• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    imaging method, imaging apparatus, and recorded matter. providing an imaging method, including: a pre-treatment liquid application step for applying a pre-treatment liquid to a recording medium including a substrate and a coating layer on at least one surface of the substrate, in that the pre-treatment liquid is applied to a surface of the recording layer with the coating layer; a drying step for drying the recording medium to which the pre-treatment liquid has been applied; and an imaging step for forming an image on the recording medium after drying by discharging a water-based ink by the inkjet method, wherein the pre-treatment liquid includes a water-soluble cationic polymer, a salt of an organic acid and water, and wherein the water-based ink includes water and negatively charged colored particles including a colorant.
    公开号:BR112015000654B1
    申请号:R112015000654-0
    申请日:2013-07-05
    公开日:2021-09-08
    发明作者:Shosuke AOAI；Tsutomu Maekawa；Michihiko Namba；Shinya Seno；Hiroshi Gotou；Akihiko Gotoh
    申请人:Ricoh Company, Ltd；
    IPC主号:
    专利说明:

    Technical Field
    [0001] The present invention relates to an imaging method, an imaging apparatus and an etched matter using a water-based ink and a pretreatment liquid. Background of the technique
    [0002] In recent years, a recording medium including a coating layer used as offset printing paper has been employed in a water-based inkjet imaging method. However, unlike a recording medium without a coating layer, inks hardly penetrate the recording medium including a coating layer. Thus, coalescence of droplets occurs on paper, and there is a problem of smearing between inks of different colors or between inks and the recording medium.
    [0003] In order to solve the problem, in a case where a water-based ink is discharged onto a recording medium including a coating layer, a method is proposed to prevent staining by promoting the agglomeration of a pigment in the ink-based in water.
    [0004] Specifically, in the method, a recording medium designed for water-based ink jet imaging is prepared and used by treating a recording medium including a coating layer so as to impart agglomeration promoting function of pigment. However, this method has a problem where the recording medium is limited.
    [0005] Meanwhile, for a recording medium without a coating layer such as plain paper, a method for applying a pre-treatment liquid that agglomerates a pigment into an ink immediately before ink discharge is proposed.
    [0006] For example, an inkjet engraving method is proposed for applying to plain paper a reaction liquid including polyallylamine and an ink composition including a colorant and a resin emulsion for printing (see PTL 1).
    [0007] Further, an inkjet recording method for applying to plain paper a reaction liquid including an ammonium salt of an organic acid and a water-soluble cationic polymer and an ink composition including a colorant and a resin emulsion for printing (see PTL 2).
    [0008] These proposals are directed to plain paper not including coating layer as the recording medium. When the recording methods by these proposals are applied to a case where a recording medium including a coating layer is used and a large amount of a pre-treatment liquid is used, eg high speed continuous printing, there are risks failure of a device carrying member and degradation of image quality due to contamination build-up. That is, when the treatment liquid is applied, the pretreatment liquid contacts the transport member before an ink jet discharge step, causing the pretreatment liquid to be transferred to the transport member. . Thus, problems arise from the occurrence of a failure in the transport member and degradation of image quality due to the accumulation of contamination.
    [0009] In order to solve the problem, an imaging method including a drying step to dry a treatment liquid has been studied, where the treatment liquid is dried quickly after being applied. The imaging method including the drying step can solve the problem of the pretreatment liquid transferred to the transport member. However, an agglomeration function of the treatment liquid degrades through the drying step. As a result, a new problem of degraded image quality arises due to the degraded smudge prevention function.
    [00010] Citation List
    [00011] Patent Literature
    [00012] [PTL 1] Japanese Patent (JP-B) No. 3206797
    [00013] [PTL 2] Filed Japanese Patent Application (JP-A) No. 2012-40778 Invention Summary Technical problem
    [00014] The present invention desires to provide an imaging method that allows imaging having favorable image quality without blemishes while suppressing the decrease in agglomeration of a pigment in an ink. Solution to Problem
    [00015] As a means to solve the above problems, an imaging method of the present invention includes: a pretreatment liquid application step for applying a pretreatment liquid to a recording medium including a substrate and a coating layer disposed on at least one surface of the substrate, wherein the pretreatment liquid is applied to a surface of the recording medium with the coating layer; a drying step for drying the recording medium to which the pretreatment liquid has been applied; and an imaging step to form an image on the recording medium after drying by discharging a water-based ink by the inkjet method, wherein the pretreatment liquid includes a water-soluble cationic polymer, a salt of ammonium of an organic acid and water, and where the water-based ink includes water and negatively charged color particles including a colorant. Advantageous Effects of the Invention
    [00016] The present invention can provide an imaging method that allows image formation having favorable image quality while suppressing the decrease in agglomeration of a pigment in an ink. Brief Description of Drawings
    [00017] FIG. 1 is a schematic configuration diagram illustrating an example of an imaging apparatus used in an imaging method of the present invention. Description of Modalities (Image formation method)
    [00018] An imaging method of the present invention includes a pretreatment liquid application step, a drying step and an imaging step, and further includes other steps as needed.
    [00019] The present inventors have found that the problems can be solved by: applying a pretreatment liquid including a water-soluble cationic polymer, an ammonium salt of an organic acid and water, which was used as a water-soluble liquid. pretreatment for a recording medium without a coating layer (plain paper), on a recording medium including a coating layer as a pretreatment liquid; drying the pretreatment liquid; and then applying a paint. <Pretreatment liquid application step>
    [00020] The step of applying pretreatment liquid is a step for applying a pretreatment liquid to a surface of a recording medium including a coating layer, wherein the recording medium includes the coating layer in at least one surface of a substrate.
    [00021] A method for applying the pretreatment liquid is not particularly restricted as long as the pretreatment liquid can be evenly applied to the surface of the recording medium, and can be selected appropriately according to the purpose. Examples of the same include a blade coating method, an gravure coating method, an gravure displacement coating method, a bar coating method, a roll coating method, a knife coating method, a method of air knife coating, a comma coating method, a U-comma coating method, an AKKU coating method, a smooth coating method, a microengraving coating method, a reverse roll coating method , a four-roll or five-roll coating method, a dip coating method, a curtain coating method, a slice coating method, and a dye coating method.
    [00022] A wet coating amount of the pretreatment liquid on the recording medium (a coating amount of the pretreatment liquid before drying the recording medium) is preferably 0.1 g/m2 to 10.0 g µg/m 2 , and more preferably 1.0 g/m 2 to 3.0 g/m 2 .
