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    • 专利摘要:
    NON-AQUEOUS PHOTOPOLYMERIZABLE INK JET INK AND INK CARTRIDGE. A non-aqueous light-curing inkjet ink including as a light-curing monomer: (a) ethylene glycol dimethacrylate; and (b) caprolactone-modified dipentaerythritol hexaacrylate or ethylene oxide-modified trimethylolpropane trimethacrylate, or both, wherein the ink includes (a) the component by 10% by mass to 95% by mass of the total light-curing monomer, and the ink includes component (b), from 5% by mass to 90% by mass of the total light-curing monomer, and wherein the ink does not include a thinning solvent.
    公开号:BR112014021597B1
    申请号:R112014021597-9
    申请日:2013-02-27
    公开日:2021-07-06
    发明作者:Takao Hiraoka
    申请人:Ricoh Company, Ltd；
    IPC主号:
    专利说明:

    Technical Domain
    [0001] The present invention relates to a non-aqueous photopolymerizable inkjet ink and an ink cartridge. Previous Technique
    [0002] Light-curing inkjet inks containing (meth)acrylic esters, and light-curing inkjet inks containing (meth)acrylic esters and vinyl ethers, in combination, are widely known (see eg PTL 1).
    [0003] However, many of the monomers used in such light-curing inkjet inks exhibit toxicity. In particular, most (meth)acrylic esters, which are cheap and easily acquired, have high skin sensitization, causing allergy to the skin placed in contact with them, but the conventional technique has not provided any solution to this problem.
    [0004] Reducing the viscosity of a light-curing inkjet ink can be easily achieved by adding a diluting solvent, but the solvent released into the atmosphere by volatilization is not desirable, in view of the environmental impact.
    [0005] A light-curing water-based inkjet ink mixed with water is currently known, but penetration drying on an impermeable substrate is not anticipated, as described later. As a result, this requires a water evaporation step for a faster and more efficient process, which requires the installation of a heat source and so on, which is not desirable in view of energy conservation.
    [0006] For a further improvement in the performance of the light cured inkjet ink, it was desired to improve the resistance of a cured film thereof by increasing the durability against abrasion and to reduce the viscosity of the same, so as not to interfere with the inkjet discharge, even though it is thickened due to mixing with various materials such as pigments and additives. List of Citations Literature Patent PTL 1 Japanese Open Patent Application (JP-A) No. 2004-526820 Invention Summary Technical Problem
    [0007] The present invention is intended to solve conventional problems and achieve the following objective. That is, the present invention aims to provide a non-aqueous photopolymerizable inkjet ink that does not involve skin sensitization and has low viscosity and improved strength in a cured film. Solution to Problem
    [0008] Below are ways to solve the problems. That is: a non-aqueous photopolymerizable inkjet ink of the present invention, as a photopolymerizable monomer: (a) ethylene glycol dimethacrylate; and (b) caprolactone-modified dipentaerythritol hexaacrylate or ethylene oxide-modified trimethylolpropane trimethacrylate, or both, wherein the ink includes (a) the component by 10% by mass to 95% by mass of the total light-curing monomer, and the ink includes (b) the component, from 5% by mass to 90% by mass with respect to the total light-curing monomer, and wherein the ink does not include a thinning solvent. Advantageous Effects of the Invention
    [0009] According to the present invention, conventional problems can be solved, and a non-aqueous light cured inkjet ink that does not involve skin sensitization and has low viscosity and better strength in a cured film can be provided.
    [00010] Likewise, the non-aqueous light curing inkjet ink of the present invention is easy to handle because of its weak odor. Although a small amount of the uncured monomeric component still exists, a coating obtained using this ink does not present any problem with regard to skin sensitization and does not cause skin sensitization when touched with fingers, etc. Therefore, a coating with a high level of security can be provided. Brief Description of Drawings
    [00011] Figure 1 is a schematic diagram illustrating an example of an ink pack of an ink cartridge of the present invention.
    [00012] Figure 2 is a schematic diagram illustrating an example of an ink cartridge of the present invention containing an ink pack. Description of Modalities (Non-aqueous light-curing inkjet ink)
    [00013] A non-aqueous photopolymerizable inkjet ink of the present invention (hereinafter, it may also be referred to as an "ink") includes a photopolymerizable monomer, and further includes other components as needed. Non-aqueous light curing inkjet ink does not include a thinning solvent. <Light-curing monomer>
    [00014] The photopolymerizable monomer is: (a) an ethylene glycol dimethacrylate; and (b) caprolactone-modified dipentaerythritol hexaacrylate or ethylene oxide-modified trimethylolpropane trimethacrylate, or both. The light-curing inkjet ink includes (a) the component at 10% by mass to 95% by mass with respect to the total of the light-curing monomer and includes (b) the component at 5% by mass to 90% by mass with respect to the total light-curing monomer.
    [00015] The present inventors have found a photopolymerizable inkjet ink including diethylene glycol dimethacrylate with a significantly small SI value, indicating a degree of sensitization equal to 1.1 compared to methacrylate, as a photopolymerizable monomer with a suitable viscosity for inkjet discharge and with negative skin sensitization (Japanese Patent Application No. 2010-278177).
