountain pen inks, ballpoint pen inks, marker pen inks, and felt-tip pen inks, and it it is particularly used with an image forming device (for example, a printer) of an inkjet engraving system. For example, inkjet ink can be used with a printer that has a function of speeding up ink setting by heating a recording paper and inkjet ink at 50oC to 200oC during, or before and after printing, and inkjet ink is particularly suitable used for ink cartridge, ink engraving method, ink engraving device, and material engraved with the tub of the present invention. (Ink Media Set)
The ink media set for use in the present invention is a combination of the ink jet ink of the present invention and recording media. <Recording Media>
The recording media is selected appropriately depending on the intended purpose without any restrictions and, for example, plain paper, glossy paper, special paper, fabric, films, OHP sheets, ordinary printing sheets can be used appropriately.
Among these, like the recording media, conventional printing sheets having liquid absorption properties within a certain range is preferable because they can record images of excellent image quality (for example, image density, color saturation, no dripping, and no color crossover). High gloss, and excellent fastening without spreading. Specifically, the preferred recording media include a recording medium containing a support and a coating layer formed on at least one surface of the support, and having an amount of pure water transfer of preferably 1 ml / m2 to 25 ml / m2, more preferably 1 ml / m2 to 10 ml / m2, and even more preferably 2 ml / m2 to 10 ml / m2 with a contact duration of 100 ms, as measured by a dynamic scanning absorptometer. Also, a recording medium having an amount of pure water transfer from 3 ml / m2 to 40 ml / m2 with a contact duration of 400 ms, as measured by a dynamic scanning absorptometer, is preferable.
The use of the inkjet ink of the present invention with such recording means makes it possible to perform image recording having excellent image quality, high brightness, and excellent fixation capacity without spreading and, therefore, gives a great effect. In the case where recording media that have small amounts of pure transferred water are used, runoff (a phenomenon in which the adjacent printed dots are connected, and the dots are left in an image) and the crossing of color (crossing between different colors ) may occur. In the case where recording media that have large amounts of pure water transferred is used, the dots of the recording ink may be smaller than the intended diameter, and as a result, a solid image cannot be filled with The paint. The use of the inkjet ink of the present invention with the aforementioned recording means can effectively prevent these problems.
In this document, the dynamic scanning absorptometer (Journal from Japan Technical Association of the Pulp and Paper Industry, vol. 48, May 1994, pp. 88-92, Kukan Shigenori) is a device that can precisely measure an amount of absorption liquid over a very short period of time. The dynamic scanning absorptometer directly reads the absorption speed based on the displacement of the meniscus in a capillary and the measurement is automatic as follows: a disk-shaped sample is prepared; the absorption head is swept over the sample in a spiral mode; the scanning speed is automatically changed according to a predetermined pattern; and a sample is used for measurements of a required number of points. The head for supplying liquid to the paper sample is connected to the capillary through a Teflon tube (registered trademark). The position of the meniscus in the capillary is automatically read by an optical sensor. More specifically, a dynamic scanning absorptometer (K 350 series model D, Kyowa Co., Ltd.) was used to measure the transfer rate of purified water or ink. The transfer quantities with contact durations from 100 ms to 400 ms can be obtained based on measurements of the transfer quantity with contact durations around these contact lengths by interpolation. -Support-
The support is selected appropriately depending on the intended purpose, without any restriction, and examples thereof include paper primarily formed from wood fibers, and a sheet material (e.g., non-woven cloth) formed from wood fibers and synthetic fibers.
The paper is appropriately selected from those known in the art depending on the intended purpose, without any restriction, and examples of it include wood pulp and recycled pulp. Examples of wood pulp include bleached hardwood kraft pulp (LBKP), bleached softwood kraft pulp (NBKP), NBSP, LBSP, GP and TMP.
Examples of materials for the recycled pulp include super whites, whites with lined marks, creamy whites, cards, extra super whites, similis paper, white color, Kent paper, white art paper, special high cut, another high cut , newspaper, and magazines shown in the standard used paper quality specification table specified by the Paper Recycling Promotion Center. Specific examples thereof include waste paper and cardboard, which may be chemical pulp paper or paper containing high yield pulp, such as sheets for printers (for example, uncoated computer paper, heat sensitive paper, and pressure sensitive paper , which are sheets related to information); used OA sheets (for example, PPC sheets), coated paper (for example, art paper, coated paper, light weight coated paper and matte paper) and uncoated paper (for example, high quality, high quality paper color, notes, letter, wrapping paper, fancy paper, medium quality paper, newspaper, wooden paper, gift wrapping paper, similis paper, pure white wrapping paper and milk carton). These can be used independently or in combination.
Paper pulp is usually produced by combining the following four steps. (1) In disaggregation, the used paper is broken into filaments by mechanical force and the chemicals in a paste former and printing ink are detached from the filaments; (2) Powder, foreign substances (such as plastics) and dirt on used paper are removed by screens and cleaners; (3) When removing ink, the printing ink from the filaments using surfactants is removed by flotation or cleaning technique; and (4) In bleaching, the filaments are bleached by oxidation or reduction.
When the used pulp is mixed, the mixing ratio of the used pulp in the total pulp content is preferably 40% or less.
Like the internal fillers used in the support, pigments conventionally known as white pigments are used. Examples of white pigments include: inorganic white pigments such as light calcium carbonate, heavy calcium carbonate, kaolin, clay, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate , satin white, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, synthetic silica, aluminum hydroxide, alumina, lithoponium, zeolite, magnesium carbonate and magnesium hydroxide; and organic pigments such as styrene plastic pigment, acrylic plastic pigment, polyethylene, microcapsules, urea resin and melamine resin. These can be used independently or in combination.
Examples of internal sizing agent used to make the support include neutral rosin based sizing agent used to make neutral sheets, alkenyl succinic anhydride (ASA), alkyl ketene dimer (AKD), and petroleum resin based sizing agent . Among these, the sizing agent based on neutral rosin and alkenyl succinic anhydride are particularly preferable. The alkyl ketene dimer is a highly effective bonding agent and only a small amount is required. However, the embossing paper surface (medium) tends to have a lower friction factor and become slippery, which may not be advantageous for transferring paper in inkjet engraving.
A thickness of the support is appropriately selected depending on the intended end without any restrictions, but it is preferably 50 μm to 300 μm. Furthermore, a base weight of the support is preferably 45 g / m2 to 290 g / m2. -Coating layer-
The coating layer contains a pigment and a binder (an agglutination agent) and can also contain a surfactant and other components.
As for the pigment, an inorganic pigment, or a combination of the inorganic pigment and an organic pigment can be used.
Examples of inorganic pigment include kaolin, talc, heavy calcium carbonate, light calcium carbonate, calcium sulfide, amorphous silica, titanium white, magnesium carbonate, titanium dioxide, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, hydroxide zinc and chloride. Among these, kaolin is particularly preferable because it shows excellent gloss and gives textures close to the offset printing paper.
Examples of kaolin include delaminated kaolin, calcined kaolin and kaolin engineered by surface modification. Considering the brightness, it is preferable that 50% by mass or more kaolin in the total kaolin content consists of kaolin having a particle size distribution in which 80% by mass or more particles have a particle size of 2 µm or less.
An amount of kaolin for use is preferably 50 parts by weight or greater with respect to 100 parts by weight of the binder. When the amount is less than 50 parts by mass, sufficient brightness cannot be obtained. There is no limit to the amount of kaolin added to the coating layer, but it is preferably 90 parts by weight or less in view of the flowability and thickening of kaolin particularly under high shear force.
Examples of organic pigment include aqueous dispersion of styrene-acryl copolymer particles, of styrene-butadiene copolymer particles, if polystyrene particles, and if polyethylene particles. These organic pigments can be used in a mixture of two or more.
An amount of organic pigment is preferably 2 parts by weight to 20 parts by weight with respect to 100 parts by weight of the total pigments contained in the coating layer. Organic pigments demonstrate excellent gloss and have lower specific gravities. Therefore, massive, shiny, high-surface coating layers are obtained. When the amount of the organic pigment is less than 2 parts by weight, the above effects are not obtained. When the amount thereof is greater than 20 parts by mass, the deteriorated flow capacity of the coating solution leads to decreased coating operation effectiveness. It, too, is economically disadvantageous in terms of cost.
Organic pigments are classified into solids, hollow and screw, in terms of their shapes. In the balance of brightness, surface coverage and flow capacity of the coating solution, the average particle diameter (D5O) of the same is preferably 0.2 μm to 3.0 μm. More preferably, the hollow pigment having a void ratio of 40% or higher is used.
As the binder, an aqueous resin is preferably used.
Like the aqueous resin, at least any of a water-soluble resin or a water-dispersible resin is preferably used. The water-soluble resin is appropriately selected depending on the intended purpose, without any restrictions. Examples of aqueous resin include: polyvinyl alcohol; modified polyvinyl alcohol such as anion-modified polyvinyl alcohol, cation-modified polyvinyl alcohol and acetal-modified polyvinyl alcohol; polyurethane; polyvinyl pyrrolidone; modified polyvinyl pyrrolidone such as a copolymer of polyvinyl pyrrolidone and vinyl acetate, a vinyl pyrrolidinone copolymer and dimethylamethyl acrylic acid, a quaternized vinyl pyrrolidone copolymer and methacrylethyl dimethylaminoethylacetic acid and pyrrolidone methylacrylamide copolymer. ; cellulose such as carboxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose; modified cellulose such as cationized hydroxyethyl cellulose; synthetic resins such as polyester, polyacrylic acid (ester), a melamine resin, modified products thereof and a polyester and polyurethane copolymer; and others such as poly (meth) acrylic acid, oxidized poly (meth) acrylamide starch, esterified phosphoric acid starch, self-modifying starch, cationized starch or various modified starches, polyethylene oxide, sodapolycrylate and alginate soda. These can be used independently, or in combination.
Among these, polyvinyl alcohol, cation-modified polyvinyl alcohol, acetal-modified polyvinyl alcohol, polyester, polyurethane and a polyester and polyurethane copolymer are particularly preferable from an ink absorption point of view.
The water-dispersible resin is appropriately selected depending on the intended purpose, without any restriction, and examples thereof include polyvinyl acetate, ethylene-vinyl acetate copolymer, polystyrene, styrene (meth) acrylate copolymer, polymer based on (meth) ) acrylate, vinyl acetate- (ester) acrylic (copolymer) copolymer, styrene-butadiene copolymer, copolymer and styrene-propylene, polyvinyl ether, and silicone-acrylic copolymer. Other examples include those that contain cross-linking agents such as methylol melamine, methylol urea, methylol hydroxypropylene urea and isocyanate copolymers and self-linkers containing units such as N-methylolacrylamide.
An amount of the aqueous resin is preferably 2 parts by weight to 100 parts by weight, more preferably 3 parts by weight to 50 parts by weight, with respect to 100 parts by weight of the pigment. The amount of aqueous resin added is determined so that the net absorption properties of the resulting recording media are adjusted within desirable ranges.
When a water-dispersible dye is used as the dye, a cationic organic compound is not necessarily added to the coating layer. The cationic organic compound added to the coating layer is selected appropriately depending on the intended purpose, without any restrictions. Examples of the same include monomers, oligomers, polymers of primary to tertiary amine and quaternary ammonium salt that react with sulfonic, carboxyl or amino groups in the direct dyes or acidic dyes in the aqueous paint to form insoluble salts. Among these, oligomers or polymers are preferable.
Examples of cationic organic compound include dimethylamine-epichlorohydrin polycondensates, poly (methyl trimerylaminoethylsulfate) methacrylate, diaryl amine-acrylamide hydrochloride polycondensates, poly (diarylamine-sulfur dioxide hydrochloride), polyarylamine hydrochloride, polyarylamine hydrochloride (arylamia-diaryl amine hydrochloride), acrylamide-diaryl amine copolymers, polyvinylamine copolymers, diciandiamide, diciandiamide condensates- ammonium chloride- urea formaldehyde, polyalkylene polyamine hydrates, diciandiamide ammonium chloride, polyethyl ammonium chloride, dimethylamine chloride poly (diaryldimethylammonium chloride), poly (diaryldimethylammonium-sulfur dioxide) chloride, poly (diaryldimethylammonium-diarylamine hydrochloride) derivatives, acrylamide copolymers-diaryl dimethylammonium chloride, acrylate-hydrochloride-acrylate derivatives, hydrochloride-copolymer derivatives polyethyleneimine such as polymers of polyethyleneimine and acrylamide, and polyethyleneiminoalkylene oxide. These can be used independently or in combination.
Among these, combinations of low molecular weight cationic organic compounds such as polycondensate dimethylamine / epichlorohydrin and polyarylamine hydrochloride, and other relatively high molecular weight cationic organic compounds such as poly (diaryldimethylammonium chloride) are preferable. Combined use improves image densities and further reduces diffusion compared to individual use.
The cationic organic compounds preferably have an equivalent cation of 3 meq / g to 8 meq / g as measured by the colloid titration method (potassium polyvinyl sulfate, toluidine blue). The equivalent cation in this range gives a desirable amount of deposition on a dry basis. To determine the equivalent cation by the colloid titration method, the cationic organic compound is diluted with water to a solids content of 0.1 mass% and no pH adjustment is conducted.
A deposition amount of the cationic organic compound is preferably 0.3 g / m2 to 2.0 g / m2 on a dry basis. When the amount of deposition of the cationic organic compound is less than 0.3 g / m2 on a dry basis, effects such as sufficiently improved image densities and reduced diffusion cannot be achieved.
The surfactant optionally added to the coating layer is appropriately selected depending on the intended purpose, without any restrictions, and either an anionic surfactant, a cationic surfactant, an amphoteric surfactant, or a nonionic surfactant can be used as the surfactant. Among these, the nonionic surfactant is particularly preferable. By adding the surfactant, the water resistance of the resulting image improves, and the resulting image has a higher image density with improved dripping.
Examples of non-ionic surfactants include higher ethylene oxide alcohol adducts, alkylphenol ethylene oxide adducts, fatty acid ethylene oxide adducts, polyalcohol fatty acid ester ethylene oxide adducts, aliphatic ethylene oxide adducts superiors, ethylene oxide adducts of fatty acid superiors, ethylene oxide adducts of fatty acid, ethylene oxide adducts of fats and oils, ethylene propylene glycol adducts, glycerol fatty acid ester, glycerol ester pentaerythritol fatty acid, sorbitol and sorbitan fatty acid ester, sugar fatty acid ester, polyhydric alcohol alchemical ether, and fatty acid amide such as alkanolamine. These can be used independently or in combination.
Polyhydric alcohol is selected appropriately depending on the intended purpose, without any restrictions, and examples of it include glycerol, trimethylol propane, pentaerythritol, sorbitol and sugar. As for ethylene oxide adducts, ethylene oxide substituted by alkylene oxide such as propylene oxide or butylene oxide can be effective as long as they remain soluble in water. The substitute rate is preferably 50% or lower. Nonionic surfactants preferably have an HLB (hydrophilic / lipophilic balance) of 4 to 15 and more preferably 7 to 13.
An amount of the surfactant is preferably 0 parts by weight to 10 parts by weight, more preferably 0.1 parts by weight to 1.0 part by weight with respect to 100 parts by weight of the cationic organic compound.
Other components can be added to the coating layer, if necessary, with the proviso that they do not adversely affect the purpose and the achievable effect of the present invention. Examples of other components include additives such as alumina powder, a pH regulator, a preservative and an antioxidant.
A method for forming the coating layer is selected appropriately depending on the intended purpose, without any restrictions. For example, the coating layer can be formed by a method in which a solution of the coating layer is impregnated or applied to the support. The method for impregnating or applying the coating layer solution is selected appropriately depending on the intended purpose, without any restrictions. For example, it can be applied by various coatings such as a conventional size press, an inlet cylinder size press, film transfer size press, blade coating, rod coating, air knife coating, and curtain lining. From a cost perspective, a conventional size press, inlet cylinder size press, or film transfer press, which is equipped on the paper making machine, can be used for impregnation or deposition, which is followed by a machine finish.