    [00023] The amount of wet coating of 0.1 g/m2 or greater enhances image quality of a recorded matter (concentration, color saturation, color spots, plumage). The amount of 10.0 g/m2 or less provides the same agglomeration effect that in the case exceeding 10.0 g/m2 can be achieved. In addition, it does not sacrifice the texture of the etched material, saves time for the drying step and does not cause a problem in terms of cost. <<Recording medium>>
    [00024] The recording medium is not particularly restricted as long as it is printing paper including the coating layer on at least one surface of the substrate, and can be selected appropriately according to the purpose.
    [00025] Printing paper including coating layer is paper with improved appearance and smoothness by applying a coating to a surface of a base paper, and the coating can be on both sides or one side of the same. Examples of the coating include a mixture of a white pigment such as kaolin and calcium carbonate with a binder such as starch.
    [00026] Examples of types of printing paper including the coating layer include art paper, coated paper, light weight coated paper, cast paper and thin coated paper.
    [00027] In the present invention, the recording medium includes the substrate and the coating layer disposed on at least one surface of the substrate, and the pretreatment liquid is applied on a surface of the recording medium with the coating layer. <<Pre-treatment liquid>>
    [00028] The pretreatment liquid includes a water-soluble cationic polymer, ammonium salt of an organic acid and water, and additionally includes other components as needed.
    [00029] Both the water-soluble cationic polymer and the ammonium salt of an organic acid have a function as a binding agent to agglomerate a pigment in a water-based paint. - Water-soluble cationic polymer -
    [00030] The water-soluble cationic polymer is not particularly restricted, and hitherto known can be used. Regardless, the water-soluble cationic polymer is preferably obtained through the polymerization of an amine monomer and epihalohydrin.
    [00031] The water-soluble cationic polymer obtained through the polymerization of these monomers includes a hydroxyl group and an ammonium cation in a main chain of the same. Furthermore, it is considered that a halogen anion released in an aqueous solution has functions to improve a buffering effect in case of contact with a paint and a agglomeration effect of a pigment.
    [00032] Examples of the cationic polymer include a polyamine-epihalohydrin copolymer, a polyamide-epihalohydrin copolymer, a polyamidepolyamine-epihalohydrin copolymer and an amine-epihalohydrin copolymer. Among these, a copolymer represented by General Formula (A) below, a copolymer including a repeating unit represented by General Formula (B) below, or a copolymer obtained by polymerizing an amine monomer, a monomer represented, is favorably used. by Structural Formula (C) below and a monomer represented by General Formula (D) below, or any combination thereof. <General Formula (A)>
    where, in the General Formula (A), R1 to R8 represent alkenyl group and a benzyl group; X represents a halogen atom; n represents an integer of 1 or 2.
    [00033] The alkyl group in R1 to R8 preferably contains 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group and a butyl group.
    [00034] Examples of the hydroxyalkyl group in R1 to R8 include the alkyl group with hydrogen atoms being partially replaced by hydroxyl groups.
    [00035] Examples of the alkenyl group in R1 to R8 include a vinyl group, an allyl group, a butenyl group, a hexenyl group and a decenyl group.
    [00036] Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.<General Formula (B)>

    [00037] where, in General Formula (B), X represents a halogen atom; m represents an integer of 1 or greater.
    [00038] Examples of the halogen atom represented by X in the General Formula (B) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.<Structural Formula (C)>
    <General Formula (D)>

    [00039] where, in the General Formula (D), X represents a halogen atom.
    [00040] Examples of the halogen atom represented by X in the General Formula (D) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
    [00041] Examples of the amine monomer include diethylene triamine, triethylene tetramine, tetraethylene pentamine and iminobispropylamine. Of these, an amine monomer represented by Structural Formula (E) below is particularly preferable as it is industrially manufactured and is readily available.<Structural Formula (E)>

    [00042] Here, a cationic quaternary ammonium type polymer or in some cases a cationic polymer which can be dispersed in water other than the above compounds can be used as the water-soluble cationic polymer.
    [00043] A mass average molecular weight of the water-soluble cationic polymer varies depending on the types of copolymer. Regardless, it is preferably in a range of 500 to 100,000 in the case of the polyamine-epihalohydrin copolymer; preferably it is in a range of 5,000,000 or less in the case of the polyamide-epihalohydrin copolymer or the polyamide polyamine-epihalohydrin copolymer; preferably it is in a range of 700 to 50,000 in the case of the amine-epihalohydrin copolymer.
    [00044] When the mass average molecular weight exceeds the respective upper limits, there are cases where no aqueous solution is formed. When it is below its lower limit, there are cases where a treatment effect with the pre-treatment liquid degrades.
    [00045] A content of the water-soluble cationic polymer with respect to a total content of the pretreatment liquid is preferably 10% by mass to 70% by mass, and more preferably 20% by mass to 60% by mass.
    [00046] When the content is 10% by mass or greater, an effect of suppressing the decrease in agglomeration after the drying step is fully demonstrated. Still, the content of 70% by mass or less provides the same image quality enhancing effect as in the case that exceeds 70% by mass while not causing difficulties in adding the ammonium salt of an organic acid or adding a material that imparts functions such as penetration and wettability different than the agglomeration effect required to coat the recording medium.
    [00047] Examples of the other water-soluble cationic polymer include salts of poly(vinylpyridine), polyalkylamino ethylacrylate, polyalkylamino ethylmethacrylate, poly(vinylimidazole), polyethylenimine, polybiguanide, polyguanide, polyamine or derivatives thereof, and polyallylamine or derivatives thereof. - Ammonium salt of organic acid -
    [00048] Favorable examples of the ammonium salt of an organic acid in terms of solubility for water include ammonium lactate, ammonium acetate, ammonium propionate, ammonium oxalate, ammonium tartrate, ammonium succinate (diammonium succinate), malonate of diammonium, ammonium malate, ammonium citrate, diammonium hydrogen citrate, triammonium citrate and ammonium L-glutamate. Among these, ammonium lactate having low corrosivity is more preferable in view of corrosivity and acid resistance against a metal member such as aluminum and SUS.
    [00049] An ammonium salt content of an organic acid with respect to the total amount of the pretreatment liquid is preferably 1% by mass to 40% by mass, and more preferably 10% by mass to 30% by mass.