    [00016] The present inventors have found that a stronger cured film suitable for inkjet discharge can be obtained by adding a polyfunctional monomer with three or more functional groups with negative skin sensitization to diethylene glycol dimethacrylate at a ratio of adequate mixing and by adequate light irradiation. Here, the SI value is described in detail below.
    [00017] In particular, it was found that by adding caprolactone-modified dipentaerythritol hexaacrylate or ethylene oxide-modified trimethylolpropane trimethacrylate, or both, as a polyfunctional monomer with three or more functional groups with negative skin sensitization, to diethylene glycol dimethacrylate in a suitable mixing ratio, a film with a certain strength, yet with less amount of light radiated during curing, and a cured film with more strength can be obtained with irradiation of the same amount of light.
    [00018] The above photopolymerizable monomer, which is negative for skin sensitization, refers to a compound that corresponds to at least one of the following skin sensitization ratings (1) to (2). (1) A compound that has a Stimulation Index (SI value) indicating a degree of sensitization in an LLNA-based skin sensitization test (Local Lymph Node Assay) less than 3 (2) a compound rated "negative for skin sensitization" or "no skin sensitization" in your MSDS (Material Safety Data Sheet)
    [00019] Regarding (1), the compound with a SI value less than 3 is considered negative for skin sensitization, as described in the literature, for example, “Functional Material” (Kino Zairyou) September 2005, Vol. , No. 9, p. 55. Lower SI value means less skin sensitization. Thus, in the present invention, it is preferable to use the monomer with the lowest SI value and the monomer with the SI value less than 3, preferably 2 or less, and even more preferably one with a value equal to 1.6 or less is used.
    [00020] Diethylene glycol dimethacrylate, as component (a), is a bifunctional monomer with negative skin sensitization, which is inexpensive and can be easily purchased. Likewise, caprolactone-modified dipentaerythritol hexaacrylate and ethylene oxide-modified trimethylolpropane trimethacrylate, as component (b), is a polyfunctional monomer with three or more functional groups with negative skin sensitization, which is inexpensive and can be easily purchased. A content of component (a) in the photopolymerizable monomer is not particularly restricted, as long as it is comprised from 10% by mass to 95% by mass, and can be suitably selected according to the purpose. However, it is preferably 10% by mass to 70% by mass. Likewise, a content of component (b) in the photopolymerizable monomer is not particularly restricted, as long as it is comprised from 5% by mass to 90% by mass, and can be suitably selected according to the purpose. However, it is preferably 30% by mass to 90% by mass. <Other components>
    [00021] The other components are not particularly restricted and can be properly selected according to the purpose. However, other photopolymerizable monomers, photoradical polymerization initiators, polymerization accelerators, dyes and others are exemplified. <<Another light-curing monomer>>
    [00022] In addition to those that have negative skin sensitization, the following (meth)acrylates and (meth)acrylamides can be used in combination with the other light-curing monomer, even if the compounds have some skin sensitization problems by themselves or present unconfirmed skin sensitization as long as they do not cause a problem such as ink.
    [00023] The other photopolymerizable monomers are not particularly restricted and can be suitably selected according to the purpose. However, examples thereof include ethylene glycol di(meth)acrylate, neopentylglycol di(meth)acrylate hydroxypivalate, Y-butyrolactone acrylate, isobornyl(meth)acrylate, formalized trimethylolpropane mono(meth)acrylate, di(meth) polytetramethylene glycol acrylate, trimethylolpropane benzoate (meth)acrylate, diethylene glycol diacrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, [CH2=CH-CO-(OC2H4) n-OCOCH=CH2 (n « 4), ditto (n « 9), ditto (n « 14), ditto (n « 23)], dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, dimethacrylate of polypropylene glycol [CH2=C(CH3)-CO-(OC3H6)n-OCOC(CH3)=CH2 (n « 7)], 1,3-butanediol diacrylate, 1,4-butanediol di(meth)acrylates, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentylglycol di(meth)acrylates, tricyclodecanedemethanol di(meth)acrylates, bisphenol A di(meth)acrylate modified with propylene oxide , dipentaerythritol hexa(meth)acrylate, (meth)acryloyl morpholino, 2-hydroxypropyl(meth)acrylamide, tetramethylolmethane tetra(meth)acrylate modified with propylene oxide, dipentaerythritol hydroxypenta(meth)arylate, hydroxypenta(meth)arylate caprolactone-modified dipentaerythritol, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, trimethylolpopane triacrylate, ethylene oxide-modified trimethylolpopane triacrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, tri(meth)acrylate ) caprolactone modified trimethylolpropane acrylate, pentaerythritol tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, ethoxylated neopentylglycol di(meth)acrylate, neopentylglycol di(meth)acrylate modified with oxide propylene, propylene oxide modified glyceryl tri(meth)acrylate, polyester di(meth)acrylate, polyester tri(meth)acrylate, polyester tetra(meth)acrylate, powdered penta(meth)acrylate polyester, polyester poly(meth)acrylate, N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylformamide, polyurethane di(meth)acrylate, polyurethane tri(meth)acrylate, polyurethane tetra(meth)acrylate, penta(meth) polyurethane acrylate, polyurethane poly(meth)acrylate and so on. <<Photoradical Polymerization Initiator>>
    [00024] A photoradical polymerization initiator is preferably used in the non-aqueous photopolymerizable inkjet ink of the present invention. The photoradical polymerization initiator is not particularly restricted and can be suitably selected according to the purpose. However, it is more preferable to use those that have negative skin sensitization.