The amount of deposition of the coating layer solution is appropriately selected depending on the intended purpose, without any restriction, but is preferably 0.5 g / m2 to 20 g / m2. More preferably 1 g / m2 to 15 g / m2 on a solid basis.
After impregnating or applying the coating layer solution, the coated solution can be dried, if necessary. In this case, the temperature for drying is appropriately selected depending on the intended purpose, without any restriction, but it is preferably about 100oC to about 250oC.
The recording medium may contain either a back layer, on the back surface of the support, or between the support and the coating layer. The recording medium may also contain other layers between the support and the back layer, and may have a protective layer over the coating layer. Each of these layers can be a single layer, or a multiple layer.
As for the recording medium, except the inkjet recording medium, common commercially available printing sheets, coated offset printing paper and engraved printing coated paper can be used.
Commercially available coated printing paper is coated paper used for commercial printing, or printing for publication, such as high gloss coated paper, ie plastered paper (size A0, size A1), size A2 coated paper, size A3 coated paper, B2 size coated paper, light weight coated paper, thin coated paper and is used for offset printing or gravure printing. Specific examples thereof include Aurora Coat (manufactured by Nippon Paper Industries Co., Ltd.), and POD Gloss Coat (manufactured by Oji Paper Co., Ltd.). <Ink Cartridge>
The ink cartridge for use in the present invention contains a container and the ink jet ink of the present invention housed in the container, and can contain further members, if necessary.
The container is not particularly restricted, and its shape, structure, size and material are appropriately selected depending on the intended purpose. For example, the container is preferably selected from those that have at least one ink bag formed from a laminated aluminum film, or a resin film.
The ink cartridge will be explained with reference to figures 1 and 2, below. Figure 1 is a diagram showing an example of the ink cartridge of the present invention, and Figure 2 is a diagram illustrating an example of modifying the ink cartridge of Figure 1.
As illustrated in figure 1, an ink bag 241 is filled with the inkjet ink of the present invention by injecting the inkjet ink from the ink inlet 242. After removing the air present inside the ink bag 241, the ink inlet 242 is fused-sealed. At the time of use, a needle equipped in a main body of the ink engraving device 101, which will be described later with reference to figure 3, is inserted into an ink outlet 243 formed by a rubber member to supply the ink in this way. to the main body of the device 101. The ink bag 241 is formed of a wrapping member such as a laminated aluminum film not permeable to air. As illustrated in figure 2, the ink bag 241 is typically housed in a plastic cartridge box 244, which is then detachably mounted on various inkjet engraving devices. The ink cartridge 201 of the present invention houses the inkjet ink (a set of inks) of the present invention therein, and can be detachably mounted on various inkjet engraving devices, particularly preferably detachably mounted on the inkjet engraving device of the present invention, which will be described below. (Inkjet Engraving Method and Inkjet Engraving Device)
The inkjet engraving method of the present invention contains at least one inkjet step, and may contain still other steps, such as a stimulus generation step and a control step, if necessary.
The ink-jet recording device of the present invention contains at least one ink-jet unit, and may contain still other units such as a stimulus generating unit and a control unit, if necessary.
The inkjet engraving method of the present invention can be carried out appropriately by means of the inkjet engraving device of the present invention, and the inkblast step can be carried out appropriately by means of the inkblast unit. In addition, the other steps mentioned above can be properly carried out using the other units mentioned above. -Ink Blasting Step and Ink Blasting Unit-
The inkjet step is applying stimulus (energy) to the inkjet ink of the present invention to make the inkjet inkjet, to thereby form an image on a recording medium.
The inkjet unit is a unit configured to apply stimulus (energy) to the inkjet ink of the present invention to make the inkjet to inkjet, to thereby form an image on a recording medium. The ink blasting unit is not particularly restricted, and examples of it include several nozzles used to eject inks.
In the inkjet head for use in the present invention, it is preferred that at least part of a liquid chamber, fluid resistance, vibration plate and nozzle member are formed of a material containing at least any silicone in the nickel. In addition, the nozzle diameter of the inkjet nozzle is preferably 30 μm or smaller, more preferably 1 μm to 20 μm.
The stimulus (energy) can be generated, for example, by the stimulus generation unit. The stimulus is appropriately selected depending on the intended end, without any restrictions, and examples of it include heat (temperature), pressure, vibrations and light. These can be used independently or in combination. Among them, heat and pressure are preferable.
The stimulus generating unit includes, for example, a heating device, a pressure device, a piezoelectric element, a vibration generator, an ultrasonic wave oscillate and light. Specific examples of the stimulus generating unit include: a piezoelectric actuator such as a piezoelectric element; a thermal actuator using a phase change due to the boiling of the liquid film caused when using an electric heat transducer such as a heating element; a shape memory actuator using a metal phase shift due to a temperature shift; and an electrostatic actuator using electrostatic force.
An inkjet modality for inkjet is not particularly restricted, and varies depending on the stimulus applied. In the case where the stimulus is heat, for example, there is a method in which a thermal energy corresponding to a recording signal is applied to the inkjet ink present in a recording head, for example, by a thermal head, to foam inkjet ink by the applied thermal energy, and droplets of inkjet ink are ejected from the openings of the recording head nozzles by pressure from the foam. In the case where the stimulus is pressure, moreover, there is a method in which a voltage is applied to a piezoelectric element adhered to the location, called a pressure chamber, in the ink flow channel into the recording head to bend the piezoelectric element and the reduction in the volume of the pressure chamber caused by the folded piezoelectric element initiates the droplet ejection of the inkjet ink from the nozzle and engraving nozzle openings.
The droplet sizes of the blasted inkjet ink are, for example, preferably 3x10-15m3 to 40x10-15m3 (3 pL to 40 pL), the ejection and blasting speed is preferably 5 m / s to 20 m / s, the activation frequency of the same is preferably 1 kHz or more, and the resolution of the same is preferably 300 dpi or more.
The inkjet engraving method can have a heating and drying step in which the recording medium in which the inkjet ink is blasted, if necessary. In this case, the recording medium can be dried by an infrared drying device, a microwave drying device, a cylinder heater, a drum heater, or hot air. In addition, the inkjet engraving method can have a fixation step as a method for leveling a surface of the formed image, or fix the image, where the fixation step is heating the recording medium to 100oC or 150oC by a heating unit to thermally fix the image. As a result of the fixing step, the brightness and fixability of the recorded image improves. As for the thermal fixation unit, a heated cylinder or drum heater having a mirror surface is appropriately used. The mirror surface (smooth part) of the cylinder heater or drum heater is brought into contact with a formed image surface to proceed to the fixation step. As for the heating temperature, the fixation cylinder heated to 100oC to 150oC is preferably used in view of the quality, safety and cost of the resulting image.
The control unit is appropriately selected depending on the intended purpose, without any restrictions, with the proviso that it can control the operation of each unit, and examples of it include a device such as a sequencer and a computer.
One embodiment for carrying out the inkjet engraving method of the present invention by a series-type inkjet engraving device will be explained below with reference to the drawings. The inkjet recording device illustrated in figure 3 contains a main body of the device 101, a paper feed tray 102 for feeding the recording sheets to the main body of the device 101, a paper discharge tray 103 for storing the embossing sheets that were fed into the main body of the device 101 and on which images were formed (engraved), and an ink cartridge loading section 104. In the upper plane of the ink cartridge loading section 104, a control 105 such as operation codes and a monitor is provided. The ink cartridge loading section 104 has a front cover 115 that can be opened to attach or detach the ink cartridge 201.
In the main body of the device 101, as shown in figures 4 and 5, a cartridge 133 is freely slidably retained in the main scan direction by a guide rod 131, which is a guide member laterally passed between the plates on the left side and right (not described), and a strut 132; and the carriage 133 is moved to scan in the direction of the arrow in figure 5 by a main scan engine (not described).
A recording head 134 composed of four inkjet recording heads that eject yellow (Y), cyan (C), magenta (M) and black (Bk) recording ink droplets is installed in the car 133 so that a plurality of ink ejection outlets are aligned in the direction that intersects the main scan direction and that the ink droplet ejection direction faces downwards. For each of the inkjet recording heads composing the recording head 134, it is possible to use, for example, a head provided with any of the following power generation units to eject ink: a piezoelectric actuator such as a piezoelectric element , a thermal actuator that uses a thermoelectric transducer such as a heating element and uses the phase shift caused by the boiling of a liquid film, a memory alloy actuator that uses a metal phase shift caused by an exchange temperature, and an electrostatic actuator that uses electrostatic force.
Also, cartridge 133 incorporates sub-tanks 135 for each color to supply the inks of each color to the recording head 134. Each sub-tank 135 is supplied and replenished with the recording ink of the present invention from the ink cartridge 201 of the loaded invention in the ink cartridge loading section 104, through an engraving ink supply tube (not described).
However, as a paper feed unit for the paper feed sheets 142 loaded in a paper loading section (pressure plate) 141 of the paper feed tray 102, a half moon cylinder (feed roller) is provided. paper 143) that feeds the paper sheets 142 one by one from the paper loading section 141, and a separation pad 144 that confronts the paper feed roller 143 and is formed of a material with a large coefficient of friction. This separation pad 144 is angled towards the side of the paper feed roller 143.
As a transport unit for transporting the paper 142 which has been fed from this paper feed unit, under the recording head 134, a conveyor belt 151 is provided for transporting the paper 142 by means of electrostatic adsorption; a counter cylinder 152 for transporting paper 142, which is sent from the paper feed unit through a guide 145, so that paper 142 is interspersed between counter counter 152 and the conveyor belt 151; a transport guide 153 for making paper 142, which is sent upward in the substantially vertical direction, changes its direction by approximately 90o and thus corresponds with conveyor belt 131; and an end pressurizing cylinder 155 inclined towards the side of the conveyor belt 151 by a compression member 154. Also, a loading cylinder 156 is provided as a loading unit for loading the surface of the conveyor belt 151.
The conveyor belt 151 is an endless belt and is able to move in circles in the transport direction of the belt, passed between a conveyor roller 157 and a tension cylinder 158. The conveyor belt 151 has, for example, a layer of surface serving as a paper adsorption surface, which is formed of a resinous material such as an ethylene-tetrafluoroethylene (ETFE) copolymer having a thickness of approximately 40 μm so that the resistance control is not conducted, and a back layer ( intermediate resistance layer, bottom layer) which is formed from the same material as the surface layer, to which resistance control is conducted using carbon. On the rear of the conveyor belt 151, a guide member 161 is placed in correspondence to a region where printing is performed by the recording head 134. In addition, as a paper unloading unit for unloading the paper 142 on which images have been recorded by the recording head 134, a separator tongue 171 is provided to separate the paper 142 from the conveyor belt 151, a paper discharge cylinder 172 and a small paper discharge cylinder 173, with the paper discharge tray 103 being placed below the paper discharge roller 172.
A double-sided paper feed unit 181 is mounted on a portion of the rear surface of the main body of the device 101 in a freely detachable mode. The double-sided paper feed unit 181 directs the paper 142 returned by rotating the conveyor belt 151 in the opposite direction and reverses it, then feeds the same between counter roller 152 and the conveyor belt 151. In addition, a feed unit manual paper 182 is provided on an upper surface of the double-sided paper feed unit 181.
In this inkjet recording device, the sheets of paper 142 are fed one by one from the paper feed unit, and the paper 142 fed upward in the substantially vertical direction is guided by the guide 145 and transported between the conveyor belt 151 and counter-cylinder 152. In addition, the direction of transport of the paper 142 is changed by approximately 90o, as one end of the paper 142 is guided by the transport guide 153 and pressed on the conveyor belt 151 by the pressurization cylinder of end 155.
On this occasion, the conveyor belt 151 is loaded by the loading cylinder 156, and the paper 142 is electrostatically adsorbed on the conveyor belt 151 and thus transported. In this document, the actuation of the recording head 134 according to an image signal while moving the carriage 133, droplets of ink are ejected on the paper 142 having stopped in order to carry out the recording for a line, and then the paper is transported over a predetermined distance, recording to the next line is performed. Upon receipt of a recording termination signal or such signal as it indicates that the rear end of the paper 142 has reached the recording region, the recording operation is terminated, and the paper 142 is discharged onto the paper discharge tray 103.
Since the amount of recording ink remaining in sub-tanks 135 has been detected as very small, a required amount of recording ink is supplied from cartridge 201 into sub-tanks 135.
As for this inkjet recording device, when the recording ink in the recording cartridge 201 of the present invention is used, it is possible to replace only the ink bag 241 inside the ink cartridge 201 by disassembling the ink cartridge housing 201 Also, even when the ink cartridge 201 is placed longitudinally and employs a front loading structure, it is possible to supply the recording ink stably. Therefore, even when the main body of the device 101 is installed with little space on it, for example, when the main body of the device 101 is stored on a shelf or when an object is placed on the main body of the device 101, it is possible replace ink cartridge 201 with ease.
Note that the example where a series-type (shuttle) inkjet recording device in which car scans are explained above, but the present invention can also be applied to an inline inkjet recording device equipped with a line type head.
Figure 7 illustrates an example of a prototype in-line printing device used for the evaluation of curl in the present invention, and as a schematic diagram illustrating an internal structure of the in-line printing device prototype (recording device of image A).
The image recording device A has a paper feed tray 1 having the structure of a pressure plate 2, and a paper feed roller 4 for feeding the recording paper 3 are mounted on a base 5.
The pressure plate 2 is rotatable about the rotational axis (a) mounted on the base 5, and pressed against the paper feed cylinder 4 by a pressure plate spring 6. A separation pad (not shown) formed from a material having a large friction coefficient such as synthetic leather is provided in the portion of the pressure plate 2 facing the paper feed roller 4 to prevent feeding of multiple embossing papers 3.
In addition, a release cam (not shown) is provided, and the release cam is configured to release the support of the paper feed roller 4 over the pressure roller 2.
In the upper structure, the pressure plate 2 is pressed downwards by the release cam to reach a certain position in the waiting state, whereby the support of the paper feed roller 4 on the pressure roller 2 is released.
In this state, the release cam is released from the pressure plate 2 and the pressure plate 2 is raised as the driving force from the transport roller 7 is transmitted to the paper feed roller 4 and the gear release cam to support the embossing paper 3 on the paper feed roller 4.
The embossing paper 3 is picked up along with the rotation of the paper feed roller 4 to start the feed paper, and is separated one by one with a separation claw.
The paper feed roller 4 rotates to send the embossing paper 3 to a document glass 10 via transport guides 8 and 9. Embossing paper 3 is passed through the transport guides 8 and 9 to be guided to the transport cylinder 7 and is then transported to the printing cylinder 7 and the clamping cylinder 11.
Then, the device is again in the waiting state where the backing of the recording paper 3 on the paper feed roller 4 is released, and the driving force from the transport roller 7 is disconnected.
The paper feed roller for manual paper feed 12 is for feeding the recording paper 3 over the manual feed tray 13 according to a recording instruction signal to thereby transport the recording paper 3 to the transport roller 7.