    [00050] When the content is 1% by mass or greater, an effect of suppressing the decrease in agglomeration after the drying step is fully demonstrated while maintaining the agglomeration of the pretreatment liquid itself before the drying step. Furthermore, when the content is 40% by mass or less, an amount of the water-soluble cationic polymer is sufficient to suppress the decrease in agglomeration after the drying step, and the effect of suppressing the decrease in agglomeration is fully demonstrated.
    [00051] The pretreatment liquid should include both the water-soluble cationic polymer and the ammonium salt of an organic acid, and a total content of the same with respect to the total amount of the pretreatment liquid is preferably 30% by mass or greater, more preferably 30% by mass to 70% by mass, and preferably additionally 40% by mass to 60% by mass.
    [00052] When the content is 30% by mass or greater, the effect of suppressing the decrease in agglomeration after the drying step is fully demonstrated. Also, when the content is 70% by mass or less, the image quality enhancing effect can be fully demonstrated while not causing difficulties in adding a material that imparts functions such as penetration and wettability other than the agglomeration effect required for overlay on the recording medium. <<Water>>
    [00053] Water is not particularly restricted, and can be selected appropriately according to the purpose. Examples thereof include: pure water such as ion exchange water, ultra-filtered water, reverse osmosis water and distilled water; and ultra-pure water.
    [00054] A water content in the pretreatment liquid is not particularly restricted, and can be selected appropriately according to the purpose. <<Other components»
    [00055] The other components are not particularly restricted, and they can be appropriately selected according to the purpose. Examples thereof include a wetting agent, a surfactant, a penetration agent, a suds suppressing agent, a pH adjuster, an antiseptic and fungicide, and a rust inhibitor. - Wetting agent -
    [00056] The wetting agent can be added to the pretreatment liquid as needed.
    [00057] The wetting agent is added for the purpose of adjusting the viscosity and fluidity of the pretreatment liquid and imparting moisture retention property for stability. Examples thereof include a water-soluble organic solvent and other wetting agents which impart wettability when dissolved in water such as sugars. -- Water-soluble organic solvent —
    [00058] The water-soluble organic solvent used as the wetting agent in the pretreatment liquid is used for the purpose of retaining water included in the pretreatment liquid.
    [00059] In this way, the increase in viscosity in the pretreatment liquid is suppressed even when water and so on in the pretreatment liquid has evaporated in the nozzles or a coating apparatus to provide the pretreatment liquid, which like a result maintains coating and discharge stability. In this view, as the water-soluble organic solvent, it is preferable to use a water-soluble organic solvent having a high equilibrium moisture content. However, from a standpoint of agglomeration effect of the pretreatment liquid, the water-soluble organic solvent preferably has a high equilibrium moisture content not excessively high.
    [00060] Here, with respect to the equilibrium moisture content, a mixture of the water-soluble organic solvent and water is exposed in the air under certain conditions of temperature and humidity, and evaporation of water in the mixture and absorption of water in the air into the water-soluble organic solvent achieves equilibrium. The equilibrium moisture content is defined as an equilibrium moisture content.
    [00061] In the present invention, 1 g of the water-soluble organic solvent weighed in a petri dish was stored in a desiccator having a temperature and humidity maintained at 23°C ± 1°C and 80% ± 3% relative humidity , respectively, by means of an aqueous solution saturated with potassium chloride until there is no change in its mass, and the equilibrium moisture content can be obtained through the following formula. Equilibrium moisture content (% by weight) = ( Mmoisture/Msolvent + Mmoisture) x 100
    [00062] where Mmoisture is an amount of moisture absorbed by the water-soluble organic solvent; Msolvent is the amount of water-soluble organic solvent.
    [00063] Examples of the water-soluble organic solvent used in the pretreatment liquid include polyhydric alcohols, polyhydric alcohol alkyl ethers, polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, compounds which contain sulfur, propylene carbonate and ethylene carbonate.
    [00064] Examples of the water-soluble organic solvent favorably used in terms of maintaining coating and discharge stability include water-soluble organic solvents having high equilibrium moisture content in an environment with a temperature of 23°C and a humidity of 80 % relative humidity of 30% by mass or greater, and preferably 40% by mass or greater.
    [00065] Polyhydric alcohols are favorably used as the water-soluble organic solvents, and specific examples thereof include: 1,2,3-butanetriol (bp (boiling point) : 175°C / pressure in bp measurement ( noticed only when not 1 atmosphere) : 33 hPa; equilibrium moisture content: 38% by mass), 1,2,4-butanetriol (bp: 190°C to 191°C / 24 hPa; equilibrium moisture content : 41% by mass), glycerin (bp: 290°C; equilibrium moisture content: 49% by mass), diglycerin (bp: 270°C / 20 hPa; equilibrium moisture content: 38% by mass), triethylene glycol (bp: 285°C, 39% by mass), tetraethylene glycol (bp: 324°C to 330°C; equilibrium moisture content: 37% by mass), diethylene glycol (bp: 245°C; content equilibrium moisture content: 43% by mass) and 1,3-butanediol (bp: 203°C to 204°C; equilibrium moisture content: 35% by mass).
    [00066] Further, examples of the water-soluble organic solvents having high equilibrium moisture content not excessively high, favorably used in view of the agglomeration effect of the pretreatment liquid 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 water-soluble organic solvents having high equilibrium moisture content at a temperature of 23 °C and a humidity of 80% relative humidity of less than 30% by mass.
    [00067] Examples of polyhydric alcohols as the water-soluble organic solvent include dipropylene glycol (bp: 232°C), 1,5-pentanediol (bp: 242°C), 3-methyl-1,3-butanediol ( bp: 203°C), propylene glycol (bp: 187°C), 2-methyl-2,4-pentanediol (bp: 197°C), ethylene glycol (bp: 196°C to 198°C), tripropylene glycol (bp: 267°C), hexylene glycol (bp: 197°C), polyethylene glycol (viscous liquid to solid), polypropylene glycol (bp: 187°C), 1,6-hexanediol (bp: 253°C to 260°C °C), 1,2,6-hexanetriol (bp: 178 °C), trimethylolethane (solid; mp (melting point): 199 °C to 201 °C) and trimethylolpropane (solid; mp: 61 °C).
    [00068] Examples of the polyhydric alcohol alkyl ethers include ethylene glycol monoethyl ether (bp: 135°C), ethylene glycol monobutyl ether (bp: 171°C), diethylene glycol monomethyl ether (bp: 194°C), diethylene glycol monoethyl ether (bp: 197°C), diethylene glycol monobutyl ether (bp: 231°C), ethylene glycol mono-2-ethyl-hexyl ether (bp: 229°C) and propylene glycol monoethyl ether (bp: 132° Ç).