    [00025] (meth)acrylic esters and (meth)acrylamides are known to be ionically polymerizable. An ionic polymerization initiator is generally expensive. In addition, since it generates strong acids and slightly strong bases even in a state where there is no radiated light, special care must be taken to impart resistance to acids and bases in paint supply pathways in a paint coating system. inkjet. Therefore, there is a restriction in the selection of the members that make up the inkjet coating system.
    [00026] On the contrary, since it is possible to use a photoradical polymerization initiator that is cheap and does not generate strong acids or strong bases for the ink of the present invention, the ink can be manufactured at reasonable cost, and selection of members constituting the inkjet coating system is easy. Here, a polymerization reaction proceeds without using a polymerization initiator, if a high-energy light source such as an electron beam, α-ray, β-ray, y-ray and X-ray is used. However, this is a problem conventionally known to date, and is not particularly explained in the present invention.
    [00027] As the photoradical polymerization initiator, a molecule cleavage photopolymerization initiator and a hydrogen abstraction photopolymerization initiator can be exemplified.
    [00028] Examples of the molecule cleavage photopolymerization initiator include: 2,2-dimethoxy-1,2-diphenyletan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1- one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2] -methylpropionyl)benzyl]phenyl}-2-methyl-1-propan-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2 -benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1,2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)butan-1-one, oxide of bis(2,4,6-trimethylbenzoyl)phenylphosphine, bis(2,6-dimethoxybenzolyl)-2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzoylphosphine oxide, 1,2-octanedion-[4 -(phenylthio)-2-(o-benzoyloxime)], ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), [4 - (methylphenylthio)phenyl]phenylmethanone and so on.
    [00029] Examples of hydrogen abstraction photopolymerization initiator include: benzophenone compounds like benzophenone, methylbenzophenone, methyl-2-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl sulfide, phenylbenzophenone and so on; and thioxanthone compounds such as 2,4-diethylthioxanthone, 2-chlorothioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, and so on.
    [00030] The negative skin sensitization photoradical polymerization initiator is not particularly restricted, as long as it is a compound corresponding to at least one of the skin sensitization assessment (1) to (2), and can be suitably selected accordingly with the purpose. Examples thereof include 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)butan-1-one, 2-methyl-1-[4-(methylthio)phenyl]- 2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1,2,4-diethylthioxanthone and so on. These can be used alone or in combination of two or more of them. <<Polymerization Accelerator>>
    [00031] Amines can be used in combination as the polymerization accelerator with the photoradical polymerization initiator.
    [00032] Examples of the polymerization accelerator include ethyl p-dimethylaminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, methyl p-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, butoxyethyl p-dimethylaminobenzoate and so on. <<Dye>>
    [00033] The non-aqueous light curing inkjet ink can be a clear ink that does not include a dye, or it can include the dye as needed. In the case of a clear paint that needs to be colorless and transparent, it is advisable to use materials such as polymerization initiator with less coloration.
    [00034] The colorant is not particularly restricted, and various pigments such as inorganic pigments, organic pigments, black pigments, yellow pigments, magenta pigments, cyan pigments, white pigments and so on hitherto known can be properly selected according to purpose.
    [00035] Examples of black pigments include carbon black, manufactured by an oven method or by a channel method.
    [00036] Examples of yellow pigments include example pigments from the yellow pigment series, such as yellow pigment 1, yellow pigment 2, yellow pigment 3, yellow pigment 12, yellow pigment 13, yellow pigment 14, yellow pigment 16, yellow pigment 17, pigment yellow 73, pigment yellow 74, pigment yellow 75, pigment yellow 83, pigment yellow 93, pigment yellow 95, pigment yellow 97, pigment yellow 98, pigment yellow 114, pigment yellow 120, pigment yellow 128, pigment yellow 129, pigment yellow 138, Yellow Pigment 150, Yellow Pigment 151, Yellow Pigment 154, Yellow Pigment 155, Yellow Pigment 180, and so on.
    [00037] Examples of magenta pigments include pigments from the red pigment series, such as pigment red 5, pigment red 7, pigment red 12, pigment red 48 (Ca), pigment red 48 (Mn), pigment red 57 (Ca), Pigment Red 57:1, Pigment Red 112, Pigment Red 122, Pigment Red 123, Pigment Red 168, Pigment Red 184, Pigment Red 202, Pigment Violet 19 and so on.