The recording paper 3 transported to the exposure glass 10 is passed under an in-line head 14. In this document, the transport speed of the recording paper and the droplet ejection time are adjusted based on a signal controlled by a circuit electrical (not shown) to form a predetermined image.
The inkjet engraving device and the inkjet engraving method of the present invention can be applied to various engravings by the inkjet engraving system, and can be particularly appropriately used for or as a jet engraving printer. ink, a facsimile, a photocopier, a printer-fax-copier device. <Ink-Etched Matter>
The ink-etched material for use in the present invention is any material etched by the ink-jet engraving device and / or the ink-jet etching method of the present invention.
The ink-engraved matter of the present invention contains a recording medium, and an image formed on the recording medium with the ink jet ink of the present invention.
Furthermore, the ink-engraved material contains a medium for recording a set of ink means and an image formed on the medium for recording with the ink jet ink of the set of ink means.
The recording media is appropriately selected depending on the intended purpose, without any restriction, and examples thereof include flat paper, glossy paper, special paper, fabric, films, OHP sheets, plain printing paper. These can be used independently or in combination.
The ink-engraved material has a high quality image without any dripping, and has excellent stability over time and, therefore, can be appropriately used in various uses such as documents to which various characters and / or images are engraved. EXAMPLES
The examples of the present invention will be explained below, but these examples are not to be construed as limiting the scope of the present invention in any way. (PRODUCTION EXAMPLE 1)
A 300 ml separable flask equipped with a stirrer, thermocouple and nitrogen inlet tube was charged with 19.828 g of N, N-dimethylacryl amide and 14.824 g of 1-butanol, and the resulting mixture was stirred while introducing the gas nitrogen in the flask. Subsequently, 0.338 g of sodium t-butoxide was added to the flask, and the resulting mixture was allowed to react at 35 ° C for 4 hours. At the end of the heating, 150 mg of phosphoric acid were added to the reaction solution, and the solution was then homogenized, followed by allowing to sand for 3 hours. The solution was then filtered to remove precipitates, and unreacted products were removed by an evaporator. The yield was 30.5 g (yield: 88%). The material obtained was subjected to 1H-NMR spectrum measurement, and peaks were observed at 0.95 ppm (3H), 1.3 ppm (4H) at 1.5 ppm (4H), 2.4 ppm (2H) , 2.9 ppm (6H), 3.4 ppm (2H) and 3.7 ppm (2H). It was found from these results that the material obtained was the amide compound represented by the following formula (1). <<> Amide Compound of Formula (1)>
[PREPARATION EXAMPLE 1) -Preparation of Water Soluble Polymeric Compound Solution A- α-male anhydride copolymer- 10.0 parts by weight olefin (T-YP112, manufactured by SEIKO PMC CORPORATION, olefin chain: C20-C24 ( R in the general formula (A) is a C18-22 alkyl group), acid value: 190 mgKOH / g, weight average molecular weight: 10,000) aqueous solution of 1N LiOH 17.34 parts by mass (1.2 times in one amount of α-olefin-maleic anhydride copolymer acid value represented by the general formula (A) ion exchange water 72.66 parts by weight
The above materials were heated and stirred by a stirrer to dissolve the α-olefin-maleic anhydride copolymer represented by the general formula (A), and the resulting solution was passed through a filter having an average pore diameter of 5 μm to remove a trace of insoluble matter, in order to prepare the aqueous solution of water-soluble polymeric compound A. (PREPARATION EXAMPLE 2) -Preparation of Surface Treated Black Pigment Dispersion Liquid-
To a 2.5N sodium sulfate solution (3,000 ml), 90 g of carbon black having a specific CTAB surface area of 150 m2 / g, and DBP oil absorption of 100 ml / 100 g were added, and the The resulting mixture was allowed to react for 10 hours with stirring at a temperature of 60oC, at the rate of 300 rpm, to proceed in this way to an oxidation treatment. The resulting reaction solution was subjected to filtration to separate the carbon black, and the separated carbon black was then neutralized with a sodium hydroxide solution, followed by subjected to ultrafiltration.
The obtained carbon black was washed with water and then dried. Then, the carbon black was dispersed in pure water so that the solids content of it should be 30% by mass, and the dispersion was then stirred sufficiently to thereby obtain a black pigment dispersion liquid. The average particle diameter (D50) of the pigment dispersion elements in the black pigment dispersion liquid was measured and the result was 103 nm. Note that for measuring the average particle diameter (D50), a particle size distribution measuring device (NANOTRACK UPA-EX150), manufactured by Nikkiso Co., Ltd.) was used. (PREPARATION EXAMPLE 3) -Preparation of Polymeric Particle Dispersion Liquid Containing Magenta Pigment - << Preparation of Polymeric Solution A>
A 1L flask equipped with a mechanical stirrer, a thermometer, a nitrogen inlet tube, a reflux tube and a drip funnel, which was sufficiently purged with nitrogen gas, was charged with 11.2 g of styrene, 2 , 8 g of acrylic acid, 12.0 g of lauryl methacrylate, 4.0 g of polyethylene glycol methacrylate, 4.0 g of styrene macrometer, and 0.4 g of mercaptoethanol, and the resulting mixture was mixed and heated at 65oC.
Then, the mixed solution of styrene (100.8 g), acrylic acid (25.2 g), lauryl methacrylate (108.0 g), polyethylene glycol methacrylate (36.0 g), hydroxyethyl methacrylate (60.0 g), styrene macromer (36.0 g), mercaptoethanol (3.6 g), methyl valeronitrile azobis (2.4 g) and methyl ethyl ketone (18 g) was added dropwise into the flask over 2.5 hours. Then, a mixed solution of azobis methylvaleronitrile (0.8 g) and methyl ethyl ketone (18 g) was added dropwise into the flask over 0.5 hours. After aging the mixture at 65 ° C for 1 hour, 0.8 g of azobis netylvaleronitrile was added to it, and the resulting mixture was further aged for 1 hour. At the end of the reaction, methyl ethyl ketone (364 g) was added to the flask to thereby obtain 800 g of polymeric solution A having a concentration of 50% by mass. <Preparation of dispersion liquid of polymeric particles containing pigment>
After sufficiently stirring a mixture of polymeric solution A (28 g), Pigment Red CI 122 (42 g), an aqueous solution of potassium hydroxide (13.6 g), methyl ethyl ketone (20 g), and exchange water ionic (13.6 g), the resulting mixture was kneaded by a roller mill. To the obtained paste, 200 g of pure water was added, the resulting mixture was stirred sufficiently, and methyl ethyl ketone and water were removed from the resulting dispersion liquid using an evaporator, followed by pressure filtration with a polyvinylidene fluoride membrane filter. having an average pore diameter of 5.0 μm to remove coarse particles from the dispersion liquid, in order to obtain a dispersion liquid of polymeric particles containing magenta pigment containing 15% by mass of the pigment, and having a solids content of 20% by mass. The average particle diameter (D5o) of the polymeric particles in the dispersion liquid of polymeric particles containing magenta pigment was measured and the result was 127 nm. Note that, for the measurement of the average particle diameter (D50), a particle size distribution measuring device (NANOTRACK UPA-EX150, manufactured by Nikkiso Co., Ltd.) was used. (PREPARATION EXAMPLE 4) -Preparation of dispersion liquid of polymeric particles containing cyan pigment-
A polymeric dispersion liquid containing cyan pigment preparation example 4 was prepared in the same way as in preparation example 3, with the proviso that the pigment was changed from Pigment Red CI 122 to a phthalocyanine pigment (Pigment Blue CI 15: 3).
The average particle diameter (D50) of the polymeric particles in the polymeric dispersion liquid containing cyan pigment obtained was measured by a particle size distribution measuring device (NANOTRACK UPA-EX150, manufactured by Nikkiso Co., Ltd.) and the result was 93 nm. (PREPARATION EXAMPLE 5) -Preparation of Polymeric Particles Dispersion Liquid Containing Yellow Pigment-
A polymeric dispersion liquid containing yellow pigment from preparation example 5 was prepared in the same manner as in preparation example 3, with the proviso that the pigment was exchanged from Pigment Red CI 122 to a yellow pigment monoazo (Pigment Yellow CI 74).
The average particle diameter (D50) of the polymeric particles in the polymeric dispersion liquid containing yellow pigment was measured by a particle size distribution measuring device (NANOTRACK UPA-EX150, manufactured by Nikkiso Co., Ltd.), and the result was 76 nm. (PREPARATION EXAMPLE 6) -Preparation of Dispersion Liquid of Polymeric Particles Containing Smoke Black Pigment-
A polymeric particle dispersion liquid containing carbon black pigment from preparation example 6 was prepared in the same way as in preparation example 3, with the proviso that the pigment was changed from Pigment Red CI 122 to carbon black) FW100, Degussa AG).
The average particle diameter (D50) of the polymeric particles in the polymeric particle dispersion liquid containing carbon black pigment was measured by a particle size distribution measuring device (NANOTRACK UPA-EX150, manufactured by Nikkiso Co., Ltd. ), and the result was 104 nm. (PREPARATION EXAMPLE 7) - Preparation of Polymeric Particulate Dispersion Liquid Containing Yellow Pigment Surfactant Pigment - Yellow Pigment Monoazo 30.0 parts by mass (Yellow Pigment CI 74, manufactured by Dainichiseika Color & Chemicals Mfg. Co. Ltd. ) Polyoxyethylene phenyl ether 10.0 parts by weight styrene, NOIGEN EA-177 manufactured by Dai-ichi Kogyo Seyaku Co., Ltd., HLB value: 15.7) Ion exchange water 60.0 parts by weight
First, the surfactant mentioned above was dissolved in ion exchange water, and to this the pigment mentioned above was mixed to moisten the pigment sufficiently. The resulting mixture was dispersed at 2,000 rpm for 2 hours by a moisture disperser (DYNO MILL KDL A, by Glen Mills) filled with zirconia beads having 0.5 mm diameters, in order to obtain a primary pigment dispersion liquid .
To the primary pigment dispersion liquid, 4.26 parts by weight of a water-soluble polyurethane resin (TAKELAC W-5661, manufactured by Mitsu Chemicals, Inc., active ingredient: 35.2 parts by weight, acid value: 40 mgKOH / g, molecular weight: 18,000) were added as an aqueous solution of water-soluble polymeric compound, and the resulting mixture was sufficiently stirred to thereby obtain a yellow pigment surfactant dispersion liquid. The average particle diameter (D5o) of the pigment dispersion elements in the polymer dispersion liquid containing yellow pigment was measured and the result was 62 nm. Note that, for the measurement of the average particle diameter (D50), a particle size distribution measuring device (NANOTRACK UPA-EX150, manufactured by Nikkiso Co., Ltd.) was used. (PREPARATION EXAMPLE 8) -Preparation of Magenta Pigment surfactant dispersion liquid-Quinacridone pigment 30.0 parts by mass (Pigment Red CI 122, manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd. Polyoxyethylene ether- β- 10.0 parts by weight naphthyl (non-ionic surfactant, RT-100 manufactured by Takemoto Oil & Fat Co., Ltd., HLB value: 18.5) Ion exchange water 60.0 parts by mass First, the surfactant mentioned above was dissolved in ion exchange water, and to this the pigment mentioned above was mixed to wet the pigment sufficiently. The resulting mixture was dispersed at 2,000 rpm for 2 hours by a moisture disperser (DYNO MILL KDL A, by Glen Mills) with zirconia beads having diameters of 0.5 mm, in order to obtain a primary pigment dispersion liquid.
To the primary pigment dispersion liquid, 7.14 parts by mass of water-soluble styrene (meth) acryl copolymer (JC-05, manufactured by SEIKO PMC CORPORATION, active ingredient: 21% by mass, acid value: 170 mgKOH / g, weight average molecular weight: 16,000) were added, and the resulting mixture was stirred enough to thereby obtain a magenta pigment surfactant dispersion liquid. The mean particle diameter (D50) of the elements dispersed in the pigment in the magenta pigment surfactant dispersion liquid was measured, and the result was 83 nm. Note that, for the measurement of the average particle diameter (D50), a particle size distribution measuring device (NANOTRACK UPA-EX150, manufactured by Nikkiso Co., Ltd.) was used. (PREPARATION EXAMPLE 9) -Preparation of Cyan Pigment Surfactant Dispersion Liquid A- Phthalocyanine pigment 30.0 parts by mass (Pigment Blue CI 15: 3, manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd. Ether polyoxyethylene phenyl 10.0 parts by weight styrene (non-ionic surfactant, NOIGEN EA-177 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. HLB value: 15.7) Ion exchange water 60.0 parts by mass First, the surfactant mentioned above was dissolved in ion exchange water and to this the pigment mentioned above was mixed to moisten the pigment sufficiently The resulting mixture was dispersed at 2,000 rpm for 2 hours by a moisture disperser (DYNO MILL KDL A, from Glen Mills) filled with zirconia beads having a diameter of 0.5 mm, in order to obtain a primary pigment dispersion liquid.
To the primary pigment dispersion liquid, 7.51 parts by weight of aqueous solution of water-soluble polymeric compound A prepared in preparation example 1 and 2.51 parts by weight of a water-soluble polymeric resin (NICHIGO POLYESTER W-0030 , manufactured by Nippon Synthetic Chemical Industry Co., Ltd., active ingredient: 29.9% by weight, acid value: 100 mgKOH / g, weight average molecular weight: 7,000) were added, and the resulting mixture was stirred sufficiently to in this way obtaining a cyan pigment surfactant dispersion liquid A. The average particle diameter (D50) of the elements dispersed in the pigment in the obtained cyan pigment surfactant dispersion liquid obtained was measured and the result was 78 nm. Note that, for the measurement of the average particle diameter (D50), a particle size distribution measuring device (NANOTRACK UPA-EX150, manufactured by Nikkiso Co., Ltd.) was used. (EXAMPLE 1) -Preparation of Inkjet Ink-
An inkjet ink from example 1 was prepared using the respective materials shown in table 2. Specifically, an organic solvent (wetting agent), that is, 10,000 parts (parts by mass, “parts” represents the same hereinafter) glycerin and 10,000 parts of 1,3-butanediol, a penetrating agent, ie 2.00 parts of 2-ethyl-1,3-hexanediol, a surfactant, ie 2.50 parts of Zonyl FS-300 (see notes below for details), and an antifungal agent, i.e., 0.005 parts of Proxel GXL (see notes below for details) were mixed, and the resulting mixture was stirred for 1 hour to mix the mixture homogeneously. To this mixture, a predetermined amount of pure water containing 10,000 parts of the amide compound represented by formula (1) and 10.00 parts of the compound represented by the following formula (8) was added, and the resulting mixture was stirred for 1 hour. To the resulting mixture, a pigment dispersion liquid (that is, the black pigment containing polymeric particles dispersion liquid of the preparation example (6), a defoaming agent (ie, a silicone defoaming agent), a pH regulator (ie 0.3 parts 2-amino-2-ethyl-1,3-propanediol) and a balance of pure water for the resulting paint to be 100 parts were added, and the mixture stirred for 1 hour. The resultant was subjected to pressure filtration with a polyvinylidene fluoride membrane filter having an average pore diameter of 0.8 μm to remove coarse particles or dust, in order to prepare an ink jet ink of example 1. << Compound of Formula (8) >>
(EXAMPLE 2)
An inkjet ink from example 2 was prepared in the same way as in example 1, with the proviso that, as shown in table 2, in addition to the amide compound represented by formula (1) (10.00 parts) and the compound represented by formula (8) (10.00 parts), 5.00 parts of the amide compound represented by structural formula (V) were added (note that the balance of pure water required for the paint to be 100 parts was different from that of example 1 by the added amount of the amide compound represented by the structural formula (V), which can also be the same in the following examples).
Structural Formula (V) (EXAMPLE 3)
An inkjet ink from example 3 was prepared in the same way as in example 1, with the proviso that, as shown in table 2, 10.00 parts of the amide compound represented by the general formula (1) and 10.00 parts of the compound represented by the structural formula (8) were replaced with 10.00 parts of the amide compound represented by the general formula (1), 10.00 parts of the compound represented by the structural formula (4), and 10.00 parts of the amide compound represented by the structural formula (V); and 10.00 parts of glycerin and 10.00 parts of 1,3-butanediol and 2.00 parts of 2-ethyl-1,3-hexanediol were replaced with 15.00 parts of glycerin and 2.00 parts of 2- ethyl-1,3-hexanediol. << Compound of Formula (4) >>
(EXAMPLE 4)
An inkjet ink from example 4 was prepared in the same way as in example 1, with the proviso that, as shown in table 2, 10.00 parts of the amide compound represented by formula (1) and 10.00 parts of compound represented by formula (8) were replaced with 10.00 parts of the amide compound represented by formula (1), 10.00 parts of the compound represented by formula (18), and 10.00 parts of the amide compound represented by structural formula ( V); and 10.00 parts of glycerin and 10.00 parts of 1,3-butanediol, and 2.00 parts of 2-ethyl-1,3-hexanediol were respectively replaced with 15.00 parts of glycerin and 2.00 parts of 2-ethyl-1,3-hexanediol.
<< Compound of Formula (18) >>
(EXAMPLE 5)
An inkjet ink of example 5 was prepared in the same manner as in example 1, with the proviso that, as shown in table 3, 50.00 parts of the black pigment dispersion liquid of preparation example 6 were replaced with 33.33 parts of the cyan pigment dispersion liquid of preparation example4; the amount of 1,3-butanediol was changed from 10.00 parts to 15.00 parts; the penetrating agent (2.00 parts of 2-ethyl-1,3-hexanediol) was not added; and the amount of Zonil FS-300 was changed from 2.50 parts to 1.25 parts. (EXAMPLE 6)
An inkjet ink from example 6 was prepared in the same way as in example 5, with the proviso that, as shown in table 3, 2.00 parts of 2,2,4-trimethyl-1,3-pentanediol were added as the penetrating agent, instead of adding (using) any 2-ethyl-1,3-hexanediol in example 5. (EXAMPLE 7)