    [00069] Examples of polyhydric alcohol aryl ethers include ethylene glycol monophenyl ether (bp: 237°C) and ethylene glycol monobenzyl ether.
    [00070] Examples of nitrogen-containing heterocyclic compounds include 2-pyrrolidone (bp: 250°C, mp: 25.5°C; equilibrium moisture content: 47% by mass to 48% by mass), N-methyl-2- pyrrolidone (bp: 202°C), 1,3-dimethyl-2-imidazolidinone (bp: 226°C), ε-caproformamide (bp: 270°C) and Y-butyrolactone (bp: 204°C to 205°C ).
    [00071] Examples of the amides include formamide (bp: 210°C), N-methylformamide (bp: 199°C to 201°C), N,N-dimethylformamide (bp: 153°C) and N,N-diethylformamide ( bp: 176°C to 177°C).
    [00072] Examples of the amines include monoethanolamine (bp: 170°C), diethanolamine (bp: 268°C), triethanolamine (bp: 360°C), N,N-dimethylmonoethanolamine (bp: 139°C), N-methyldiethanolamine (bp: 243°C), N-methylethanolamine (bp: 159°C), N-phenylethanolamine (bp: 282°C to 287°C) and 3-aminopropyldiethylamine (bp: 169°C).
    [00073] Examples of the sulfur-containing compounds include dimethyl sulfoxide (bp: 139°C), sulfolane (bp: 285°C) and thiodiglycol (bp: 282°C).
    [00074] Among the water-soluble organic solvents, polyhydric alcohols are preferably used in view of coating stability and discharge and agglomeration effect of the pretreatment liquid, and glycerin, 1,3-butanediol and 3-methyl- 1,3-butanediol are more preferable.
    [00075] A content of the water-soluble organic solvent in the pretreatment liquid is not particularly restricted, and can be selected appropriately according to the purpose. Regardless, preferably it is 5% by mass to 80% by mass, and more preferably 10% by mass to 20% by mass.
    [00076] When the content of the water-soluble organic solvent is 80% by mass or less, drying properties of the recording medium with the pretreatment liquid applied to it do not degrade regardless of the types of the water-soluble organic solvent. Furthermore, since an amount of agglomeration agent added to the pretreatment liquid is sufficient, agglomeration of the pretreatment liquid does not significantly degrade. On the other hand, when the content of the water-soluble organic solvent is 5% by mass or greater, water included in the pretreatment liquid does not easily vaporize. Thus, there is no risk of water vaporization, which raises the viscosity of the pre-treatment liquid and causes defects in the coating step.
    [00077] Like other wetting agents, materials that dissolve in an aqueous solution and exhibit a function as a wetting agent can be used. Preferable examples thereof include sugars.
    [00078] Examples of sugars include monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides) and polysaccharides.
    [00079] Specific examples thereof include glucose, mannose, fructose, ribose, xylose, arabinose, galactose, maltose, cellobiose, lactose, sucrose, trehalose and maltotriose.
    [00080] Here, polysaccharides refer to sugars in a broad sense, and is used to mean substances existing quite a lot in nature such as α-cyclodextrin and cellulose.
    [00081] Still, examples of derivatives of these sugars include sugars reducing sugars (for example, sugar alcohols (represented by the General Formula: HOCH2(CHOH)nCH2OH, where n represents an integer from 1 to 6)), oxidized sugars (by eg aldonic acids, uronic acids and so on), amino acids and thioacids.
    [00082] Among these, sugar alcohols are preferable, and specific examples thereof include maltitol and sorbitol. - Surfactant -
    [00083] The pretreatment liquid used in the present invention may include a surfactant in order to reform the wettability of the recording medium and to improve an image of the recorded matter in terms of concentration, color saturation and white dots (meaning space that remains in an image of the recorded matter).
    [00084] A content of the surfactant with respect to the total amount of the pretreatment liquid is preferably 0.001% by mass to 5% by mass, and more preferably 0.05% by mass to 2% by mass.
    [00085] Addition of the surfactant is effective when the content is 0.001% by mass or greater. When the content is 5% by mass or less, the same effect as in the case exceeding 5% by mass can be achieved.
    [00086] Examples of the surfactant include a fluorosurfactant, a silicone surfactant, a nonionic surfactant, an anionic surfactant and a betaine surfactant. Among these, the nonionic surfactant is favorably used in view of improved granularity.
    [00087] Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene glycol ester, polyoxyethylene fatty acid amide, polyoxyethylene fatty acid ester, polyoxyethylene polyoxypropylene glycol, glycerin ester, sorbitan ester , sucrose ester, polyoxyethylene glycerin ester ethers, polyoxyethylene sorbitan ester ethers, polyoxyethylene sorbitol ester ethers, alkanolamide fatty acid, amine oxide, polyoxyethylene alkyl amine, glycerin fatty acid ester, sorbitan fatty acid ester polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester and alkyl(poly)glycoxide. - Penetration agent -
    [00088] The pretreatment liquid used in the present invention preferably includes, as a penetration agent, a non-wetting polyol compound or a glycol ether compound, respectively having 8 to 11 carbon atoms, or both of the same. Furthermore, they preferably have a solubility of 0.2% by mass to 5% by mass in water at 25°C.
    [00089] Among these, 2-ethyl-1,3-hexanediol [solubility: 4.2% by mass (25°C)] and 2,2,4-trimethyl-1,3-pentanediol [solubility: 2.0% in mass (25°C)] are particularly preferred.
    [00090] Examples of the other non-wetting polyol compound include aliphatic diols 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-hexene-1,2- diol.
    [00091] Other penetration agents that can be used in combination are not particularly restricted as long as they are dissolved in the pretreatment liquid to adjust to desired properties, and they can be selected appropriately according to the purpose. Examples thereof include: alkyl and allyl ethers of a polyhydric alcohol such as diethylene glycol monophenyl ether, ethylene glycol monophenyl ether, ethylene glycol monoallyl ether, diethylene glycol monophenyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether and tetraethylene glycol chlorophenyl ether ether; and lower alcohols such as ethanol.