    [00038] Examples of cyan pigments include pigments from the blue pigment series, such as blue pigment 1, blue pigment 2, blue pigment 3, blue pigment 15, blue pigment 15:3, blue pigment 15:4, blue pigment 16, blue pigment 22, pigment blue 60, blue VAT 4, blue VAT 60 and so on.
    [00039] Examples of white pigments include: alkaline earth metal sulphates such as barium sulphate; alkaline earth metal carbonates such as calcium carbonate; silicas such as fine powder silicic acid and synthetic silicates; calcium silicate, alumina, alumina hydrates, titanium oxide, zinc oxide, talc, clay and so on.
    [00040] Likewise, various inorganic pigments or organic pigments can be used according to the need, in view of the physical properties.
    [00041] In addition, in the non-aqueous light-curing inkjet ink, it is possible to use as the other components, according to the need: polymerization inhibitors such as 4-methoxy-1-naphthol, methyl-hydroquinone, hydroquinone, t- butylhydroquinone, di-t-butylhydroquinone, methoquinone, 2,2'-dihydroxy-3,3'-di-(α-methylcyclohexyl)-5,5'-dimethyldiphenylmethane, p-benzoquinone, di -t-butyldiphenylamine, 9,10-di-n-butoxyanthracene, 4,4'-[1,10-dioxo-1,10-decanedylbis(oxy)]bis[2,2,6,6-tetramethyl] -1-piperidinyloxy and so on; polymeric pigment surfactants or dispersants containing a polar group, such as esters of higher fatty acids containing polyether, an amino group, a carboxyl group or a hydroxyl group, polyether containing polydimethylsiloxane compounds, an amino group, a carboxyl group or a hydroxyl group in a side chain or at one end, and fluoroalkyl compounds containing polyether, an amino group, a carboxyl group or a hydroxyl group.
    [00042] The physical properties of the non-aqueous light curing inkjet ink are not particularly restricted and can be properly selected according to the purpose. However, it is desirable that they meet the required specifications of the inkjet discharge head to be used. Various discharge heads are commercially available from many manufacturers, including those having a wide range of temperature control functions. In view of such circumstances, the ink has a viscosity preferably from 2mPa^s to 150mPa^s. Especially, the viscosity at 25°C is preferably from 5mPa^s to 18mPa^s. However, as above, it is also possible to make use of the temperature control function presented by the discharge heads. When viscosity is very high at 25°C, the head can be heated to lower the ink viscosity as needed. Considering this, and assuming that the heating condition is 60°C, the ink viscosity at 60°C is preferably equal to 2mPa^s to 20mPa^s, and more preferably equal to 5mPa^s to 18mPa^s.
    [00043] The viscosity of the ink is considered to be successfully reduced as long as the ink meets the viscosity of 5mPa^s to 18mPa^s at 25°C or 2mPa^s to 20mPa^s at 60°C.
    [00044] Likewise, considering the film strength of a film formed by curing the ink based on the scratching hardness by a pencil method indicated by JIS-K-5600-5-4, the film strength is preferably to hardness of pencil B in a curing case with a luminosity of 0.2 mW/cm2 and an irradiation intensity equal to 1200 mJ/cm2; the film strength is more preferably the hardness of HB pencil in the case of curing with a luminosity of 0.2 mW/cm2 and an irradiation intensity of 800 mJ/cm2; and the film strength is even more preferably equal to the hardness of pencil B, in the case of curing with a luminosity of 0.2 mW/cm2 and an irradiation intensity of 400 mJ/cm2.
    [00045] Cured film strength is considered to be successfully improved if the film strength is above the preferred film strength. (Cartridge)
    [00046] An ink cartridge of the present invention includes the above ink of the present invention and a container, and additionally includes other members, such as an ink pack, as required.
    [00047] An ink of the present invention can be used in a container, which is used as an ink cartridge. This way, there's no need to touch ink directly in operations such as changing ink, and there's no need to worry about smudges on fingers or clothing. In addition, you can prevent foreign material, such as dust, from getting into the ink.
    [00048] The container is not particularly limited, and its shape, structure, size and material and other aspects are suitably selected according to the purpose. For example, the container preferably includes an ink pack formed from a laminated aluminum film, or resin film.
    [00049] The above ink cartridge is explained with reference to Figure 1 and Figure 2. Figure 1 is a schematic diagram illustrating an example of an ink cartridge 241 ink pack, and Figure 2 is a schematic diagram illustrating an ink cartridge 200 in which the ink pack 241 of Figure 1 is contained in a cartridge case 244.
    [00050] As illustrated in Figure 1, an ink is filled in the ink pack 241 from an ink inlet 242 and then the air remaining in the ink pack is discharged, and the ink inlet 242 is closed by merger. In use, ink is supplied to the apparatus by placing a needle from the apparatus body into an ink outlet 243 of a rubber member. Ink package 241 is formed from a packaging material such as laminated aluminum film without air permeability. Thus, as illustrated in Figure 2, it is generally contained in a plastic cartridge case 244, which is used as an ink cartridge 200 by detachably mounting various inkjet recording apparatus.
    [00051] It is preferable that the ink cartridge of the present invention seals detachably mounted in an inkjet recording apparatus. In this way, ink replacement or replacement can be simplified, and practicality can be improved.