An inkjet ink from example 7 was prepared in the same way as in example 5, with the proviso that, as shown in table 3, 10.00 parts of the amide compound represented by formula (1) and 10.00 parts of compound represented by formula (4) were replaced with 10.00 parts of the amide compound represented by formula (1), 10.00 parts of the compound represented by formula (8), and 5.00 parts of the amide compound represented by structural formula ( V); and, as the penetrating agent, 2.00 parts of 2-ethyl-1,3-hexanediol were added while no penetrating agent was added in example 5. (EXAMPLE 8)
An inkjet ink from example 8 was prepared in the same way as in example 7, with the proviso that, as shown in table 3, 15.00 parts of 1,3-butanediol were replaced with 15.00 parts of 3 -methyl- 1,3-butanediol. (EXAMPLE 9)
An ink jet ink of example 9 was prepared in the same way as in example 7, with the proviso that, as shown in table 4, 33.33 parts of the cyan pigment dispersion liquid of preparation example 4 were replaced with 33.33 parts of the yellow pigment dispersion liquid of preparation example 5; 10.00 parts of the amide compound represented by formula (1), 10.00 parts of the compound represented by formula (8), and 5.00 parts of the amide compound represented by structural formula (V) were replaced with 20.00 parts of amide compound represented by formula (1), 10.00 parts of the compound represented by formula (18), and 5.00 parts of the amide compound represented by structural formula (V) and 10.00 parts of glycerin, 15.00 parts of 1,3-butanediol, and 2.00 parts of 2-ethyl-1,3-hexanediol were replaced with 10.00 parts of glycerin, 15.00 parts of 1.3-butanediol and 2.00 parts of 2.2 , 4-trimethyl-1,3-pentanediol. (EXAMPLE 10)
An inkjet ink from example 10 was prepared in the same way as in example 9, with the proviso that, as shown in table 4, 20, 00 parts of the amide compound represented by formula (1), 10.00 parts of compound represented by formula (18), and 5.00 parts of the amide compound represented by structural formula (V) were replaced with 30.00 parts of the amide compound represented by formula (1), 5.00 parts of the compound represented by formula (V) 18) and 5.00 parts of the amide compound represented by the structural formula (V); and 2.00 parts of 2,2,4-trimethyl-1,3-pentanediol were replaced with 1.00 parts of 2,2,4-trimethyl-1,3-pentanediol and 1.00 part of 2-ethyl- 1,3-hexanediol. (EXAMPLE 11)
An inkjet ink of example 11 was prepared in the same way as in example 9, with the proviso that, as shown in table 4, 33.33 parts of the polymeric dispersion liquid containing yellow pigment of preparation example 5 were replaced with 53.33 parts of the polymer particle dispersion liquid containing magenta pigment from preparation example 3; 20.00 parts of the amide compound represented by formula (1), 10.00 parts of the compound represented by formula (18) and 5.00 parts of the amide compound represented by structural formula (V) were replaced with 10.00 parts of the compound amide represented by formula (1), 7.50 parts of the compound represented by formula (8), and 6.00 parts of the amide compound represented by structural formula (V); 10.00 parts of glycerin, 15.00 parts of 1,3-butanediol, and 2.00 parts of 2,2,4-trimethyl-1,3-pentanediol were replaced with 10.00 parts of glycerin and 2.00 parts of 2-ethyl-1,3-hexanediol; and the surfactant was changed from ZONYL FS-300 to 1.00 part of KF-643 (see notes below for details). (EXAMPLE 12)
An inkjet ink of example 12 was prepared in the same manner as in example 11, with the proviso that, as shown in table 4, 53.33 parts of the polymer particle dispersion liquid containing magenta pigment from preparation example 3 were replaced with 30.00 parts of the black pigment dispersion liquid from preparation example 2; 10.00 parts of the amide compound represented by formula (1), 7.50 parts of the compound represented by formula (8) and 6.00 parts of the amide compound represented by structural formula (V) were replaced with 12.50 parts of the compound amide represented by formula (1), 10.00 parts of the compound represented by formula (18) and 7.50 parts of the amide compound represented by structural formula (V); and 10.00 parts of glycerin, 10.00 parts of 2-ethyl-1,3-hexanediol and the penetrating agent (ie 2.00 parts of 2-ethyl-1,3-hexanediol) were replaced with 10 .00 parts of glycerin, 15.00 parts of 2-methyl-1,3-butanediol and, as the penetrating agent, 2.00 parts of 2-ethyl-1,3-hexanediol, respectively. (EXAMPLE 13)
An inkjet ink of example 13 was prepared in the same manner as in example 9, with the proviso that, as shown in table 5, 33.33 parts of the polymeric dispersion liquid containing yellow pigment of preparation example 5 they were replaced with 13.90 parts of the dispersion liquid of polymeric particles containing yellow pigment surfactant pigment of preparation example 7; 5.38 parts of the acrylic silicone emulsion (see notes below for details) were added as a water dispersible resin; 20.00 parts of the amide compound represented by formula (1), 10.00 parts of the compound represented by formula (18) and 5.00 parts of the amide compound represented by structural formula (V) were replaced with 15.00 parts of the compound amide represented by formula (1), 10.00 parts of the compound represented by formula (8) and 10.00 parts of the amide compound represented by structural formula (V); 10.00 parts of glycerin, 15.00 parts of 1,3-butanediol and 2.00 parts of 2,2,4-trimethyl-1,3-pentanediol were replaced with 10.00 parts of 1,3-butanediol and 20.00 parts of 3-methyl-1,5-pentanediol and 2.00 parts of 2-ethyl-1,3-hexanediol; and the surfactant was changed from 1.25 parts of ZONYL FS-300 to 1.00 parts of KF-643 (see notes below for details). (EXAMPLE 14)
An inkjet ink of example 14 was prepared in the same manner as in example 13, with the proviso that, as shown in table 5, 13.90 parts of the polymeric dispersion liquid containing yellow pigment from preparation example 7 were replaced with 28.57 parts of the magenta pigment surfactant dispersion liquid from preparation example 8; 15.00 parts of the amide compound represented by formula (1), 10.00 parts of the compound represented by formula (8) and 10.00 parts of the amide compound represented by structural formula (V) were replaced with 7.50 parts of the compound amide represented by formula (1), 10.00 parts of the compound represented by formula (18) and 5.00 parts of the amide compound represented by structural formula (V); and 10.00 parts of glycerin, 20.00 parts of 3-methyl-1,5-pentanediol, and 2.00 parts of 2-ethyl-1,3-hexanediol were replaced with 10.00 parts of glycerin, 14, 00 parts of 1,3-butanediol, and 2.00 parts of 2-ethyl-1,3-hexanediol. (EXAMPLE 15)
An inkjet ink of example 15 was prepared in the same manner as in example 13, with the proviso that, as shown in table 5, 13.90 parts of the polymeric dispersion liquid containing yellow pigment of preparation example 7 were replaced with 14.67 parts of the polymeric dispersion liquid containing cyan pigment from preparation example 9; 10.00 parts of the amide compound represented by formula (1), 10.00 parts of the compound represented by formula (8), and 10.00 parts of the amide compound represented by structural formula (V) were replaced with 7.50 parts of amide compound represented by formula (1), 10.00 parts of the compound represented by formula (18), and 5.00 parts of the amide compound represented by structural formula (V); and 10.00 parts of glycerin, 20.00 parts of 3-methyl-1,5-pentanediol and 2.00 parts of 2-ethyl-1,3-hexanediol were replaced with 10.00 parts of glycerin, 17.00 1,3-butanediol arts and 2.00 parts of 2-ethyl-1,3-hexanediol. (EXAMPLE 16)
An inkjet ink of example 16 was prepared in the same manner as in example 13, with the proviso that, as shown in table 5, 13.90 parts of the polymeric dispersion liquid containing yellow pigment of preparation example 7 were replaced with 50.00 parts of the polymeric dispersion liquid containing black pigment from preparation example 6; 5.38 parts of the acrylic silicone resin emulsion contained in the paint of example 13 have not been added; 15.00 parts of the amide compound represented by formula (1), 10.00 parts of the compound represented by formula (8) and 10.00 parts of the amide compound represented by structural formula (V) were replaced with 3.00 parts of the compound amide represented by formula (1), 5.00 parts of the compound represented by formula (8) and 5.00 parts of the amide compound represented by structural formula (V); 10.00 parts of glycerin, 20.00 parts of 3-methyl-1,5-pentanediol and 2.00 parts of 2-ethyl-1,3-hexanediol were replaced with 15.00 parts of glycerin, 10.00 parts 2-methyl-1,3-butanediol and 2.00 parts of 2-ethyl-1,3-hexanediol; and 2.50 parts of ZONYL FS-300 (the surfactant) were added. (EXAMPLE 17)
An inkjet ink from example 17 was prepared in the same manner as in example 13, with the proviso that, as shown in table 6, 13.90 parts of the polymeric dispersion liquid containing yellow pigment from preparation example 7 were replaced with 14.67 parts of the cyan pigment surfactant dispersion solution from preparation example 9; 5.38 parts of the acrylic silicone resin emulsion were replaced with 4.44 parts of polyurethane (see notes below for details); 15.00 parts of the amide compound represented by formula (1), 10.00 parts of the compound represented by formula (8), and 10.00 parts of the amide compound represented by structural formula (V) were replaced with 10.00 parts of amide compound represented by formula (1), 3.00 parts of the compound represented by formula (8), and 50.00 parts of the amide compound represented by structural formula (V); 10.00 parts of glycerin, 20.00 parts of 3-methyl-1,5-pentanediol and 2.00 parts of 2-ethyl-1,3-hexanediol were replaced with 10.00 parts of glycerin and 2.00 parts 2,2,4-trimethyl-1,3-pentanediol; and 0.50 part of SOFTAL FP-7025 was added. (EXAMPLE 18)
An ink jet ink of example 18 was prepared in the same manner as in example 12, with the proviso that, as shown in table 6, 25, 00 parts of the polymeric dispersion liquid containing black pigment treated on the surface of the example preparation 2, 5.38 parts of the acrylic silicone resin emulsion, 11.50 parts of the amide compound represented by formula (1), 10.00 parts of the compound represented by formula (8), 8.50 parts of the amide compound represented by the structural formula (V), 8.00 parts of glycerin, 2.00 parts of 2-ethyl-1,3-hexanediol, 1.25 parts of ZONYL FS-300, 0.05 part of Proxel GXL, 0, 10 part of the silicone defoaming agent KM-72F and 0.9 part of 2-amino-2-ethyl-1,3-propanediol (the pH regulator) were used. (EXAMPLE 19)
An ink jet ink of example 19 was prepared in the same way as in example 18, with the proviso that, as shown in table 6, 11.50 parts of the amide compound represented by formula (1), 10.00 parts of compound represented by formula (8), 8.50 parts of the amide compound represented by structural formula (V), 8.00 parts of glycerin and 2.00 parts of 2-ethyl-1,3-hexanediol were replaced with 10.00 parts of the amide compound represented by formula (1), 10.00 parts of the compound represented by formula (8), 11.50 parts of the amide compound represented by structural formula (V), 12.00 parts of glycerin, and 1.00 parts of 2-ethyl-1,3-hexanediol, respectively. (EXAMPLE 20)
An inkjet ink of example 20 was prepared in the same way as in example 18, with the proviso that, as shown in table 6, 25, 00 parts of the black pigment dispersion solution treated on the surface of preparation example 2 were replaced with 18.67 parts of the black pigment dispersion liquid treated on the surface of preparation example 2 and 16.00 parts of the polymer dispersion liquid containing black pigment from preparation example 6; and instead of the respective materials used in example 18, 2.69 parts of the acrylic silicone resin emulsion 8.50 parts of the amide compound represented by formula (1), 10.00 parts of the compound represented by formula (8), 11 , 50 parts of the amide compound represented by the structural formula (V), 10.00 parts of glycerin and 2.00 parts of 2-ethyl-1,3-hexanediol were used. (EXAMPLE 21)
An inkjet ink of example 21 was prepared in the same manner as in example 5, with the proviso that, as shown in table 7, 33.33 parts of the cyan pigment containing polymeric particle dispersion liquid of preparation example 4 they were replaced with 3.00 parts of the cyan pigment containing polymeric particle dispersion liquid from preparation example 4 and 14.89 parts of the cyan pigment surfactant dispersion liquid from preparation example 9; and instead of the respective materials used in example 5, 11.50 parts of the amide compound represented by formula (1), 12.50 parts of the compound represented by formula (8), 10.00 parts of the amide compound represented by structural formula ( V), 10.00 parts of glycerin, 1.00 parts of 2-ethyl-1.30hexanediol, 1.25 parts of ZONYL FS-300, 0.05 part of Proxel OXL, 0.10 part of the silicone defoaming agent KM-72F and 0.03 part of 2-amino-2-ethyl-11,3-propanediol (the pH regulator) were used. (EXAMPLE 22)
An inkjet ink from example 22 was prepared in the same way as in example 11, with the proviso that, as shown in table 7, 53.33 parts of the polymer particle dispersion liquid containing magenta pigment from preparation example 3 they were replaced with 5.00 parts of the polymeric particles dispersion liquid containing magenta pigment from preparation example 3 and 24.11 parts of the magenta surfactant dispersion liquid from preparation example 8; and instead of the respective materials used in example 11, 8.50 parts of the amide compound represented by formula (1), 10.00 parts of the compound represented by formula (8), 10.00 parts of the amide compound represented by the structural formula ( V), 10.00 parts of glycerin, 1.00 parts of 2-ethyl-1,3-hexanediol, 1.25 parts of ZONYL FS-300, 0.05 parts of Proxel GXL, 0.10 parts of defoaming agent of KM-72F silicone and 0.03 parts of 2-amino-ethyl-1,3-propanediol (the pH regulator). (COMPARATIVE EXAMPLE 1)
An inkjet ink from comparative example 1 was prepared in the same way as in example 1, with the proviso that, as shown in table 7, 10.00 parts of the amide compound represented by formula (1) and 10.00 parts of the compound represented by formula (8) were not used (not added); and 10.00 parts of glycerin, 10.00 parts of 1,3-butanediol and 2.00 parts of 2-ethyl-1,3-hexanediol were replaced with 17.50 parts of glycerin, 17.50 parts of 1, 3-butanediol and 2.00 parts of 2-ethyl-1,3-hexanediol. (COMPARATIVE EXAMPLE 2)
An inkjet ink from comparative example 2 was prepared in the same manner as in example 12, with the proviso that, as shown in table 7, 30.00 parts of the black pigment dispersion liquid treated on the surface of the preparation example 2 were replaced with 26.67 parts of the polymeric dispersion liquid containing black pigment treated on the surface of Preparation Example 2; 12.25 parts of the amide compound represented by formula (1), 10.00 parts of the compound represented by formula (18) and 7.50 parts of the amide compound represented by structural formula (V) were represented by structural formula (V); and 10.00 parts of glycerin and 2.00 parts of 2-ethyl-1,3-hexanediol were replaced with 20.00 parts of glycerin, 7.50 parts of 2-methyl-1,3-butanediol, 7.50 parts of 1,3-butanediol and 2.00 parts of 2-ethyl-1,3-hexanediol. (COMPARATIVE EXAMPLE 3)
An inkjet ink from comparative example 3 was prepared in the same manner as in example 12, with the proviso that, as shown in table 8, 12.25 parts of the amide compound represented by formula (1), 10.00 parts of the compound represented by formula (8) and 7.50 parts of the amide compound represented by structural formula (V) were not used; and 10.00 parts of glycerin and 2.00 parts of 2-ethyl-1,3-hexanediol were replaced with 30.00 parts of glycerin, 7.50 parts of 2-methyl-1,3-butanediol, 15.50 parts of 1,3-butanediol and 1.00 part of 2-ethyl-1,3-hexanediol. (COMPARATIVE EXAMPLE 4)
An inkjet ink from comparative example 4 was prepared in the same way as in example 1, with the proviso that, as shown in table 8, 50.00 parts of the polymeric dispersion liquid containing black pigment from the preparation example 6 were replaced with 53.33 parts of the polymer dispersion liquid containing black pigment from preparation example 6; 10.00 parts of the amide compound represented by formula (1) and 10.00 parts of the compound represented by formula (8) were not used (not added); 10.00 parts of glycerin, 10.00 parts of 1,3-butanediol and 2.00 parts of 2-ethyl-1,3-hexanediol were replaced with 27.50 parts of 2-methyl-1,3-butanediol and 5.00 parts of propylene glycol; 2.50 parts of ZONYL FS-300 were replaced with 1.00 parts of KF-643. (COMPARATIVE EXAMPLE 5)
An inkjet ink from comparative example 6 was prepared in the same way as in comparative example 1, with the proviso that, as shown in table 8, 10.00 parts of the amide compound represented by formula (1), which were not added in comparative example 1, 17.50 parts of glycerin, 17.50 parts of 1,3-butanediol and 2.00 parts of 2-ethyl-1,3-hexanediol were added with 20.00 parts of glycerin, 17.50 parts of 1,3-butanediol and 2.00 parts of 2-ethyl-1,3-hexanediol. (COMPARATIVE EXAMPLE 6)
An inkjet ink from comparative example 6 was prepared in the same way as in comparative example 1, with the proviso that, as shown in table 8, 10.00 parts of the compound represented by formula (4), which were not added in comparative example 1, they were also added; and 17.50 parts of glycerin, 17.00 parts of 1,3-butanediol and 2.00 parts of 2-ethyl-1,3-hexanediol were replaced with 20.00 parts of glycerin, 17.50 parts of 1, 3-butanediol and 2.00 parts of 2-ethyl-1,3-hexanediol. (COMPARATIVE EXAMPLE 7)
An inkjet ink from comparative example 7 was prepared in the same way as in comparative example 1, with the proviso that, as shown in table 9, 10.00 parts of the amide compound represented by formula (8), which were not added in comparative example 1, have been added; and 17.50 parts of glycerin, 17.00 parts of 1,3-butanediol and 2.00 parts of 2-ethyl-1,8-hexanediol were replaced with 20.00 parts of glycerin and 17.50 parts of 1, 3-butanediol. (COMPARATIVE EXAMPLE 8)
An inkjet ink from comparative example 8 was prepared in the same way as in comparative example 1, with the proviso that, as shown in table 9, 10.00 parts of the compound represented by formula (18), which were not added in comparative example 1, they were also added; and 17.50 parts of glycerin, 17.50 parts of 1,3-butanediol and 2.00 parts of 2-ethyl-1,3-hexanediol were replaced with 20.00 parts of glycerin, 17.50 parts of 1, 3-butanediol and 2.00 parts of 2-ethyl-1,3-hexanediol. (COMPARATIVE EXAMPLE 9)
An inkjet ink from comparative example 9 was prepared in the same way as in comparative example 1, 5 with the proviso that, as shown in table 9, 17.50 parts of glycerin, 17.50 parts of glycerin, 17, 50 parts of 1,3-butanediol and 2.00 parts of 2-ethyl-1,3-hexanediol were replaced with 20.00 parts of glycerin, 22.00 parts of 3-methyl-1,3-butanediol and 2, 00 10 parts of 2-ethyl-1,3-hexanediol. TABLE 2