    [00092] A content of penetration agent in the pretreatment liquid is preferably 0.1% by mass to 5.0% by mass. When the content is 0.1% by mass or greater, an effect of penetrating into the pretreatment liquid can be achieved. When the content is 5.0% by mass or less, the solubility of the penetrating agent in a solvent is low. Thus, there is no risk of saturation effect of improving permeability through solvent separation. - Foam suppressing agent -
    [00093] The pretreatment liquid used in the present invention may include a suds suppressing agent in order to suppress foaming (that is to say a thin film forming liquid that winds air). In general, foaming hardly occurs in a liquid having a high surface tension such as water as a force acts to reduce a liquid's surface area as much as possible. On the contrary, foaming easily occurs in a liquid having a low surface tension and a high viscosity. Formed bubbles are maintained, and it is difficult to defoam them.
    [00094] The pretreatment liquid used in the present invention has a decreased surface tension and an increased viscosity when it includes the water-soluble cationic polymer, the water-soluble organic solvent or the surfactant. The pretreatment liquid is easily foamed in this way. Thus, the suds suppressing agent is favorably used.
    [00095] In the present invention, the surface tension significantly decreases when the pretreatment liquid includes the nonionic surfactant. In this case, foaming can be suppressed by using a component commonly insoluble in a liquid as the foam suppressing agent and spreading this component onto a surface of the bubbles.
    [00096] However, the insoluble component in a liquid reduces the discharge stability and storage stability. Thus, in the present embodiment, the suds suppressing agent represented by Formula (6) below is favorably used when the pretreatment liquid includes the nonionic surfactant. HOR1R3C-[CH2]n-CR2R4OH ... (6)
    [00097] where, in Formula (6), R1 and R2 respectively represent an alkyl group having 3 to 6 carbon atoms; R3 and R4 respectively represent an alkyl group having 1 to 2 carbon atoms; n represents an integer from 1 to 6.
    [00098] The suds suppressing agent represented by Formula (6) is very compatible with the nonionic surfactant, and the suds suppressing agent is efficiently incorporated into foam films. A difference in surface tension between the nonionic surfactant and the foam suppressing agent is considered to form a locally unbalanced surface of the foam films, destroying the bubbles.
    [00099] Examples of the suds suppressing agent represented by Formula (6) include 2,4,7,9-tetramethyl decane-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 in view of its foam suppression effect and high compatibility with the pretreatment liquid.
    [000100] A content of the suds suppressing agent in the pretreatment liquid is preferably 0.01% by mass to 10% by mass, and more preferably 0.02% by mass to 5% by mass.
    [000101] When the suds suppressing agent content is 0.01% by mass or greater, sufficient suds suppressing effect can be achieved. When the content is 10% by mass or less, sufficient suds suppressing effect can be achieved, and there is no risk of the suds suppressing agent becoming insoluble in the pretreatment liquid. - pH adjuster -
    [000102] The pH adjuster is not particularly restricted as long as it can adjust a pH in a range of 4 to 8 without adversely affecting the paint to be formulated, and can be selected appropriately according to the purpose.
    [000103] When the pH of the pretreatment liquid exceeds 8, there is a possibility that the agglomeration effect significantly degrades. Also, when the pH is less than 4, there is a possibility that rollers and so on of a transport member come into contact with the pretreatment liquid corrosion, causing a transport function to fail.
    [000104] Examples of the pH adjuster include alcohol amines, alkali metal element hydroxides, ammonium hydroxides, phosphonium hydroxides and alkali metal carbonates.
    [000105] Examples of the amine alcohols include diethanolamine, triethanolamine and 2-amino-2-ethyl-1,3-propanediol.
    [000106] Examples of the hydroxides of the alkali metal elements include lithium hydroxide, sodium hydroxide and potassium hydroxide.
    [000107] Examples of ammonium hydroxides include ammonium hydroxide and quaternary ammonium hydroxide.
    [000108] Examples of phosphonium hydroxides include quaternary phosphonium hydroxide.
    [000109] Examples of alkali metal carbonates include lithium carbonate, sodium carbonate and potassium carbonate. - Antiseptic and fungicide -
    [000110] Examples of the antiseptic and fungicide include sodium dehydroacetate, sodium sorbate, sodium 2-pyridinephosphine-1-oxide, sodium benzoate, sodium pentachlorophenol and a sodium component of 1,2-benzisothiazolin-3-one. - Rust inhibitor -
    [000111] Examples of the rust inhibitor include acid sulfites, sodium thiosulfate, ammonium thiodiglycollate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite and 1,2,3-benzotriazole. <Drying step>
    [000112] The drying step is a step to dry the recording medium in which the pretreatment liquid has been applied.
    [000113] As the step to dry the pretreatment liquid deposited on the recording medium, one possible method is artificially drying to an extent then a carrier member failure or image quality degradation due to contamination buildup it does not occur because of the transfer of the pretreatment liquid deposited on the recording medium to the transport member in contact with it between the step of applying the pretreatment liquid and imaging by a discharged ink. A drying temperature preferably is 40°C to 130°C, and more preferably 80°C to 100°C. When the drying temperature is less than 40°C, there are cases where a drying time is excessively long. There is a possibility that drying temperature exceeding 130°C damages the recording medium.
    [000114] Examples of the drying method include a heat drum method, an oven method, a hot air blow method, a preheater method and a heat roller method. A combination of these can also be used.
    [000115] Also, "drying" after application of the pretreatment liquid does not mean that the recording medium appears to be apparently dry due to the pretreatment liquid absorbed by the recording medium, but it does mean that the pretreatment liquid treatment cannot maintain a liquid state due to evaporation of liquids such as moisture in the pretreatment liquid and solidifies. <Image formation step>
    [000116] The image forming step is a step to form an image by discharging a water-based ink into the recording medium after drying by the inkjet method.
    [000117] A step for depositing an ink in a recording method of the present embodiment is to apply and deposit an ink on a recording medium that has the pre-treatment liquid of the present embodiment deposited therein and went through the drying step of pretreatment liquid to thereby form an image on this recording medium. As a method for depositing ink, a method of discharging ink by applying a stimulus (energy) using a predetermined device to thereby deposit ink on the recording medium is favorably used. Specifically, hitherto known inkjet recording methods can be used. Examples of such inkjet recording methods include an inkjet recording method for recording an image onto a recording medium such as continuous paper using in-line heads and an inkjet recording method of scanning heads.