    [00052] A coated substrate is not particularly restricted and can be suitably selected according to the purpose. Examples thereof include paper materials, plastics, metals, ceramics, glass and composites thereof. Since a penetration drying effect can be expected with a substrate having high quality paper absorbency, it is possible to use a water-based ink or an oil-based ink which does not dry quickly. In contrast, with an impermeable substrate such as gloss coated paper, plastic films, plastic molds, ceramics, glass, metals, and so on, it is more practical to use a quick-drying ink.
    [00053] Therefore, the impermeable substrate is preferable as the coated substrate, since the ink of the present invention is cured immediately by light irradiation. Among these, polyethylene, polypropylene, polyethylene terephthalate, polycarbonate, an ABS resin, polyvinyl chloride, polystyrene, other polyester, polyamide, vinyl materials and plastic films or plastic molds made from composite materials thereof are more preferable. Examples
    [00054] From this point onwards, the present invention is specifically explained by the demonstration of examples and comparative examples, but the present invention is not limited by these examples. <<SI value assessment method>>
    [00055] An SI value of a light-curing monomer, and so on, was measured in the manner described below according to a skin sensitization test based on an LLNA (local lymph node assay). [Test materials] <<Positive control>>
    [00056] As the positive control, an α-hexylcinnamaldehyde (HCA; manufactured by Wako Pure Chemical Industries, Ltd.) was used. <<Vehicle>>
    [00057] As a vehicle, a mixture of acetone (manufactured by Wako Pure Chemical Industries, Ltd.) and olive oil (manufactured by Fudimi Pharmaceutical Co. Ltd.) in a volume ratio of 4:1 was used. <<Used animals>>
    [00058] Before being treated with the test substances, the positive control or the vehicle control, female mice were acclimated for 8 days, including 6 days of quarantine. No abnormalities were found in all animals during the quarantine/acclimatization period. Based on the body weights measured 2 days before the start of sensitization, they were classified into 2 groups (4 mice/group) by the stratified random sampling method of body weight, so that the body weight of each individual was ± 20% of the average body weight of all individuals. Each animal was 8 weeks to 9 weeks old at the time of onset of sensitization. The animals remaining after categorization were excluded from the test.
    [00059] The animals were individually identified by applying oily paint to their tails during the test period, and also their cages were identified. <<Accommodation environment>>
    [00060] During the entire period of housing, including the quarantine/acclimatization period, the animals were housed in an animal room with a barrier system, which was defined as follows: temperature from 21°C to 25°C, 40 % to 70% relative humidity, 10 times/hour to 15 times/hour air circulation frequency and 12 hours in the lighting cycle (lighting from 7:00 to 19:00). The housing cages used were those made of polycarbonate, and four animals were housed in each cage.
    [00061] The animals received ad libitum solid diet for MF laboratory animals (manufactured by Oriental Yeast Co., Ltd.). Likewise, using a water supply bottle, they were given tap water ad libitum, to which sodium hypochlorite (PURELOX, manufactured by OYALOX Co., Ltd.) was added, so that the chlorine concentration was equal to about 5 ppm. The padding used was SUNFLAKE (fir, shavings obtained with an electric planer) (manufactured by Charles River Inc.). Diet and feeding equipment were autoclaved (121 °C, 30 min) before use.
    [00062] The cage and pad were replaced with new ones at the time of categorization and removal of the ear lymph node (i.e., the time when the animals were transferred from the animal room) and the water supply bottle and shelf were replaced by new ones at the time of categorization. [Test Method] <<Composition of the group >>
    [00063] The group composition used for measuring the SI value is shown in table 1. Table 1
    [Preparation] <<Test substance>>
    [00064] Table 2 shows the quantity of the test substance. The test substance was weighed into a measuring flask, and the volume of the test substance was made up to 1 ml with vehicle. The solution thus prepared was placed in an airtight container under protection from light (made of glass). Table 2
    <<Positive control>>
    [00065] 0.25 g of HCA was accurately weighed, and a vehicle was added to the HCA to have the volume of 1 mL, to thereby prepare a 25.0% w/v solution. The solution thus prepared was placed in an airtight container under protection from light (made of glass). <<BrdU>>
    [00066] In a measuring vial, 200 mg of 5-bromo-2'-deoxyuridine (BrdU, manufactured by NACALAI TESQUE, Inc.) was accurately weighed. Then, physiological saline (manufactured by OTSUKA PHARMACEUTICAL CO., LTD.) was added to the measuring flask and dissolved by applying ultrasonic waves. The volume of the resulting solution was adjusted to 20 ml to prepare a solution with a concentration equal to 10 mg/ml (BrdU preparation solution). The preparation solution was filter sterilized with a sterile filter filter and placed in a sterile container. <<Preparation Day and Storage Period>>