TABLE 3


TABLE 4


TABLE 5


TABLE 6


TABLE 7


TABLE 8


TABLE 9


The abbreviations in tables 2 to 9 above represent the following materials. Note 1: “acrylic silicone resin emulsion” is POLYSOL ROY6312 manufactured by Shows Highpolymer Co., Ltd., which has a solids content of 37.2% by weight, the average particle diameter of 171 nm, and the temperature minimum film formation (MFT) of 20oC. Note 2: “Polyurethane emulsion” is HYDRAN APPROXIMATELY-101H manufactured by DIC Corporation having a solids content of 45% by mass, the average particle diameter of 160 nm, and the minimum film formation temperature (MFT) of 20oC . Note 3: “KF-643” is a polyether modified silicone compound manufactured by Shin-Etsu Chemical Co., Ltd., having an active ingredient of 100% by weight. Note 4: “ZONYL FS-300” is polyoxyethylene perfluoroalkyl ether manufactured by EI DuPont de Nemours and Company, having an active ingredient of 40% by weight. Note 5: “SOFTANOL EP-7025 is polyoxyalkylene alkyl ether manufactured by Nippon Shokubai Co., Ltd., having an active ingredient of 100% by weight. Note 6: “Proxel GXL” is an antifungal agent containing 1,2-benzisothiazolin-3-one as a main component, active ingredient of 20% by weight and containing dipropylene glycol. Note 7: “KM-72F” is a self-emulsifying silicone defoaming agent manufactured by Shin-Etsu Chemical Co., 5 Ltd., having an active ingredient of 100% by weight. Note: “Amide compound (1)” is the amide compound represented by the following formula (1).
Formula (1) 10 Note: "Compound (4)" is the compound represented by the following formula (4).
Formula (4) Note: "Compound (8)" is the compound represented by the following formula (8).
Formula (8) Note: "Compound (18)" is the compound represented by the following formula (18).
Formula (18) Note: “Amide compound (V)” is the amide compound represented by the following structural formula (V).
Structural Formula (V)
In addition, in table 1, “Equil.” It is used as an abbreviation for “Equilibrium” and “Penetrating Agent” is the same as the penetrating agent described in this report. The equilibrium moisture contents of the organic solvents for use in the examples and comparative examples were determined as follows. The temperature and humidity inside a desiccator were controlled at a temperature of 23oC ± 1oC and the relative humidity of 80% to ± 3% using a saturated aqueous solution of potassium chloride / sodium chloride. In this dissector, a plate in which organic solvent was weighed and placed in 1 g was stored, and the equilibrium moisture content was measured by the following equation.
Equilibrium moisture content (%) = Amount of water absorbed in the organic solvent / (Amount of organic solvent + Amount of water absorbed in the organic solvent) x 100
In the mode described above, the equilibrium moisture content of polyhydric alcohol, that is, glycerin (boiling point: 290oC, EMC: 49% by mass) and 1,3-butanediol (boiling point: 203oC-204oC, EMC: 35% by mass), was 30% by mass or more at 23oC, and the unit was 80% RH.
When using the following recording sheets (1) to (5) and the inkjet ink of example 8, the image quality assessment was carried out as follows. - Recording Sheet (1) -
Commercially available sheet (product name: Aurora Coat, manufactured by Nippon Paper Industries Co., Ltd., base weight 104.7 g / m2). - Engraving Sheet (2) - POD Gloss Coat (manufactured by Oji Paper Co., Ltd., base weight: 100 g / m2) - Engraving Sheet (3) - Space DX (engraving paper) (manufactured by Nippon Paper Industries Co., Ltd., base weight: 56.5 g / m2) - Embossing Sheet (4) - Matte inkjet coated paper (product name: Super Fine Paper, manufactured by SEIKO EPSON CORPORATION). - Recording Sheet (5) - Clear polyester film (product name: Lumirror U10, manufactured by TORAY Industries Inc., thickness: 100 μm)
An amount of pure water transferred to each of the engraving sheets (1) to (5) was measured as follows. The results are described in table 10. <Measurement of the Quantity of Pure Water Transfer by the Dynamic Scanning Absorbometer>
A pure water absorption curve was measured using a dynamic scanning absorptometer (KS350D), manufactured by Kyowaseiko Corporation), with respect to each of the recording sheets (1) to (5). The absorption curve was obtained by plotting a slanted straight line from the amount of transfer (ml / m2) and the square root of the contact duration. The amount of transfer after a certain period was determined by 5 interpolation. TABLE 10
<Sheet Quality Assessment>
An image quality test was performed by an inkjet recording device (IPSiO GXe-5500, 10 manufactured by Ricoh Company Limited) using the inkjet ink of example 3 on the recording sheets (1) to ( 5). The results are shown in table 11. <Flowing>
The degree of runoff (irregularity in image density) in the solid image formation portion of the image obtained was visually observed and evaluated. For the evaluation criteria, staggered samples (gradation from weak / 1.0 to good / 5.0) was used. <Splash marks>
The offset blur caused from the black solid image formation portion obtained for the black background portions by a splash was visibly observed and evaluated. The evaluation criteria and classifications are as follows: Classification 1: Clearly recognized Classification 2: Poorly recognized Classification 3: Not recognized <Bright> The degree 60 brightness of the obtained black solid image portion was measured by a shine (4501, manufactured by BYK Gardener). <Drying Properties>
A map was printed in the same way as in the image density assessment test, which can be explained later, and a filter paper was pressed against the “■” portion on the printed black solid image surface. The results were evaluated whether or not the ink was transferred to the filter paper. [Evaluation Criteria] A: No ink transfer stains were observed. B: A slight stain from the ink transfer was observed. C: Stains from ink transfer were observed. TABLE 11
Note that the data for the brightness of the recording medium 5 (5) were not available because the brightness of the same cannot be measured since the ink was not dry. The inkjet inks of examples 1 to 17 and comparative examples 1 to 9 were evaluated in the following ways. The results are shown in tables 12 and 13. 10 <Measurement of Ink Viscosity> The viscosity of the ink was measured using a viscometer (RE-550L) manufactured by Toki Sangyo Co., Ltd.) at 25oC. <Measuring the pH of the ink> The pH of the ink was measured using a pH meter (HM-30R, manufactured by TOA-DKK CORPORATION) at 25oC. <Paint Surface Tension Measurement>
The surface tension of the paint was measured by an automatic surface tensiometer (CBVP-Z, manufactured by Kyowa Interface Science Co., Ltd.) at the paint temperature of 25oC. -Preparation of Print Assessment-
In the controlled environment where the temperature was adjusted to 23 ° C ± 0.5 ° C, and the humidity was adjusted to 50% RH ± 5% RH, an inkjet printer (IPSiO GXe-5500, manufactured by Ricoh Company Limited) for use in The impression was adjusted by varying the activation voltage of a piezoelectric element to unify a quantity of ink to be injected, so that the same quantity of ink can be deposited in each recording medium. <Image Density>
A map including a 64-point symbol “■” produced using Microsoft Word 2000 was printed on MyPaper (manufactured by Ricoh Company Limited), the color in the “■” portions on a printed surface was measured by X-Rite939 and the result was evaluated based on the following evaluation criteria. As for the print mode, the "Flat Paper - Standard High Speed" mode has been switched to the "No Color Correction" mode in the user settings for flat paper using a driver that came with a printer. [Evaluation Criteria] I: Black: 1.20 or more Yellow: 0.80 or more Magenta: 1.00 or more Cyan: 1.00 or more II: Black: 1.10 or more, but less than 1 , 20 Yellow: 0.70 or more, but less than 0.80 Magenta: 0.90 or more, but less than 1.00 Cyan: 0.90 or more, but less than 1.00 III: Black : less than 1.10 Yellow: less than 0.70 Magenta: less than 0.90 Cyan: less than 0.90 <Color Saturation>
A graph was printed on MyPaper (manufactured by Ricoh Company Limited) in the same way as in the image density assessment test, the “■” portions on a printed surface were measured by X-Rite939 and the result was evaluated based on the following criteria evaluation. Like the print mode, the "Flat Paper - Standard High Speed" mode was switched to the "No Color Correction" mode in the user settings for flat paper using a driver that came with the printer. The ratio of the measured color saturation values and the color saturation values (yellow: 91.34, magenta: 74.55. Cyan: 62.82) of the standard colors (Japan Color ver. 2) was calculated and the capacity staining was evaluated based on the ratio calculated based on the following criteria. [Evaluation Criteria] 1) Yellow 1: 0, 9 or more II: 0, 8 or more, but less than 0.9 III: less than 0.8 2) Magenta 1: 0, 8 or more II: 0, 75 or more, but less than 0.8 III: less than 0.75 3) Cyan 1: 0, 85 or more II: 0, 8 or more, but less than 0.85 III: less than that 0.8 [Wave Quantity Evaluation>
A solid image was printed by means of a printer prototype with in-line head as illustrated in figure 7 under the following printing conditions, and the height of the rear curl (curl of the paper when the paper was placed on a flat table with the printed surface face down) of the printed paper right after printing (within ten seconds after unloading from the printer) and the height of the paper curl after leaving the printed paper for 1 day on a flat table with the printed surface facing low was assessed. (1) Evaluation Printer: In-line printer prototype (see figure 7) (2) Evaluation means: MyPaper (PPC) manufactured by Ricoh Company Limited (3) Printing condition: recording density of 118 dpc x 236 dpc (300 dpi x 600 dpi), 526.3 cm2 / A4 print area, and 5.6 g / m2 ink deposition and ejection quantity (4) Evaluation environment: 23 ° C ± 0.5 ° C, 50 % RH ± 5% RH (5) Ripple measurement: Right after printing (within 10 seconds after unloading from the printer) or after being left for 1 day, the A4 size recording medium was placed calmly on a flat table with the wavy face facing up, and the height of the wave was measured by measuring the heights of the four corners of the recording medium with a JIS_1 scale, and obtaining the average value of the measured values from the four corners. When the recording medium waved significantly to form a cylindrical shape, a diameter of the cylinder was measured. [Rating criteria]
The results of the evaluation were classified as the following four classifications. A: less than 10 mm B: 10 mm or more but less than 40 mm C: 40 mm or more D: Wavy in a cylindrical shape <Ejection Stability>
A map having solid color images, each occupying 5% of the area of A4 size paper, which was formed by Microsoft Word 2000, was printed continuously on 200 sheets of MyPaper (manufactured by Ricoh Company Limited). Then, irregular ejections from each nozzle were assessed. As for the print mode, the "Flat Paper - High Standard Speed" mode has been switched to the "No Color Correction" mode in the user settings for flat paper using a driver that came with a printer. [Evaluation Criteria] No irregular ejection was observed. II: Irregular ink ejections were observed slightly. III: Irregular ink ejections were observed, or no ink was ejected from some parts of the nozzles. [Ink Storage Stability>
The viscosity of the ink before storage and the viscosity of the ink after being stored for 7 days at 70oC in a sealed container were measured by a viscometer, and the degree of stability in storage was determined from the viscosities measured by the following equation. The results were evaluated based on the following evaluation criteria. Ink storage stability (%) = [(viscosity after storage) / (viscosity before storage)] x100 [Evaluation Criteria] I: 100% ± 10% or less II: 100% ± more than 10%, but less than 20% III: 100% ± 20% or more TABLE 12
TABLE 13
Some data was not available in comparative example 4 because the ink in comparative example 4 had high viscosity so that a clean image, as obtained 5 with other inks, cannot be obtained. Therefore, a similar assessment cannot be carried out. PREPARATION EXAMPLE 1A) -Preparation of dispersion liquid of polymeric particles containing Black pigment Modified on 10 Surface 1- In room temperature environment, 100 g of Black Pearls® 1000 (carbon black having a BET surface area of 343 m2 / g and 105 ml / 100 g DBPA available from Cabot Corporation, 100 mmol of the compound represented by the following formula (VI), and 1 l of highly pure ion exchange water were mixed using a Silverson Mixer (6,000 rpm). In the case where the pH of the obtained suspension is greater than 4, 100 mmol of nitric acid were added. Thirty minutes later, sodium nitrite (100 mmol) dissolved in a small amount of highly pure ion exchange water was gradually added to the suspension. The resultant was heated to 60oC with stirring, to thus react for 1 hour. As a result, a modified pigment in which the compound of formula (VI) was added to the carbon black was generated. Subsequently, the pH of the resultant was adjusted to 10 with an aqueous solution of NaOH, in order to obtain a modified dispersion liquid in a time of 30 minutes. The dispersion liquid containing the pigment bound to at least one geminal bisphosphonic acid group or geminal bisphosphonate group and highly pure ion exchange water were used and subjected to ultrafiltration with a permeable membrane, and the resultant was further subjected to ultrasonic dispersion, to in this way to obtain a modified pigment dispersion liquid, whose pigment solids content was concentrated to 20% by weight. The degree of surface treatment was 0.75 mmol / g and the average particle diameter by volume (D50) as measured by the particle size distribution measuring device (NANOTRACK UPA-EX150, 5 manufactured by Nikkiso Co., Ltd.) was 120 nm. In addition, the sodium ion content was measured using the TOA-DKK IM-32P ion meter, the result was 27,868 ppm and the phosphorus (P) content as measured by the elemental analysis was 2.31% by mass. 10 <Compound of Formula (VI)>
(PREPARATION EXAMPLE 2A) -Preparation of Dispersion Liquid of Polymeric Particles Containing Black Pigment Modified on 15 Surface 2- The ProcessAll 4HV Mixer (4 l) was loaded with 500 g of Black Pearls® 880 (carbon black having surface area 220 m2 / g BET of 105 ml / 100 g DBPA available from Cabot Corporation, 1L of highly pure ion exchange water and 1 ml of the compound of formula (VI). Subsequently, the resulting mixture was mixed strongly at 300 rpm for 10 minutes, with heating at 60 ° C. To this, 20 wt% of an aqueous solution of sodium nitrite [1 mol equivalent to the compound of formula (VI)] was added over 15 minutes. The resulting mixture was mixed and stirred for 3 hours with heating at 60 ° C. The reagent was removed while diluting with 750 ml of highly pure ion exchange water. The obtained modified pigment dispersion liquid and highly pure ion exchange water were used and subjected to ultrafiltration with a permeable membrane and the resultant was further subjected to ultrasonic dispersion to thereby obtain a modified pigment dispersion liquid, the solids content. of the pigment from which it was concentrated to 20% by mass. The degree of surface treatment was 0.5 mmol / g and the average particle diameter by volume (D5o) as measured by the particle size distribution measuring device (NANOTRACK UPA-EX150, manufactured by Nikkiso Co., Ltd.) was 104 nm. In addition, the sodium ion content was measured using a TOA-DKK IM-32P ion meter and the result was 19,940 ppm and the phosphorus (P) content as measured by the elemental analysis was 2.20% by mass. Preparation of Polymeric Particles Dispersion Liquid Containing Surface Modified Black Pigment 3-