    [000118] In the step for depositing an ink, a method of driving a recording head as a means for discharging the ink is not particularly restricted, and can be selected appropriately according to the purpose. Examples thereof include: a piezoelectric element actuator using PZT (lead zirconate titanate); a method of applying thermal energy; a method using an on-demand type head with an actuator using an electrostatic force; and an engraving method with a continuous injection head of a charge control type.
    [000119] Flexible control of discharging the liquid droplet is considered difficult in the method of applying thermal energy, and there tend to be large variations in the quality of a recorded image depending on the types of recording medium. However, this problem can be solved by applying the pre-treatment liquid on the recording medium, and a recorded material with high and stable quality can be obtained regardless of the types of the recording medium. <<Water based ink>>
    [000120] The water-based ink includes water and negatively charged colored particles including a colorant, and additionally includes other components as required.
    [000121] In water-based ink, negatively charged colored particles including a colorant are dispersed in water and so on by electrostatic repulsion.
    [000122] Ink colors are not particularly restricted, and can be selected appropriately according to the purpose. Examples of these include yellow, magenta, cyan and black. A color image can be recorded when an ink set including two or more types of inks of these colors is used, and a color image can be recorded when an ink set including inks of at least three colors is used.
    [000123] This ink is favorably used in an inkjet recording method with a recording apparatus such as a so-called piezo recording apparatus (see JP-A No. 02-51734), so-called thermal recording apparatus ( see JP-A No. 61-59911) and so-called electrostatic recording apparatus (see JP-A No. 06-71882). Furthermore, this ink is favorably used, for example, in a recording apparatus which heats a recording medium and the ink to a predetermined temperature during recording or before and after recording to promote the fixation of an engraved matter. Furthermore, this ink is used in a recording apparatus which heats a recording medium and the ink to 50°C to 200°C, for example, during recording or before and after recording to promote the fixation of an engraved matter.
    [000124] Physical properties of water-based ink are not particularly restricted, and they are selected appropriately according to the purpose. For example, it preferably has a viscosity and a surface tension in the following ranges. The ink viscosity at 25°C preferably is 5 mPa-s to 20 mPa-s. An ink viscosity of 5 mPa-s or greater provides an effect of enhancing the density and quality of a recorded image. Meanwhile, an ink viscosity of 20 mPa-s or less provides favorable discharge stability.
    [000125] Here, viscosity can be measured at 25°C using a RE-550L viscometer, manufactured by Toki Sangyo Co., Ltd.
    [000126] The ink surface tension at 25°C preferably is 20 mN/m to 35 mN/m, and more preferably 20 mN/m to 30 mN/m. The ink surface tension of 20 mN/m to 35 mN/m increases ink penetration and provides favorable drying properties, resulting in decreased nucleation spots even when recording on plain paper. Also, an area of the recording medium with liquid composition deposited on it is easily wetted, which increases the color saturation of the recorded matter and enhances white spots. When the surface tension exceeds 35 mN/m, the ink does not easily level out on the recording medium (even out means that the ink wets and spreads evenly on the surface of the recording medium), which can lead to drying time. prolonged. - Colorant -
    [000127] Like the colorant, a pigment is mainly used in view of weather resistance, but a colorant can be used in combination within a range so as not to degrade weather resistance for color tone adjustment. This pigment is not particularly restricted, and can be selected appropriately according to the purpose. For example, black or colored inorganic pigments and organic pigments are used. These pigments can be used alone or in combination of two or more.
    [000128] Examples of the inorganic pigment include: titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red and chromium yellow; and carbon black prepared by a method known hitherto such as contact method, furnace method and thermal method.
    [000129] Examples of the organic pigment include azo pigments (including lake azo, insoluble azo pigments, condensed azo pigments, azo chelate pigments and so on), polycyclic pigments (eg phthalocyanine pigments, perylene pigments, perinone pigments , anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments and so on), dye-type chelates (e.g., basic dye-type chelate, chelate type acid dye and so on), nitro pigments, nitrous pigments and aniline black. Among these pigments in particular, those which are quite compatible with water are favorably used.
    [000130] Specific examples of the most favorably used pigments for black include: carbon black such as furnace black, lamp black, acetylene black and channel black (C.I. 7 Pigment Black); metals such as copper, iron (Pigment Black C.I.11) and titanium oxide; and organic pigments such as aniline black (C.I.1 Pigment Black).
    [000131] Specific examples thereof for color include CI Pigment Yellow 1, 3, 12, 13, 14, 17, 24, 34, 35, 37, 42 (yellow iron oxide), 53, 55, 74, 81, 83 , 95, 97, 98, 100, 101, 104, 108, 109, 110, 117, 120, 128, 138, 150, 151, 153, 183, CI Pigment Orange 5, 13, 16, 17, 36, 43, 51, CI Pigment Red 1, 2, 3, 5, 17, 22, 23, 31, 38, 48:2 (Permanent Red 2B(Ca)), 48: 3, 48: 4, 49: 1, 52: 2 , 53: 1, 57: 1 (Bright 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, Pigment Violet CI 1 (Lake Rhodamine ), 3, 5: 1, 16, 19, 23, 38, CI Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3 (Phthalocyanine Blue), 16, 17: 1, 56, 60 , 63, and CI Pigment Green 1, 4, 7, 8, 10, 17, 18, 36.
    [000132] In the present invention, the colorant is dispersed in water as negatively charged particles. In this case, favorable modalities of dispersing the pigment in water include the following first through third modalities.
    [000133] In the first embodiment, a dispersoid in which a water-insoluble or poorly water-soluble colorant included in the fine polymer particles (which may also be referred to as "resin coated pigment") is dispersed in water as a dispersing medium to obtain a polymer emulsion (water dispersion of fine polymer particles including a colorant). Here, in this case, it is referred to as "emulsion" in the present invention even though the dispersoid includes a solid.
    [000134] In the second modality, a pigment having at least one type of a hydrophilic group on a surface thereof and having the ability to disperse water in the absence of a dispersant (which may also be referred to as "self-dispersing pigment") is dispersed in Water.
    [000135] In the third modality, a pigment is dispersed in water with an anionic dispersant or a nonionic dispersant.
    [000136] Examples of the polymer emulsion used in the first embodiment include: a dispersoid in which the pigment is encapsulated in fine polymer particles; and a dispersion of a dispersoid with the pigment adsorbed onto a surface of fine polymer particles dispersed in a dispersion medium. In this case, it is not necessary for the pigment to be completely encapsulated or adsorbed; rather, the pigment can be dispersed in the emulsion to a degree that the effect of the present invention is not impaired. Examples of polymers that form the polymer emulsion (polymers in the fine polymer particles) include an anionic vinyl polymer, a polyester polymer, and a polyurethane polymer. Among these, anionic vinyl polymer and polyester polymer are preferable.