    [00067] The positive control preparation was done the day before the start of sensitization and stored in a cool place, except during use. Vehicle and test substance preparations were prepared on the day of sensitization. The BrdU preparation solution was prepared 2 days before administration and stored in a cold place until the day of administration. [Awareness and administration of BrdU] <<Awareness>>
    [00068] Each of the test substance preparations (25 µL), the positive control preparation and the vehicle were applied to both ears of each animal using a micropipette. This treatment was performed once a day for three consecutive days. <<BrdU Administration>>
    [00069] About 48 hours after the final sensitization, the BrdU preparation (0.5 mL) was administered intraperitoneally once to each animal. [Observation and Examination] <<General conditions>>
    [00070] All animals used for the test were observed once or more times a day from the day of initiation of sensitization until the day of atrial lymph node removal (ie the day when the animals were transferred from the animal room) . Notably, the day of observation was counted from the day of onset of sensitization, being considered as Day 1. <<Measurement of body weight>>
    [00071] The body weight of each animal was measured on the day of initiation of sensitization and on the day of atrial lymph node removal (ie the day when the animals were transferred from the animal room). Likewise, the mean of body weights and their standard error were calculated for each group. <<Auricular lymph node removal and mass medication>>
    [00072] About 24 hours after administration of BrdU, the animals were allowed to be euthanized, and their auricular lymph nodes were sampled. The tissue surrounding each atrial lymph node was removed, and the atrial lymph nodes of both ears were weighed at the same time. In addition, the mean weights of the auricular lymph nodes and their standard error were calculated for each group. After measuring the weights, each subject's atrial lymph nodes were stored in the frozen state using a BIO MEDICAL REFRIGERATOR, set to -20°C. <<BrdU intake measurement>>
    [00073] After returning to room temperature, the auricular lymph nodes were crushed with the gradual addition of saline and suspended therein. The suspension thus obtained was filtered and then placed in the wells of a 96-well microplate, with 3 wells, being used per individual. The suspensions thus dispensed were measured for BrdU intake by the ELISA method. The reagents used were those from a commercially available kit (Cell Proliferation ELISA, BrdU colorimetric, Cat. No. 1647229, manufactured by Roche Diagnostics Inc.). A multiplate reader (FLUOSTAR OPTIMA, manufactured by BMG LABTECH Inc.) was used to measure the absorbance of each well (OD: 370 nm to 492 nm, corresponding to the intake of BrdU), and the mean absorbance of the 3 wells for each subject was used as the BrdU measurement for the subject. [Evaluation of results] <<Calculation of Stimulation Index (SI)>>
    [00074] As shown in the formula below, the BrdU intake measurement for each subject was divided by the average of the BrdU intake measurements in the vehicle control group to calculate the SI value for the subject. The SI value of each test group was the mean of the individuals' SI values. Likewise, the standard error of the SI values was calculated for each test group. Notably, the SI value has been rounded to the second decimal place and displayed to the first decimal place.
    [Examples 1 to 10, Comparative Examples 1 to 2]
    [00075] Paints were obtained by mixing the materials (a) to (c) below, in a mixing ratio indicated in the respective columns of Examples 1 to 10 and Comparative Examples 1 to 2 in Table 3 (the numbers are are in bulk parts). (a) Diethylene glycol dimethacrylate as a bifunctional monomer with negative skin sensitization (b) Dipentaerythritol hexaacrylate modified with caprolactone and trimethylolpropane trimethacrylate modified with ethylene oxide as a polyfunctional monomer with negative skin sensitization (c) Initiator of photoradical polymerization with negative skin sensitization
    [00076] The details of a, b1 to b2 and c1 to c3 in Table 3 are as follows. A value in parentheses at the end is the SI value of the LLNA test from the skin sensitization test (1). In addition, a description of "negative skin sensitization" or "no skin sensitization" in parentheses at the end denotes the assessment of "negative skin sensitization" or "no skin sensitization" in the MSDS (sheet of material safety data) in the skin sensitization test (2).
    [00077] The SI value valuation method is as described above. a: Diethylene glycol dimethacrylate "2G", manufactured by Shin-Nakamura Chemical Co., Ltd. (1.1) b1: Caprolactone modified dipentaerythritol hexaacrylate "DPCA60", manufactured by Nippon Kayaku Co., Ltd. (skin sensitization) negative, evaluated on MSDS) (Test method: OECD test guideline 406) b2: Trimethylolpropane trimethacrylate modified with ethylene oxide "TMPT-3EO", manufactured by Shin-Nakamura Chemical Co., Ltd. (1.0) c1: 1 -hydroxycyclohexylphenylketone (absence of skin sensitization, assessed on MSDS) (Test method: OECD test guideline 406) c2: 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl) )butan-1-one (no skin sensitization, assessed on MSDS) (Test method: OECD test guideline 406) c3: Equimolar mixture of 2,4-diethylthioxanthone (1.4) and 2-ethyl-p-dimethylaminobenzoate hexyl (no skin sensitization, assessed on MSDS) (Test method: OECD test guideline 406)
    [00078] For each ink, the viscosity at 25 °C, 45 °C and 60 °C (mPa's) and the film strength were measured. The results are shown in Table 3.