The ProcessAll 4HV Mixer (4 l) was loaded with 500 g of Black Pearls® 880 (carbon black having BET surface area of 220 m2 / g and 105 ml / 100 g DBPA) available from Cabot Corporation, IL, of highly water pure ion exchange, and 175 mmol of the compound of formula (VII). Subsequently, the resulting mixture was mixed strongly at 300 rpm for 10 minutes, with heating at 60 ° C. To this, 20 wt% of an aqueous sodium nitrite solution [175 mmol equivalent to the compound of formula (VII)] was added over 15 minutes. The resulting mixture was mixed and stirred for 3 hours with heating at 60 ° C. The reagent was removed while diluting with 750 ml of highly pure ion exchange water. The obtained modified pigment dispersion liquid and highly pure ion exchange water were used, and subjected to ultrafiltration with a permeable membrane, and the resultant was further subjected to ultrasonic dispersion, in order to obtain a modified pigment dispersion liquid, the solids content of the pigment from which it was concentrated to 20% by weight. The degree of surface treatment was 0.35 mmol / g and the average volume particle diameter (D50) as measured by the particle size distribution measuring device (NANOTRACK UPA-EX150, manufactured by Nikkiso Co., Ltd.) was 114 nm. In addition, the sodium ion content was measured using the TOA-DKK IM-32P ion meter, and the result was 12, 792 ppm, and the phosphorus (P) content as measured by the elemental analysis was 1.08% in large scale. <Compound of Formula (VII)>
(PREPARATION EXAMPLE 4A) -Preparation of Polymeric Particles Dispersion Liquid Containing Surface Modified Magenta Pigment 1-
At room temperature, 100 g of Red Pigment CI 122 with small particle diameters available from Sun Chemical, 50 mmol of the compound of formula (VII), 1 l of highly pure ion exchange water were mixed using the Silverson mixer (6,000 rpm). Thirty minutes later, to the resulting suspension, sodium nitrite (100 mmol) dissolved in a small amount of highly pure ion exchange water was added gradually. The resultant was heated to 60oC with stirring, to thus react for 1 hour. As a result, a modified pigment in which the compound of formula (VII) was added to Pigment Red C.I. 122 was generated. Subsequently, the pH of the resultant was adjusted to 10 with an aqueous solution of NaOH, in order to obtain a modified dispersion liquid in a time of 30 minutes. The dispersion liquid containing the pigment bound to at least one geminal bisphosphonic acid group or geminal bisphosphonate group and highly pure ion exchange water were used and subjected to ultrafiltration with a permeable membrane, and the resultant was further subjected to ultrasonic dispersion to in this way to obtain a modified pigment dispersion liquid, the solids content of the pigment from which it was concentrated to 20% by mass. The degree of surface treatment was 0.50 mmol / g, and the average particle diameter by volume (D50) as measured by the particle size distribution measuring device (NANOTRACK UPA-EX150, manufactured by Nikkiso Co., Ltd .) was 111 nm. In addition, the phosphorus (P) content as measured by the elemental analysis was 0.26% by mass. -Preparation of Polymeric Particles Dispersion Liquid Containing Surface Modified Magenta Pigment 2-
At room temperature, 690 g of SMART Magenta 3122BA (CI 122 Pigment Red dispersion liquid treated on the surface, the pigment content was 14.5% by mass), available from Sensient Techologies Corporation, 50 mmol of the formula compound (VII) and 500 ml of highly pure ion exchange water were mixed using a Silverson Mixer (6,000 rpm). Thirty minutes later, to the resulting suspension, sodium nitrite (100 mmol) dissolved in a small amount of highly pure ion exchange water was added gradually. The resultant was heated to 60oC with stirring, to thus react for 1 hour. As a result, a modified pigment in which the compound of formula (VII) was added to Pigment Red C.I. 122 was generated. Subsequently, the pH of the resultant was adjusted to 10 with tetramethyl ammonium hydroxide, to thereby obtain a modified dispersion liquid within 30 minutes. The dispersion liquid containing the pigment attached to at least one geminal phosphonic acid group or bisphosphonic acid tetramethyl ammonium salt group and highly pure ion exchange water were used and subjected to ultrafiltration with a permeable membrane, and the result was still subjected to ultrasonic dispersion, in order to obtain a modified pigment dispersion liquid, the solids content of the pigment from which it was concentrated to 20% by mass. The degree of surface treatment was 0.50 mmol / g, and the average particle diameter by volume (D5o) as measured by the particle size distribution measuring device (NANOTRACK UPA-EX150, manufactured by Nikkiso Co., Ltd .) was 106 nm. In addition, the phosphorus (P) content as measured by the elemental analysis was 0.25% by mass. (PREPARATION EXAMPLE 6A) -Preparation of Surface Treated Cyan Pigment Dispersion 1-
In the room temperature environment, 690 g of SMART Cyan 3154BA (polymeric particle dispersion liquid containing Pigment Blue CI 15: 4 pigment treated on the surface, 14.5% by mass pigment content) available from Sensient Technologies Corporation, 50 mmol of the compound of formula (VI) and 500 ml of highly pure ion exchange water were mixed by means of a Silverson Mixer (6,000 rpm). Thirty minutes later, to the resulting suspension, sodium nitrite (100 mmol) dissolved in a small amount of highly pure ion exchange water was added gradually. The resultant was heated to 60oC with stirring, to thus react for 1 hour. As a result, a modified pigment in which the compound of formula (VI) was added to Pigment Blue C.I. 15: 4 was generated. Subsequently, the pH of the resultant was adjusted to 10 with tetramethyl ammonium hydroxide, to thereby obtain a modified dispersion liquid within 30 minutes. The dispersion liquid containing the pigment bound to at least one geminal bisphosphonic acid group or tetramethyl ammonium salt group of geminal bisphosphonic acid and highly pure ion exchange water were used and subjected to ultrafiltration with a permeable membrane, and the result was still subjected to ultrasonic dispersion, in order to obtain a modified pigment dispersion liquid, the solids content of the pigment from which it was concentrated to 20% by mass. The degree of surface treatment was 0.50 mmol / g, and the average particle diameter by volume (D5o) as measured by the particle size distribution measuring device (NANOTRACK UPA-EX150, manufactured by Nikkiso Co., Ltd .) was 113 nm. In addition, the phosphorus (P) content as measured by the elemental analysis was 0.27% by mass. (PREPARATION EXAMPLE 7A) -Preparation of the Dispersion Liquid of Polymeric Particles Containing Modified Yellow Pigment Surface 1-
In the room temperature environment, 690 g of SMART Yellow 3074BA (CI 74 Pigment Yellow dispersion liquid treated on the surface), the pigment content of 14.5% by mass) available from Sansient Technologies Corporation, 50 mmol of the formula compound (VII) and 500 ml of highly pure ion exchange water were mixed using a Silverson Mixer (6,000 rpm). Thirty minutes later, to the resulting suspension, sodium nitrite (100 mmol) dissolved in a small amount of highly pure ion exchange water was added gradually. The resultant was heated to 60oC with stirring, to thus react for 1 hour. As a result, a modified pigment in which the compound of formula (VII) was added to Pigment Yellow C.I. 74 was generated. Subsequently, the pH of the resultant was adjusted to 10 with tetramethyl ammonium hydroxide, to thereby obtain a modified dispersion liquid within 30 minutes. The dispersion liquid containing the pigment attached to at least one geminal bisphosphonic acid group or tetrabutyl ammonium salt group of geminal bisphosphonic acid and highly pure ion exchange water were used and subjected to ultrafiltration with a permeable membrane, and the result was still subjected to ultrasonic dispersion, in order to obtain a modified pigment dispersion liquid, the solids content of the pigment from which it was concentrated to 20% by mass. The degree of surface treatment was 0.50 mmol / g and the average particle diameter by volume (D5o) as measured by the particle size distribution measuring device (NANOTRACK UPA-EX150, manufactured by Nikkiso Co., Ltd.) was 142 nm. In addition, the phosphorus (P) content as measured by the elemental analysis was 0.26% by mass. (PREPARATION EXAMPLE 8A) -Preparation of Dispersion Liquid of Polymeric Particles Containing Black Pigment Modified on the Surface 4-
To a 2.5N sodium sulfate solution (3,000 ml), 90 g of carbon black having a specific BET surface area of 150 m2 / g, and DBP oil absorption of 100 ml / 100 g was added and the mixture The resulting mixture is allowed to react for 10 hours with agitation at a temperature of 60oC, at the rate of 300 rpm, in order to proceed as an oxidation treatment. The resulting reaction solution was subjected to filtration to separate the carbon black, and the separated carbon black was then neutralized with a sodium hydroxide solution, followed by being subjected to ultrafiltration.
The obtained carbon black was washed with water and then dried. Then, the carbon black was dispersed in pure water so that the solids content of the pigment should be 20% by mass, and the dispersion was then stirred sufficiently to thereby obtain a black pigment dispersion liquid. The average particle diameter (D50) of the pigment dispersion elements in the black pigment dispersion liquid was measured by a particle size distribution measuring device (NANOGTRACK UPA-EX150, manufactured by Nikkiso Co., Ltd.) and the result was 103 nm. (PREPARATION EXAMPLE 9A) <Preparation of Polymeric Particles Dispersion Liquid Containing Magenta Pigment> -Preparation of the Polymeric Solution A- A 1 liter flask equipped with a mechanical stirrer, a thermometer, a nitrogen inlet tube, a reflux and a drip funnel, which was sufficiently purged with nitrogen gas, was charged with 11.2 g of styrene, 2.8 g of acrylic acid, 12.0 g of lauryl methacrylate, 4.0 g of polyethylene glycol methacrylate , 4.0 g of styrene macromer and 0.4 g of mercaptoethanol, and the resulting mixture was mixed and heated to 65oC. Then, a mixed solution of styrene (100.8 g), acrylic acid (25.2 g), lauryl methacrylate (108.0 g), polyethylene glycol methacrylate (36.0 g), hydroxyethyl methacrylate (60, 0 g), styrene macromer (36.0 g), mercaptoethanol (3.6 g), methyl valeronitrile azobis (2.4 g), and methyl ethyl ketone (18 g) was added dropwise into the flask over 2.5 hours. Then, a mixed solution of azobis methylvaleronitrile (0.8 g) and methyl ethyl ketone (18 g) was added dropwise into the flask over 0.5 hours. After the mixture was aged at 65oC for 1 hour, 0.8 g of methylvaleronitrile azobis was added to it, and the resulting mixture was further aged for 1 hour. At the end of the reaction, methyl ethyl ketone (364 g) was added to the flask, in order to obtain 800 g of Polymeric Solution A having a concentration of 50% by mass.
Preparation of the Dispersion Liquid of Polymeric Particles Containing Pigment-
After sufficiently stirring a mixture of Polymeric Solution A (28 g), Pigment Red CI 122 (42 g), an aqueous solution of 1 mol / l potassium hydroxide (13.6 g), methyl ethyl ketone (20 g) , and ion exchange water (13.6 g), the resulting mixture was kneaded by a roller mill. To the obtained paste, 200 g of pure water was added, the resulting mixture was stirred sufficiently, and methyl ethyl ketone and water were removed from the resulting dispersion liquid using an evaporator, followed by being subjected to pressure filtration with a membrane filter. polyvinylidene fluoride having an average pore diameter of 5.0 μm to remove coarse particles from the dispersion liquid, to thereby obtain a polymer particle dispersion liquid containing magenta pigment having a pigment solids content of 15% by weight, and having a solids content of 20% by weight. The average particle diameter (D50) of the polymeric particles in the polymeric dispersion liquid containing magenta pigment obtained was measured by a particle size distribution measuring device (NANOTRACK UPA-EX150, manufactured by Nikkiso Co., Ltd.) and the result was 127 nm. (PREPARATION EXAMPLE 10A) -Preparation of Dispersion Liquid of Polymeric Particles Containing Cyan Pigment-
A polymeric dispersion liquid containing cyan pigment was prepared in the same manner as in preparation example 9A, with the proviso that the pigment was exchanged from Pigment Red C.I. 122 to a phthalocyanine pigment (Pigment Blue C.I. 15: 3). The average particle diameter (D50) of the polymeric particles in the polymeric dispersion liquid containing cyan pigment obtained was measured by a particle size distribution measuring device (NANOTRACK UPA-EX150, manufactured by Nikkiso Co., Ltd.) , and the result was 93 nm. (PREPARATION EXAMPLE 11A) -Preparation of Polymeric Particles Dispersion Liquid Containing Yellow Pigment-
A polymeric dispersion liquid containing yellow pigment was prepared in the same manner as in preparation example 8A, with the proviso that the pigment was exchanged for Pigment Red C.I. 122 for a yellow monoazo pigment (Pigment Yellow C.I. 74). The average particle diameter (D50) of the polymer particles in the yellow pigment containing polymer particle dispersion liquid was measured by a particle size distribution measuring device (NANOTRACK UPA-EX150, manufactured by Nikkiso Co., Ltd. ), and the result was 76 nm. (PREPARATION EXAMPLE 12A) -Preparation of Dispersion Liquid of Polymeric Particles Containing Smoke Black Pigment-
A polymer particle dispersion liquid containing carbon black pigment was prepared in the same manner as in preparation example 9A, with the proviso that the pigment was changed from Pigment Red CI 122 to carbon black (FW110, by Degussa AG). The average particle diameter (D50) of the polymeric particles in the polymeric dispersion liquid containing yellow pigment was measured by a particle size distribution measuring device (NANOTRACK UPA-EX150, manufactured by Nikkiso Co., Ltd.), and the result was 104 nm. (EXAMPLES 1A to 14A) <Preparation of Inkjet Ink> First, as shown in tables 1A to 4A, organic solvents (wetting agent), penetrating agents, a surfactant, an antifungal agent, and water were mixed and the mixture The resulting mixture was stirred for 1 hour to homogeneously mix the mixture. Depending on the mixture, a water-dispersible resin was added and stirred for 1 hour. Then, a water-dispersible dye (a pigment dispersion liquid), a defoaming agent and a pH regulator were added and the mixture was stirred for 1 hour. The resulting dispersion liquid was subjected to pressure filtration with a polyvinylidene fluoride membrane filter having an average pore diameter of 1.2 μm to remove coarse particles or dust, to thereby prepare each ink jet ink of the examples 1A to 14A. TABLE 1