    [000137] Like the anionic vinyl polymer and polyester polymer, polymers disclosed in JP-A No. 2000-53897, JP-A No. 2001-139849 and so on can be used.
    [000138] The self-dispersing pigment of the second modality is a pigment with surface modification binding at least one type of a hydrophilic group on a pigment surface directly or through another atomic group. Examples of a method used for this surface modification include: a method of chemically attaching a predetermined anionic functional group (functional group such as sulfonic group and carboxyl group) to the pigment surface; and a wet oxidation treatment method using at least any one of a hypoalous acid such as hypochlorous acid and salts thereof. Among these, an embodiment in which the pigment having a carboxyl group attached to the surface thereof is dispersed in water is particularly preferable. The carboxyl group bonded on the pigment surface improves the pigment dispersion stability, provides a high quality image and improves the water resistance of the recording medium after recording. Furthermore, a paint including the self-dispersing pigment of the second modality has new superior dispersibility after drying. Thus, the ink does not cause clogging even when recording is suspended for a period of time and the moisture in the ink filled in the nozzles of a recording device has evaporated. Therefore, favorable recording is easily possible with just a simple clearing operation.
    [000139] In order to obtain such functionalities, the self-dispersible pigment has a volume mean particle diameter (D50) in the ink of preferably 0.01 μm to 0.16 μm. Here, D50 is also referred to as an average diameter, meaning a certain particle diameter where a group of particles with a larger diameter and a group of particles with a smaller diameter have equal amounts when the particles are divided into two groups in the particle diameter (eg volume mean particle diameter). Here, in the present invention, when the self-dispersing pigment of the second modality is used, the ink preferably includes a resin that can be dispersed in water explained later for improved hold capacity (scratch resistance) and improved colorant coloring property in the medium of recording.
    [000140] When the self-dispersing pigment is self-dispersing carbon black, examples of the anionic functional group bonded with the carbon black include -COOM, -SO3M, -PO3HM, -PO3M2, -SO2NH2 and -SO2NHCOR (where M represents an alkali metal, an ammonium or an organic ammonium; R represents an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have one or more substituents or a naphthyl group which may have one or more substituents). Of these, -COOM and -SO3M are preferable.
    [000141] Further, when “M” in the functional group is alkali metal, lithium, sodium, potassium and so on are used, for example. When “M” is organic ammonium, mono- to tri- (mono-, di- or tri-) methyl ammonium, mono- to triethyl ammonium and mono- to trimethanol ammonium are used, for example. The functional group can be bonded to the surface of carbon black through another atomic group. Examples of another atomic group include an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have one or more substituents, and a naphthyl group which may have one or more substituents. Specific examples of the functional group bonded to the carbon black surface through the atomic group include -C2H4COOM (where M represents an alkali metal or a quaternary ammonium) and -PhSO3M (where Ph represents a phenyl group; M represents an alkali metal or a quaternary ammonium).
    [000142] When the self-dispersing pigment is a colored pigment, in order to obtain a colored pigment including an anionic functional group, it is possible to introduce the anionic functional group (for example, -COONa) by a method such as oxidation treatment of the colored pigment with sodium hypochlorite, sulphonation, and reaction with a diazonium salt.
    [000143] In the third modality, the pigment is dispersed by the anionic dispersant or the non-ionic dispersant. Examples of this anionic dispersant include: polyoxyethylene alkyl ether acetates, alkylbenzene sulfonates (NH4, Na, Ca); alkyl diphenyl ether disulfonates (NH4, Na, Ca); sodium dialkylsuccinate sulfonates; sodium naphthalene sulfonate formaldehyde condensed; polycyclic polyoxyethylene phenyl ether sulfates (NH4, Na) and laurates; and polyoxyethylene alkyl ether sulfates and oleates. Among these, as specific examples of the anionic dispersant, sodium dioctyl sulfosuccinate and ammonium polyoxyethylene styrene phenyl ether sulfonate are preferable.
    [000144] The nonionic dispersant having an HLB value of 10 to 20, and examples thereof include polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, polyoxyethylene phenyl polycyclic ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylphenyl ether ethers, polyoxyethylene alkyl amines, polyoxyethylene alkyl amides and acetylene glycol. Among these, as specific examples of the nonionic dispersant, polyoxyethylene lauryl ether, polyoxyethylene-β-naphthyl ether, polyoxyethylene sorbitan monooleate and polyoxyethylene styrenephenyl ether are more preferable. Here, even when non-ionic dispersant is used, the water-based paint can be negatively charged as a complete system using a negatively charged resin emulsion in combination.
    [000145] In the third modality, the pigment dispersion is dissolved in an aqueous medium. Then the organic pigment or the inorganic pigment is added, and it is sufficiently wetted. It is then subjected to high speed agitation, dispersed in a disperser using balls such as a crimping mill and ball mill, kneading and dispersing in a kneader-disperser using a shear force such as a roller mill, or dispersion using a disperser ultrasonic, and in this way the pigment dispersant is prepared. Here, a product of such a dispersing and kneading step generally includes coarse particles, which cause clogging in the nozzles and providing paths in the recording apparatus. Thus, it is necessary to remove particles having a particle diameter of 1 µm or larger using a filter or centrifuge.
    [000146] In the present invention, the dispersant is preferably used in a range of 1 part by mass to 100 parts by mass with respect to 100 parts by mass of the pigment, and more preferably 10 parts by mass to 50 parts by mass. When the amount of dispersant is small, the pigment cannot be sufficiently refined. When the amount of dispersant is in excess, an excess component of the dispersant that is not adsorbed to the pigment affects the ink's physical properties. This can cause blurring of a recorded image or degradation of water resistance and scratch resistance. Here, in the present invention, when the third modality pigment is used, the ink preferably includes a resin which can be dispersed in water discussed later for improved flexibility (scratch resistance) and improved colorant property of the colorant in the recording medium.