    [00079] Viscosity was measured by adjusting the circulating water temperature at constant temperature to 25 °C, 45 °C and 60 °C by a rotating cone-plate viscometer, manufactured by Toki Sangyo Co., Ltd. The temperature temperature of 25 °C assumes a typical temperature and temperatures of 45 °C and 60 °C assume specifications for commercial inkjet discharge heads, such as GEN4, manufactured by Ricoh Printing Systems, Ltd., for example, with which the heating is possible.
    [00080] Here, the viscosity measurement at 45 °C or 60 °C was omitted if the paints had a sufficiently low viscosity without heating.
    [00081] Regarding the film strength, the ink was subjected to ink jet discharge on a commercially available polycarbonate film ("IUPILON E-2000", manufactured by Mitsubishi Engineering-Plastics Corporation, with a thickness of 100 μm) , which was cured by light irradiation by an "LH6" UV irradiating device, manufactured by Fusion Systems Co., Ltd. with an illumination of 0.2 mW/cm2, and thus a solid film was obtained. This film was evaluated for scratch hardness by the pencil method indicated by JIS-K-5600-5-4. Pencil hardness is H, F, HB and B, in descending order of hardness.
    [00082] First, the ink was handled as described below. The paint was placed in an aluminum pouch with a shape illustrated in Figure 1, which was sealed so that no air bubbles were drawn into it. The sealed pouch with the ink was placed in a plastic in the cartridge illustrated in Figure 2. In a wrapper to contain this cartridge, an ink path was disposed from the cartridge to the GEN4 head, manufactured by Ricoh Printing Systems, Ltd. Desse In this way, the ink was subjected to inkjet discharge, and a solid film was prepared. Here, an ink droplet application amount was adjusted so that the solid film had a thickness of about 30 µm.
    [00083] The solid printed film prepared in this way was cured under light conditions of 400 mJ/cm2, 800 mJ/cm2 and 1200 mJ/cm2 in a wavelength region corresponding to a UVA region, and was subjected to the test of film resistance. Table 3
    * 1: The value indicates an amount in one state, including carbon black "No. 10" manufactured by Mitsubishi Chemical Corporation, and a dispersant "SOLSPERSE 32000" manufactured by Lubrizol Japan Ltd. with a mass ratio of 3:1 . * 2: Viscosity was not measured as discharge possibly occurred below temperature. *3: Not cured (with liquid residue or adhesion). * 4: No evaluation was performed as it was not possible to download.
    [00084] From Examples 1 to 3, by using the bifunctional monomer a and the monomer b1 with a high viscosity, but considered to be easily polymerized due to its 6 functional groups, it was confirmed that a film with sufficient strength (hardness of pencils F or H) can be obtained by irradiating light at 1,200 mJ/cm2. However, as in Comparative Example 1, a sufficiently cured film could not be obtained under the above evaluation conditions when the polyfunctional monomer with three or more functional groups was not used in combination.
    [00085] Furthermore, it was confirmed that a film with a certain resistance with lower irradiation intensity, or a film with more resistance with the same irradiation intensity can be obtained by adjusting the mixing rate of b1.
    [00086] However, as in Comparative Example 2, it was confirmed that ink jet discharge was not possible due to the excessively high viscosity of the ink with an excess amount of b1.
    [00087] From Examples 4 to 6, by adjusting the mixing ratio of the bifunctional monomer a and the polyfunctional monomers b, it was confirmed that the film with a pencil hardness H, by irradiation with light at 1200 mJ/cm2 can be obtained with the ink having a viscosity lower than that of Example 3. There is a possibility that the heating conditions may be facilitated if the ink has low viscosity, which is preferable from an energy conservation point of view. Likewise, by irradiation with light at 800 mJ/cm2, a film with pencil hardness H was obtained, which was stronger than the other examples.
    [00088] From Examples 2, 7 and 8, it was confirmed that different types of photoradical polymerization initiators can be used. Photoradical polymerization initiators can be suitably selected as needed because they vary in terms of solubility, degree of coloration, price and other factors depending on their types.
    [00089] From Examples 2, 9 and 10, although they are inferior in terms of comparing to those without dyes, it was confirmed that those that had dyes are inferior compared to those without dyes, but they could provide films with some degree of resistance if a selection of the photoradical polymerization initiator was appropriate.
    [00090] In the present case, the odor of the paints of all examples and comparative examples was weak, and considerations regarding special handling were not necessary.
    [00091] Also Table 3 shows the results of irradiation with light with an illumination of 0.2 mW/cm2. For example, in Example 1, a case with a luminosity of 2 mW/cm2 and an irradiation intensity of 1,200 mJ/cm2 resulted in an uncured film. Furthermore, in Example 3, with a luminosity of 2 mW/cm2, a case with an irradiation intensity of 1,200 mJ/cm2 resulted in a film strength of a H pencil hardness, and in a case with an irradiation intensity of 800 mJ/cm2 resulted in a film strength of a pencil hardness F, and no difference was observed in the case of luminosity of 0.2 mW/cm2. However, a case with an irradiation intensity equal to 400 mJ/cm2 resulted in a film strength of a pencil hardness less than 6B. Furthermore, in Example 4 with a luminosity of 2 mW/cm2, a case with an irradiation intensity of 1,200 mJ/cm2 resulted in a film strength of an HB pencil hardness, and in a case with an irradiation intensity of 800 mJ/cm2 resulted in a film strength of a B pencil hardness.