TABLE 2

TABLE 3

TABLE 4

The abbreviations in Tables 1A to 4A represent as follows: SENSIJET SMART Magenta 3122BA: manufactured by Sensient Technologies Corporation (surface treated pigment dispersion liquid) SENSIJET SMART Cyan 3154BA: manufactured by Sensient Technologies Corporation (surface treated pigment dispersion ) SENSIJET SMART Yellow 3074BA: manufactured by Sensient 10 Technologies Corporation (surface treated pigment dispersion) SENSIJET Black SDP2000: manufactured by Sensient Technologies Corporation (surface treated pigment dispersion) 15 Acrylic silicone resin emulsion: POLYSOL ROY6312, manufactured by Showa Highpolymer Co., Ltd., which has a solids content of 39.9% by weight, an average particle diameter of 171 nm, and a minimum film-forming temperature (MFT) of 20oC.
Fluororesin A emulsion; LUMIFLON FE4300, manufactured by Asahi Glass Co., Ltd., having a solids content of 50% by mass, the average particle diameter of 150 nm, and MFT of 30oC or less.
Polyurethane emulsion: HYDRAN APPROXIMATELY-101H, manufactured by DIC Corporation, having a solids content of 45% by mass, the average particle diameter of 160 nm, and the minimum film formation temperature (MFT) of 20oC KF-643 : polyether modified silicone compound (manufactured by Shin-Etsu Chemical Co., Ltd., having 100% by weight active ingredient) Zonyl FS-300: polyoxyethylene perfluoroalkyl ether (manufactured by EI DuPont de Nemours and Company, having 40% by weight active ingredient) Surfynol 104E: acetylene glycol compound (manufactured by Nissin Chemical Industry Co., Ltd., having 50% by weight active ingredient, containing ethylene glycol) Softanol EP-7025: alkyl ether of polyoxyalkylene (manufactured by Nipon Shokubai Co., Ltd., 100% by weight active ingredient) Proxel GXL: an antifungal agent having 1,2- (manufactured by Avecia Biologies Limited, having the active ingredient by 20% by weight, containing dipropylene glycol ) Amide compound of formula (1): composition amide product represented by the following formula (1)
Formula (1) Amide compound of formula (2): amide compound represented by the following formula (2)
Formula (2) Amide compound of formula (3): amide compound represented by the following formula (3)
Formula (3) Compound of formula (4): compound represented by the following formula (4)
Formula (4) following formula (8)
following formula (10)
10 Formula (10) Compound of formula (18): compound represented by the following formula (18)
Formula (18) Amide compound of formula (V): amide compound represented by the following structural formula (V)
Structural Formula (V) Compound of formula (VIIa) - (q): compound represented by the following general formula (VIIa) - (q) C6F13-CH2CH (OH) CH2OHCH2CH2O) 21-C12H25 General Formula (VIIa) - (q)
The physical properties of each inkjet ink in Examples 1A to 4A were measured by the following evaluation methods. The results are shown in table 3A.
Note that the viscosity and pH of the paint were measured in the same way as in examples 1 and 22 and comparative examples 1 to 9.
In addition, the dynamic surface tension of the inkjet ink and the viscosity of the inkjet ink after moisture evaporation were measured as follows. <Measurement of Dynamic Paint Surface Tension>
The dynamic surface tension of each of the prepared paints was measured using SITA_DynoTester (available from SITA) at 25oC with the duration of the bubble on the surface of 15 ms as in the maximum bubble pressure method. <Viscosity measurement after moisture evaporation>
The inks in the examples and comparative examples were placed in a glass dish having an opening diameter of 33 mm, weighed and collected in 2.5 g by means of an accurate top plate electric balance capable of measuring up to 4 digits a from the decimal point. Then, the ink was stored in a thermostat (model PL-3KP, manufactured by ESPEC) adjusted at a temperature of 23oC ± 0.5oC, and a humidity of 15% ± 5% RH under normal pressure and each sample was taken from 30 in 30 minutes to measure the mass and viscosity of the remaining paint. This procedure continued for 5 hours. Then, the moisture evaporation rate and the remaining ink viscosity when the moisture was evaporated were plotted on a graph, and the ink viscosity when the moisture evaporation rate was 30% was read. Judging standards for paint viscosity after moisture evaporation are described below. [Viscosity when the moisture evaporation rate was 30%] A: lower than 100 mPa-s 5 B: 100 mPa-s at 500 mPa-s C: higher than 500 mPa-s The viscosity of the remaining paint it was measured by means of a viscometer (RE-550L, manufactured by Toki Sangyo Co., Ltd.) at 25oC. 10 Moisture evaporation rate (% by mass) = (1-mass of paint remaining / mass of paint before moisture evaporation) x 100 Note that the component evaporated from the paint was assumed to be all water. 15 TABLE 5
-Ink Blasting Step (Image Formation Stage) -
In the environment adjusted to 23oC ± 0.5oC, and 50% ± 5% RH, an inkjet recording device (IPSiO GXe-5500, manufactured by Ricoh Company Limited) was adjusted to give the same amount of deposition in the (MyPaper, manufactured by Ricoh Company Limited) by varying the drive voltage of a piezoelectric element to give the same amount of paint ejection. Then, the printing mode of the inkjet recording device was set to “Flat Paper - High Speed” and then the images were formed.
The inkjet inks of examples 1A to 14A were evaluated by the following methods. The results are shown in table 6A.
Image density, staining, fixability, and ink depositions on a maintenance device were evaluated in the ways described below.
Note that the evaluations on the corrugated quantity, ejection stability and ink storage stability were carried out in the same way as in examples 1 to 22 and comparative examples 1 to 9. <Image Density>
A map including a 64-point “■” symbol produced using Microsoft Word 2000 was printed on MyPaper (manufactured by Ricoh Company Limited), the color in the “■” portions on a printed surface was measured by X-Rite939, and the result was evaluated based on the following evaluation criteria. As for the print mode, the "Flat Paper - Standard High Speed" mode has been switched to the "No color correction" mode in the user settings for flat paper using a driver that came with a printer. [Evaluation Criteria] A: Black, 1.25 or more Yellow, 0.80 or more Magenta, 1.00 or more Cyan, 1.5 or more B: Black, 1.20 or more, but less than 1 , 25 Yellow, 0.75 or more, but less than 0.80 Magenta, 0.95 or more, but less than 1.00 Cyan, 1.00 or more, but less than 1.05 C: Black , 1.15 or more, but less than 1.20 Yellow, 0.70 or more, but less than 0.75 Magenta, 0.90 or more, but less than 0.95 Cyan, 0.95 or more, but less than 1.00 D: Black, but less than 1.15 Yellow, less than 0.70 Magenta, less than 0.90 Cyan, less than 0.95 “Ink staining and fixing > A map including a 64-point “■” symbol produced using Microsoft Word 2000 was printed on Mypaper (manufactured by Ricoh Company Limited) in the same way as in the image density assessment. Then, the resulting ink was dried for 24 hours in the environment having a temperature of 23 ° C ± 2oC, relative humidity of 50% ± 15%. The “■” portion on the printed surface was rubbed, for 10 returns, with JIS L0803 Cotton no 3 adhered to a CM-1 watch gauge with double-sided tape. Then, the deposition of ink on the cotton fabric was measured by X-Rite939 (manufactured by X-Rite), the density of the deposited ink, part of which the background color of the cotton fabric that was deduced was judged based on the following rating criteria. [Evaluation Criterion 1] “Flat, High Speed Paper Mode” A: less than 0.01 B: 0.01 or more, but less than 0.025 C: 0.025 or more, but less than 0.05 ( threshold for practical application) D: 0.05 or more <Ink Deposition in the Maintenance Device> - Ink Blasting Step (Image Formation Stage) - In the environment adjusted to 28oC ± 0.5oC and 15% ± 5% RH, an inkjet recording device (IPSiO GXe-5500, manufactured by Ricoh Company Limited) was used, and a drive voltage for a piezoelectric element varied to give the same amount of ejection of the ink, followed by a head cleaning operation continuously 10 times every 1 hour. After performing this operation for 10 hours, that is, performing head cleaning 100 times in total, the device was left to remain for 12 hours and then the existence of any ink deposition in a cleaner portion of the maintenance device and in a wire cleaning portion of it was observed visually. [Evaluation Criteria] I: no ink deposition was observed II: a slight amount of ink deposition was observed III: ink depositions were observed TABLE 6
Then, the inkjet ink prepared in example 1A was used on the embossing sheets (1) to (5) which were the same as in examples 1 to 22 and comparative examples 5 to 9, and the evaluation of the quality of image was taken in the following ways. <Image Quality Assessment> When using the inkjet ink of example 1A, the images were printed on the recording sheets (1) to 10 (5) using an inkjet printer (IPSiO GXe- 5500 , manufactured by Ricoh Company Limited) with the "Glossy Paper - High Quality Ink" mode setting with "No Color Correction," and the resulting image was evaluated for image quality. 15 The results are shown in table 7A. Image density, wrinkling, staining and fixation capacity were assessed as follows. Note that the dripping and splash marks were evaluated as follows as in examples 1 to 22 and comparative examples 1 to 9. <Image Density>
A map including a 64-point “■” symbol produced using Microsoft Word 2000 was printed on each recording sheet.
The color in the “■” portions on a printed surface was measured by X-Rite939, and the result was evaluated based on the following evaluation criteria. As for the print mode, the "Glossy Paper - High Quality Print" mode has been changed to have "No Color Correction" in the user settings for flat paper using a driver that came with a printer. [Evaluation Criterion 1] - “Glossy Paper - High Quality Print Mode” A: Black, 2.0 or more B: Black, 1.9 or more, but less than 2.0 C: Black, 1, 8 or more, but less than 1.9 D: Black, less than 1.8 <Wrinkle>
A map including a solid mono-colored image “■■■” in 3 cm x 15 cm size produced using
Microsoft Word 2000 was printed on each recording sheet. Shortly after the formation of the image with the inkjet ink, a wrinkle occurrence was evaluated visually, and if the transport failure can occur in the following step, it was judged based on the following evaluation criteria.
As for the print mode, the "Glossy Paper - High Quality Print" mode has been changed to have "No Color Correction" in the user settings for flat paper using a driver that came with a printer. [Evaluation Criteria] A: There was no wrinkling (no transport problem). B: Wrinkling occurred slightly (no transport problem). C: Wrinkling has occurred (no significant transportation problem) D: Wrinkling has occurred significantly (a transportation problem). <Staining, Fixing Capacity>
As with the image density assessment, a map including a 64-point "■" symbol produced using Microsoft Word 2000 was printed on each recording sheet.
Then, the resulting impression was dried for 24 hours at a temperature of 23 ° C ± 2oC, and a humidity of 50% ± 15% RH. The “■” portion of the printed surface was wiped, 5 for 10 returns, with JIS L0S03 Cotton no 3 adhered to a CM-1 watch gauge with double-sided tape. Then, the deposition of ink on the cotton fabric was measured by X-Rite939 (manufactured by X-Rite), the density of the deposited part of the ink from which the background color of the cotton fabric was deduced was judged based following evaluation criteria. [Evaluation Criterion 1] - “Glossy Paper Mode - High Quality Printing” A: less than 0.05 15 B: 0.05 or more, but less than 0.1 C: 0.1 or more, but less than 0.15 (threshold for practical use) D: 0.15 or more TABLE 6
Note that the data for the image density of the recording sheet (5) has not been evaluated because the recording sheet (5) cannot be dried. 5 [PREPARATION EXAMPLE 1B] -Preparation of surface-modified black pigment dispersion liquid- In room temperature environment, 100 g of Black Pearls® (carbon black having a BET surface area of 10 343 m2 / g and DBPA of 105 ml / 100 g) available from Cabot Corporation, 100 mmol of sulfanilic acid and 1 l of highly pure ion exchange water were mixed using a Silverson Mixer (6,000 rpm). In the case where the pH of the obtained suspension was more than 4, 100 mmol of nitric acid were added. Thirty minutes later, to the resulting suspension, sodium nitrite (100 mmol) dissolved in a small amount of highly pure ion exchange water was added gradually. The resultant was heated to 60oC with stirring, to thus react for 1 hour. As a result, a modified pigment to which sulfanilic acid was added to carbon black was generated. Subsequently, the pH of the resultant was adjusted to 9 with 10 wt% tetrabutyl ammonium hydroxide solution (methanol solution), to thereby obtain a modified dispersion liquid within 30 minutes. The dispersion liquid containing the pigment bound to at least one sulfanilic acid group or tetrabutyl ammonium salt group and highly pure ion exchange water was used and subjected to ultrafiltration with a permeable membrane, and the resultant was further subjected to ultrasonic dispersion. , in order to obtain a modified pigment liquid and dispersion, the solids content of the pigment from which it was concentrated to 20% by mass. The degree of surface treatment was 0.75 mmol / g and the average volume particle diameter (D50) as measured by the particle size distribution measuring device (NANOTRACK UPA-EX150, manufactured by Nikkiso Co., Ltd.) was 120 nm. (PREPARATION EXAMPLE 2B) -Preparation of the Modified Black pigment dispersion liquid on the surface 2- The ProcessAll 4HV Mixer (4 l) was loaded with 500 g of Black Pearls® 880 (carbon black having a 220 m2 BET surface area / g, and 100 ml / 100 g DBPA available from Cabot Corporation, 1 l of highly pure ion exchange water, and 1 mole of 4-amino benzoic acid. Subsequently, the resulting mixture was mixed strongly at 300 rpm for 10 minutes, with heating at 60 ° C. To this, 20 wt% of an aqueous solution of sodium nitrite (1 mol equivalent to 4-amino benzoic acid) was added over 15 minutes. The resulting mixture was mixed and stirred for 3 hours with heating at 60 ° C. The reagent was removed while diluting with 750 ml of highly pure ion exchange water. Subsequently, the pH of the resultant was adjusted to 9 with 10 wt% tetrabutyl ammonium hydroxide solution (methanol solution), to thereby obtain a modified dispersion liquid within 30 minutes. The dispersion liquid containing the pigment attached to at least one group of amino benzoic acid or tetrabutyl ammonium salt group of amino benzoic acid and highly pure ion exchange water were used and subjected to ultrafiltration with a permeable membrane, and the result was still subjected to ultrasonic dispersion, in order to obtain a modified pigment dispersion liquid, the solids content of the pigment on which it was surface was 0.5 mmol / g and the volume average particle diameter (D50) as measured by the measuring device particle size distribution (NANOTRACK UPA-EX150, manufactured by Nikkiso Co., Ltd.) was 104 nm. (PREPARATION EXAMPLE 3B) -Preparation of Surface-Modified Black Pigment Dispersion Liquid 3- The ProcessAll 4HV Mixer (4 l) was loaded with 500 g of Black Pearls® 880 (carbon black having 220 m2 BET surface area / g, and 105 ml / 100 g DBPA available from Cabot Corporation, 1 l of highly pure ion exchange water, and 175 mmol of 4-amino benzoic acid. Subsequently, the resulting mixture was mixed strongly at 300 rpm for 10 minutes, with heating at 60 ° C. To this, 20 wt% of an aqueous sodium nitrite solution [175 mmol equivalent to 4-amino benzoic acid] was added over 15 minutes. The resulting mixture was mixed and stirred for 3 hours with heating at 60 ° C. The reagent was removed while diluting with 750 ml of highly pure ion exchange water. Subsequently, the pH of the resultant was adjusted to 9 with 10 wt% aqueous tetraethyl ammonium hydroxide solution, to thereby obtain a modified dispersion liquid within 30 minutes. The dispersion liquid containing the pigment bound to at least one group of amino benzoic acid or tetraethyl ammonium salt group of amino benzoic acid and highly pure ion exchange water was used and subjected to ultrafiltration with a permeable membrane and the result was further submitted to ultrasonic dispersion, in order to obtain a modified pigment dispersion liquid, the solids content of the pigment from which it was concentrated to 10% by mass. The degree of surface treatment was 0.35 mmol / g and the average volume particle diameter (D50) as measured by the particle size distribution measuring device (NANOTRACK UPA-EX150, manufactured by Nikkiso Co., Ltd.) was 114 nm. (PREPARATION EXAMPLE 4B) -Preparation of the Modified Black Pigment Dispersion Liquid 4- The self-dispersing Aqua-Black 162 carbon black dispersion liquid (1 kg) (manufactured by Tokai Carbon Co., Ltd., the content of pigment solids: 19.2% by mass)) was subjected to purification by acid deposition with an aqueous solution of 0.1N HCl. Subsequently, the pH of the resultant was adjusted to 9 with a 40% by weight benzyltrimethyl ammonium hydroxide solution (methanol solution), to thereby obtain a modified dispersion liquid within 30 minutes. The dispersion liquid containing the pigment bound to at least one group of carboxylic acid or benzyltrimethyl ammonium salt of carboxylic acid and highly pure ion exchange water was used and subjected to ultrafiltration with a permeable membrane, and the resultant was further subjected to dispersion ultrasonic, in order to obtain a modified pigment dispersion liquid, the solids content of the pigment from which it was concentrated to 20% by mass. The volume average particle diameter (D50) as measured by the particle size distribution measuring device (NANOTRACK UPA-EX150, manufactured by Nikkiso Co., Ltd.) was 100 nm. (PREPARATION EXAMPLE 5B) -Preparation of Surface-Modified Black Pigment Dispersion Liquid 5- SENSIJET Black SDP2000 pigment dispersion liquid (1 kg) (pigment solids content: 14.5% by mass) available from Sensient Technologies Corporation was subjected to purification by acid deposition with an aqueous solution of 0.1N HCl. Subsequently, the pH of the resultant was adjusted to 9 with a 10 wt% tetrabutyl ammonium hydroxide solution (methanol solution), to thereby obtain a modified dispersion liquid within 30 minutes. The dispersion liquid containing the pigment bound to at least one carboxylic acid group, a sulfonic acid group, a tetrabutyl ammonium salt group of carboxylic acid, or a tetrabutyl ammonium salt group of sulfonic acid and highly pure exchange water ionic was used and subjected to ultrafiltration with a permeable membrane and the resultant was further subjected to ultrasonic dispersion, in order to obtain a modified pigment dispersion liquid, the content and solids of which was concentrated to 20% by mass. The volume average particle diameter (D50) as measured by the particle size distribution measuring device (NANOTRACK UPA-EX150, manufactured by Nikkiso Co., Ltd.) was 120 nm. (PREPARATION EXAMPLE 6B) -Preparation of Surface Modified Magenta Pigment Dispersion Liquid 1- SMART Magenta Pigment Dispersion Liquid 3122BA (CI 122 Red Pigment Dispersion Liquid (1 kg) treated on the surface, the solids content of pigment: 14.5% by mass)), available from Sensient Technologies Corporation, was subjected to purification by the disposal of acid with an aqueous solution of 0.1N HCl. Subsequently, the pH of the resultant was adjusted to 9 with a 10 wt% aqueous solution of tetraethyl ammonium hydroxide, to thereby obtain a modified dispersion liquid within 30 minutes. The dispersion liquid containing the pigment bound to at least one group of amino benzoic acid or a group of tetraethyl ammonium salt of amino benzoic acid and highly pure ion exchange water was used and subjected to ultrafiltration with a permeable membrane, and the resulting it was also subjected to ultrasonic dispersion, in order to obtain a modified pigment dispersion liquid, the solids content of the pigment of which was concentrated to 20% by mass. The volume average particle diameter (D50) as measured by the particle size distribution measuring device (NANOTRACK UPA-EX150, manufactured by Nikkiso Co., Ltd.) was 104 nm. (PREPARATION EXAMPLE 7B) -Preparation of the Surface Treated Cyan Pigment Dispersion Liquid 1- SMART Cyan 3154BA pigment dispersion liquid (the 15: 4 (1 kg) Blue Pigment Dispersion Liquid treated on the surface, the content pigment solids: 14.5% by mass)) available from Sansient Technologies Corporation was subjected to purification by acid deposition with 0.1N aqueous HCl solution. Subsequently, the pH of the resultant was adjusted to 9 with a 40% by weight benzyltrimethyl ammonium hydroxide solution (methanol solution), to thereby obtain a modified dispersion liquid within 30 minutes. The dispersion liquid containing the pigment bound to at least one amino benzoic acid group or benzyltrimethyl ammonium salt group of aminobenzoic acid and highly pure ion exchange water was used and subjected to ultrafiltration with a permeable membrane, and the result was further subjected to ultrasonic dispersion, in order to obtain a modified pigment dispersion liquid, the solids content of the pigment from which it was concentrated to 20% by mass. The volume average particle diameter (D50) as measured by the particle size distribution measuring device (NANOTRACK UPA-EX150, manufactured by Nikkiso Co., Ltd.) was 116 nm. (PREPARATION EXAMPLE 8B) -Preparation of Surface Modified Yellow Pigment Dispersion Liquid 1- SMART Yellow 3074BA pigment dispersion liquid (1 kg) (CI 74 Yellow Pigment dispersion liquid treated on the surface, solids content of pigment: 14.5% by mass) available from Sensient Technologies Corporation was subjected to purification by acid deposition with an aqueous solution of 0.1N HCl. Subsequently, the pH of the resultant was adjusted to 9 with 10 wt% tetrabutyl ammonium hydroxide solution (methanol solution), to thereby obtain a modified dispersion liquid within 30 minutes. The dispersion liquid containing the pigment attached to at least one group of amino benzoic acid or tetrabutyl ammonium salt group of amino benzoic acid and highly pure ion exchange water was used and subjected to ultrafiltration with a permeable membrane, and the result was still subjected to ultrasonic dispersion to obtain a modified pigment dispersion liquid, the pigment solids content of which was concentrated to 20% by mass. The volume average particle diameter (D50) as measured by the particle size distribution measuring device (NANOTRACK UPA-EX150, manufactured by Nikkiso Co., Ltd.) was 145 nm. (EXAMPLES 1B TO 13B) <Inkjet Ink Preparation> First, as shown in tables 1B to 3B, organic solvents (wetting agent), penetrating agents, a surfactant, an antifungal agent and water were mixed and the mixture The resulting mixture was stirred for 1 hour to homogeneously mix the mixture. Depending on the mixture, a water-dispersible resin was added and stirred for 1 hour. Then, a water-dispersible dye (a pigment dispersion liquid), added and the mixture stirred for 1 hour. The resulting dispersion liquid was subjected to pressure filtration with a polyvinylidene fluoride membrane filter having an average pore diameter of 1.2 μm 5 to remove coarse particles or dust, in order to prepare each ink jet ink of the examples 1B to 13B. TABLE 1B

TABLE 2B

TABLE 3B

The abbreviations in tables 1B to 3B represent the following: SENSIJET SMART Magenta 3122BA: manufactured by Sensient Technologies Corporation (surface treated pigment dispersion liquid) SENSIJET SMART Cyan 3154BA: manufactured by Sensient Technologies Corporation (treated pigment dispersion liquid on the surface) SENSIJET SMART Yellow 3074BA: manufactured by Sensient Technologies Corporation (surface treated pigment dispersion liquid) SENSIJET Black SDP2000: manufactured by Sensient Technologies Corporation (surface treated pigment dispersion liquid) Acrylic silicone resin emulsion: POLYSOL ROY6312, manufactured by Shows Highpolymer Co., Ltd., which has a solids content of 39.9% by weight, an average particle diameter of 171 nm, and a minimum film-forming temperature (MFT) of 20oC. Fluororesin A: LUMIFLON FE4300 emulsion, manufactured by Asahi Glass Co., Ltd., having a solids content of 50% by weight, the average particle diameter of 150 nm, and an MFT of 30oC or lower. KF-643: polyether modified silicone compound (manufactured by Shin-Etsu Chemical Co., Ltd., having 100% by weight active ingredient). Zonyl FS-300: polyoxyethylene perfluoroalkyl ether (manufactured by EI DuPont de Nemours and Company, having an active ingredient of 40% by mass) Surfynol 104E: acetylene glycol compound (manufactured by Nissin Chemical Industry Co., Ltd., having 50% by weight active ingredient, containing ethylene glycol) Softanol EP-7025: polyoxyalkylene alkyl ether (manufactured by Nippon Shokubai Co., Ltd., active ingredient: 100% by weight) Proxel GTL: an antifungal agent having 1.2 - benzisothiazolin-3-one as a main component (manufactured by Svecis Biological Limited, having an active ingredient of 20% by weight, containing dipropylene glycol) Amide compound of formula (1): amide compound represented by the following formula (1)
Amide compound of formula (2): represented by the following formula (2)
Amide compound of formula (3): amide compound represented by the following formula (3)
10 Formula (3) Compound of formula (8): compound represented by the following formula (8)
Formula (8) Compound of formula (10): compound represented by the following formula (10)
Formula (10) Amide compound of formula (V): amide compound represented by the following structural formula (V)
Formula (V) Compound of formula (VIIa) - (q): compound represented by the following general formula (VIIa) - (q) C6F13-CH2CH (OH) CH2OHCH2CH2O) 21-C12H25 General formula (VIIa) - (q) The properties The physical characteristics of each of the inkjet inks in Examples 1B to 13B were measured and evaluated using the following evaluation methods. The results are shown in table 4B. Note that the viscosity, pH, surface tension and viscosity measurements after moisture evaporation were performed in the same way as in examples 1A to 14A. TABLE 4B
-Ink Blasting Stage (5 Image Formation Stage- In the environment adjusted to 23oC ± 0.5oC, and 50% ± 5% RH, an inkjet engraving device (IPSiO GXe-5500, manufactured by Ricoh Company Limited) was set to give the same amount of deposition on the recording media 10 (MyPaper, manufactured by Ricoh Company Limited) by varying the drive voltage of a piezoelectric element to give the same amount of ink ejection. printing device of the inkjet recording device was set to “Flat Paper - High Speed” and then 15 images were formed. Then, examples 1B to 14B were evaluated by the following evaluation methods. The results are shown in the table 5B Note that the image density, wavy quantity, ejection stability, storage stability, 5 staining, fixation capacity and ink dispersion in the maintenance device were evaluated in the same way as in examples 1A to 14A . TABLE 5B
The modalities of the present invention are as follows: 10 <1> An inkjet ink containing: water; an organic solvent; a surfactant; and a colorant, in which the organic solvent contains at least one polyhydric alcohol having an equilibrium moisture content of 30% by mass or more at a temperature of 23oC and humidity and 80% RH, at least one amide compound represented by the general formula (I), and at least one selected from the group consisting of compounds represented by the following general formulas (11) to (IV)
General Formula (I) where R is a C4-C6 alkyl group,
General Formula (II) where R1 is a hydrogen atom or a C1-C2 group and R2 is a C1-C4 alkyl group,
General Formula (III) where R 'is a C1-C2 alkyl group, and R3 is a hydrogen atom, a C1-C8 alkyl group, a cyclic alkyl group or an aromatic group,
General Formula (IV) where R4 and R5 are both a C1-C8 alkyl group. <2> The inkjet ink according to <1>, wherein the colorant is a colorant containing at least one functional group selected from the group consisting of COOM, - SO3M, -PO3HM, -PO3M2, -CONM2, - SO3NM2, -NH-C6H4-COOM, -NH- C6H4-SO3M, -NH-C6H4-PO3HM, -NH-C6H4-PO3M2, -NH-C6H4-CONM2, and - NH-C6H4-SO3NM2, where M is an ion of quaternary ammonium. <3> The inkjet ink according to <1>, in which the colorant is a modified pigment, which has been modified with a group of geminal bisphosphonic acid or a group of geminal bisphosphonate. <4> The inkjet ink according to <3>, in which the dye is a modified pigment, which has been modified with a group represented by any of the following structural formula (1), (2), (3) or (4):
Structural Formula (1)
Structural Formula (2)
Structural Formula (3) where X + is Li +, K +, Na +, NH4 +, N (CH3) 4 +, N (C2H5) 4+. N (C3H7) 4+, or N (C4H9) 4 +
Structural Formula (4) where X + is Li +, K +, Na +, NH4 +, N (CH3) 4 +, N (C2H5) 4+. N (C3H7) 4+, or N (C4H9) 4+. 5 <5> The inkjet ink according to any one of <1> to <4>, wherein the organic solvent contains the amide compound represented by the following structural formula (V):
10 Structural Formula (V) <6> Inkjet ink according to any of <1> to <5>, where the colorant is a black pigment, a cyan pigment, a magenta pigment, a yellow pigment, or a mixture of the previous pigments. 15 <7> Inkjet ink according to any of <1> to <6>, where the surfactant contains at least one selected from the group consisting of a silicone surfactant, a fluorotensive, an acetylene glycol surfactant , and an acetylene alcohol surfactant. <8> Inkjet ink according to any of <1> to <7>, where inkjet ink has a dynamic surface tension of 35 mN / m or less at 25oC and with a time bubble duration on the surface of 15 ms in the maximum bubble pressure method. <9> An inkjet engraving method, containing: Apply stimulus to inkjet ink as defined in any of <1> to <8> to make inkjet ink, to thereby form an image on a recording medium, in which the stimulus is selected from heat, pressure, vibration and light. <10> An inkjet recording device, containing: <inkjet ink as defined in any of <1> to <8>; and an inkjet unit configured to apply stimulus to ink to make ink for inkjet, to thereby form an image on a recording medium, in which the stimulus is selected from heat, pressure, vibration and light. INDUSTRIAL APPLICABILITY
The inkjet ink of the present invention can form images of excellent image quality, particularly excellent image density, color saturation, and image strength (for example, water resistance and high strength), on plain paper, and has excellent drying speed, high-speed print matching and ejection stability from the nozzles, and is capable of forming high-quality images. Consequently, the inkjet ink of the present invention can be used appropriately for an ink cartridge, ink-etched matter, an ink-jet engraving device and an ink-jet etching method.
In addition, the inkjet ink of the present invention can form high quality images close to those of industrial printing with excellent drying properties and less bleeding (irregularities in image density) when it is used on ordinary printing paper (a recording medium having a low absorption of ink containing a support and a coating layer formed on at least one surface of the support, and to which a quantity of pure water transferred as measured by a dynamic scanning absorptometer with contact duration 100 ms is 1 ml / m2 to 35 ml / m2, and an amount of pure water transferred as measured with a contact duration of 400 ms is 3 ml / m2 to 40 ml / m2).
The inkjet recording device and the inkjet recording method of the present invention can be applied to various recordings of the inkjet recording system and, for example, can be particularly appropriately used as, or for a printer inkjet engraving, a facsimile device, a photocopier, a device composed of a printer-facsimile-photocopier. REFERENCE SIGNAL LISTS 1 paper feed tray 2 pressure plate 3 embossing paper 4 paper feed roller 5 base 6 pressure plate spring 7 transport cylinder 8 transport guide 9 transport guide 10 exposure glass 11 pinch roller 12 roller and paper feed for 5 10 15 20 manual paper feed 13 manual feed tray 14 in-line head 102 main body of the device 102 paper feed tray 103 paper discharge tray 104 cartridge loading section ink 105 control unit 111 top cover 112 front cover 115 front cover 131 guide rod 132 support 133 carriage 134 recording head 135 subtank 141 paper loading section 142 paper 143 paper feed roller 144 separation pad 145 guide 151 conveyor belt 152 counter cylinder 153 guide 154 compression member 155 end pressurization cylinder 156 charge cylinder 15 7 transport cylinder 5 158 tension cylinder 161 guide member 171 separation tab 172 paper discharge cylinder 173 paper discharge cylinder 10 181 sided double paper feed unit 182 manual paper feed unit 201 ink cartridge 241 ink bag 15 242 ink inlet 243 ink outlet 244 cartridge box on rotational axis 5 10 15

权利要求:
Claims (10)
[0001]
1. Inkjet ink characterized by comprising: water; an organic solvent; a surfactant; and a colorant, in which the organic solvent contains at least one polyhydric alcohol having an equilibrium moisture content of 30% by weight or more at a temperature of 23 ° C and humidity of 80% RH, at least one amide compound represented by the general formula (I), and at least one compound selected from the group consisting of compounds represented by the following general formula (II) for (IV):
[0002]
2. Inkjet ink according to claim 1, characterized in that the colorant is a colorant containing at least one functional group selected from the group consisting of -COOM, -SO3M, -PO3HM, -PO3M2, -CONM2, - SO NM, -NH-C6H4-COOM, -NH-C6H4-SO3M, -NH-C6H4-PO3HM, -NH-C6H4-PO3M2, -NH-C6H4-CONM2, and -NH-C6H4-SO3NM2, where M is one quaternary ammonium ion 5.
[0003]
3. Inkjet ink, according to claim 1, characterized by the fact that the colorant is a modified pigment, which has been modified with a geminal biophosphonic acid group or a geminal biophosphonate group. 10
[0004]
4. Inkjet ink according to claim 3, characterized by the fact that the colorant is a modified pigment, which has been modified with a group represented by any of the structural formulas shown below (1), (2) , (3) or (4):
[0005]
5. Inkjet ink according to claims 1 to 4, characterized in that the organic solvents comprise the amide compound represented by the following structural formula (V):
[0006]
6. Inkjet ink according to claims 1 to 5, characterized in that the colorant is a black pigment, a cyan pigment, a magenta pigment, a yellow pigment, or a mixture of the previous pigments.
[0007]
7. Inkjet ink according to claims 1 to 6, characterized by the fact that the surfactant contains at least one compound selected from the group consisting of a silicone surfactant, a fluoride surfactant, a acetylene glycol surfactant, and a acetylene alcohol surfactant.
[0008]
8. Inkjet ink according to claims 1 to 7, characterized by the fact that the inkjet ink has a dynamic surface tension of 35 mN / M or less at 25 ° C and with a time of surface bubble life of 15ms in a maximum bubble pressure method.
[0009]
9. Inkjet engraving method characterized by comprising: applying stimulus to the inkjet ink as defined in any one of claims 1 to 8; and an ink jet unit configured to apply stimulus to the ink to cause the ink jet to form an image on a recording medium, in which the stimulus is selected from heat, pressure, vibration and light.
[0010]
10. Inkjet engraving device comprising: inkjet ink as defined in claims 1 to 8; and an ink jet unit configured to apply ink stimulus to cause the ink to thus form an image on a recording medium, 15 in which the stimulus is selected from heat, pressure, vibration and light.

类似技术:

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同族专利:

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公开号 | 公开日

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EP2686393B1|2018-02-07|

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KR20130133044A|2013-12-05|

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BR112013023754A2|2016-12-06|

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US9028600B2|2015-05-12|

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AU2012229778B2|2014-08-07|

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WO2012124790A1|2012-09-20|

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JP2012207202A|2012-10-25|

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AU2012229778A1|2013-08-29|

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CN103429677A|2013-12-04|

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JP5825126B2|2015-12-02|

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CN103429677B|2014-10-01|

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EP2686393A4|2015-04-29|

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EP2686393A1|2014-01-22|

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US20140002539A1|2014-01-02|

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KR101493638B1|2015-02-13|

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JP2021046514A|2019-09-20|2021-03-25|株式会社リコー|Ink, ink set, printed matter, printing method, and printing apparatus|

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WO2021061769A1|2019-09-24|2021-04-01|Sanford L.P.|Reverse photochromic inks including encapsulated reverse photochromic colorants, and associated methods and writing instruments|

法律状态:
2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-07-16| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

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2020-07-21| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-12-01| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 09/03/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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JP2011055543|2011-03-14|

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JP2011-055543|2011-03-14|

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JP2012021907A|JP5825126B2|2011-03-14|2012-02-03|Ink jet ink, ink jet recording method, and ink jet recording apparatus|

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JP2012-021907|2012-02-03|

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PCT/JP2012/056791|WO2012124790A1|2011-03-14|2012-03-09|Inkjet ink, inkjet recording method, and inkjet recording device|

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