    [00092] As described above, it was confirmed that irradiation with light with less luminosity was more effective in order to obtain a film with a certain resistance with less irradiation intensity, or a film with more resistance with the same irradiation intensity.
    [00093] Below are described aspects of the present invention: <1> Non-aqueous light curing ink jet ink, including as a light curing monomer: (a) ethylene glycol dimethacrylate; and (b) caprolactone-modified dipentaerythritol hexaacrylate or ethylene oxide-modified trimethylolpropane trimethacrylate, or both, in which the paint includes (a) the component in 10% by mass to 95% by mass of the total total light-curing monomer and includes (b) the component at 5% by mass to 90% by mass of the total light-curing monomer, and wherein the ink does not include a thinning solvent. <2> Ink cartridge, including: the inkjet ink according to <1>; and a container.
    权利要求:
    Claims (8)
    [0001]
    1. Light-curing inkjet ink characterized by the fact that it comprises, as a light-curing monomer: (a) diethylene glycol dimethacrylate; and (b) caprolactone-modified dipentaerythritol hexaacrylate or ethylene oxide-modified trimethylolpropane trimethacrylate, or both, wherein the light-curing inkjet ink is negative for skin sensitization, wherein an amount of the component (a ) in the paint is 10% by mass to 95% by mass with respect to the light-curing monomer as a whole, and an amount of component (b) in the paint is from 5% by mass to 90% by mass with respect to the light-curing monomer as a whole, and in which the ink is free from a thinning solvent.
    [0002]
    2. Photopolymerizable inkjet ink according to claim 1, characterized in that it further comprises a photoradical polymerization initiator, wherein the photoradical polymerization initiator is at least one selected from the group consisting of 2,2-dimethoxy- 1,2-diphenyletan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy- 2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methyl-1-propan-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1,2- dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)butan-1-one, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,6) oxide -dimethoxybenzolyl)-2,4,4-trimethylpentylphosphine, 2,4,6-trimethylbenzoylphosphine oxide, 1,2-octanedion-[4-(phenylthiol)-2-(o-benzoyloxime)], ethanone-1-[9 -ethyl-6-(2-methylbenzoyl)-9H -carbazol-3-yl]-1-(O-acetyloxime), [4-(methylphenylthio)phenyl]phenylmethanone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl )butan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1,2 ,4-diethylthioxanthone, benzophenone, methyl-benzophenone, methyl-2-benzylbenzoate, 4-benzoyl-4'-methyldiphenyl sulfide, phenylbenzophenone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, isopropylthioxanthone and 1-chloro-4-propylthioxanthone.
    [0003]
    3. Light-curing inkjet ink, according to claim 1, characterized in that it further comprises a dye.
    [0004]
    4. Light-curing inkjet ink, according to any one of claims 1 to 3, characterized in that the ink has a viscosity of 5 mPa-s to 18 mPa-s at 25 °C.
    [0005]
    5. Light-curing inkjet ink, according to any one of claims 1 to 3, characterized in that the ink has a viscosity of 2 mPa-s to 20 mPa-s at 60 °C.
    [0006]
    6. Light-curing inkjet ink according to any one of claims 1 to 5, characterized in that the scraping hardness of a cured film is F or harder by a pencil method based on JIS-K-5600 -5-4, where the cured film is formed by curing the ink with a luminosity of 0.2 mW/cm2 and an irradiation intensity of 1,200 mJ/cm2.
    [0007]
    7. Light-curing inkjet ink, according to any one of claims 1 to 6, characterized in that the amount of component (b) in the ink is from 30% by mass to 90% by mass.
    [0008]
    8. Ink cartridge (200) characterized in that it comprises: the inkjet ink as defined in any one of claims 1 to 7; and a container (241).
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    同族专利:
    公开号 | 公开日
    EP2820094A1|2015-01-07|
    US20150042731A1|2015-02-12|
    BR112014021597A2|2017-06-20|
    US9574097B2|2017-02-21|
    EP2820094B1|2019-12-04|
    RU2014139844A|2016-04-20|
    KR20140117589A|2014-10-07|
    KR101657387B1|2016-09-13|
    WO2013129699A1|2013-09-06|
    JP2013181114A|2013-09-12|
    CN104144992A|2014-11-12|
    EP2820094A4|2015-02-25|
    JP5803746B2|2015-11-04|
    CA2866026A1|2013-09-06|
    CN104144992B|2016-05-11|
    CA2866026C|2016-07-12|
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-09-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-03-02| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-05-04| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-07-06| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 27/02/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2012-046301|2012-03-02|
    JP2012046301A|JP5803746B2|2012-03-02|2012-03-02|Photopolymerizable inkjet ink, ink cartridge|
    PCT/JP2013/056198|WO2013129699A1|2012-03-02|2013-02-27|Non-aqueous photopolymerizable inkjet ink and ink cartridge|
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