    [000147] Additionally, to stabilize the pigment dispersion, a water-soluble polymer compound having a mass average molecular weight of 30,000 or less can be used in combination. As the water-soluble polymer compound, a water-soluble acrylic resin of styrene, a water-soluble acrylic resin, water-soluble polyurethane, water-soluble polyester, a water-soluble styrene-maleic acid copolymer and a copolymer of α - olefin - water soluble maleic acid having a mass average molecular weight of 30,000 or less is generally preferred. Among these, the water-soluble polyurethane, the water-soluble polyester and the water-soluble α-olefin-maleic acid copolymer represented by Formula (7) below

    [000148] wherein, in Formula (7), R represents an alkyl group having 6 to 22 carbon atoms; n represents 30 to 100.
    [000149] The α-olefin - water soluble maleic acid copolymer represented by Formula (7) has an acid value of preferably 100 mg KOH/g to 400 mg KOH/g. When the acid value is less than 100 mg KOH/g, solubility may degrade. On the other hand, when the acid value exceeds 400 mg KOH/g, the viscosity of the pigment dispersion increases, and there are risks of easily degrading the discharge and easily degrading the dispersion stability of the pigment dispersion.
    [000150] The α-olefin - water soluble maleic acid copolymer of Formula (7) has a mass average molecular weight of preferably 5,000 to 20,000. When the mass average molecular weight is less than 5,000, the dispersion stability of the pigment dispersion may degrade. On the other hand, when the mass average molecular weight exceeds 20,000, pigment dispersion viscosity may increase due to poor solubility.
    [000151] A content of the water-soluble polymer compound in terms of solid content preferably is 1 part by mass to 100 parts by mass, and more preferably 5 parts by mass to 50 parts by mass with respect to 100 parts by mass of the pigment. When the content of the water-soluble polymer compound is less than 1 part by mass, there are cases of insufficient effect to improve dispersion stability. On the other hand, the viscosity of the paint increases when the content exceeds 100 parts by mass. As a result, there are possibilities that the discharge stability degrades and that increasing the amount no longer changes the effect of improving the dispersion stability.
    [000152] The pigment as a colorant has a volume average particle diameter in the water-based ink of preferably 150 nm or less, and more preferably 100 nm or less. When the volume mean particle diameter exceeds 150 nm, the discharge stability rapidly degrades, which can easily cause nozzle clogging or ink deflection. When the volume mean particle diameter is 100 nm or less, the discharge stability improves, and additional color saturation of an image also improves.
    [000153] A content of pigment as a colorant in water-based paint is not particularly restricted, and can be selected appropriately according to the purpose. Regardless, preferably it is 1% by mass to 15% by mass, and more preferably 2% by mass to 12% by mass. In addition, the polymer emulsion of the first modality in which the pigment is coated with the fine anionic polymer particles, the self-dispersing pigment of the second modality, and the water-dispersible colorant of the third modality can be mixed and used in combination. <<Water>>
    [000154] Water is not particularly restricted, and can be selected appropriately according to the purpose. Examples thereof include: pure water such as ion exchange water, ultra-filtered water, reverse osmosis water and distilled water; and ultra pure water.
    [000155] A water content in water-based paint is not particularly restricted, and can be selected appropriately according to the purpose. <<Other components»
    [000156] Examples of the other components include a wetting agent, a surfactant, a penetration agent, a suds suppressing agent, a pH adjuster, an antiseptic and fungicide and a rust inhibitor.
    [000157] Like the other components, those exemplified as the other components in the pretreatment liquid can be used. (Image Formation Device)
    [000158] An imaging apparatus of the present invention includes:
    [000159] a pretreatment liquid application unit configured to apply a pretreatment liquid on a recording medium including a substrate and a coating layer on at least one surface of the substrate, wherein the pretreatment liquid treatment is applied to a surface of the recording medium with the coating layer,
    [000160] a drying unit configured to dry the recording medium on which the pretreatment liquid has been applied, and
    [000161] an image forming unit configured to form an image on the recording medium after drying by discharging a water-based ink by the inkjet method.
    [000162] It additionally includes other units as needed.
    [000163] The imaging apparatus can be particularly favorably applied to an imaging apparatus which performs ink jet recording on a recording medium transported at high speed.
    [000164] That is, when the recording medium is transported by a transport member at high speed from 10 m/min to 200 m/min, for example, a series of steps, namely the application of a pre-treatment liquid In particular, drying and applying an ink as in the present invention can suppress the occurrence of a carrier member failure or image quality degradation due to contamination buildup, and also provides an effect that image quality does not degrade even in the case of artificial drying.
    [000165] Here, an image forming apparatus for forming an image by applying the pretreatment liquid used in the present invention to the recording medium, drying the coated pretreatment liquid and then applying the ink to the recording medium is explained using a specific example from FIG. 1.
    [000166] FIG. 1 illustrates an image forming apparatus used for an ink jet recording method that records an image on a recording medium such as continuous paper using in-line heads.
    [000167] In FIG. 1, a recording medium 101 includes a coating layer on at least one surface thereof. A pretreatment liquid applying unit 102 applies a pretreatment liquid onto a surface of the recording medium with the coating layer (pretreatment liquid applying step), and then a drying unit 103 dries the pre-treatment liquid (drying step). Next, a printing unit 104 discharges a water-based ink jet onto the surface of the recording medium with the pretreatment liquid applied and dried by the ink jet method to thereby form an image (forming step. image), and a recording medium 105 including the image formed thereon is obtained. (Recorded material)
    [000168] An engraved matter of the present invention includes an image recorded by the imaging method of the present invention.
    [000169] Embossed matter provides high blemish-free image quality and superior stability over time, and can be favorably used for various applications such as documents with multiple characters or images embossed on it. Examples
    [000170] Hereinafter, the present invention is further described in detail with reference to Examples, however they should not be interpreted as limiting the scope of the present invention. <Preparing the ink>
    [000171] Water-based paints used in the examples and comparative examples are prepared by a conventional method as follows.
    [000172] Here, product names and manufacturers of pigment dispersions used in the following paint preparation examples as follows.
    [000173] Black dispersion: PABK49M, manufactured by Kao Corporation
    [000174] Cyan dispersion: PAC205, manufactured by Kao Corporation
    [000175] Magenta dispersion: PAM206, manufactured by Kao Corporation
    [000176] Yellow dispersion: PAY204, manufactured by Kao Corporation
    [000177] Here, each of the above dispersions disperses in a water-based ink as negatively charged colored particles including a colorant.[Ink Preparation Example 1]• Cyan dispersion ... 20.0% by mass• 1,3-Butanediol ... 23.0% by mass• Glycerin ... 8.0% by mass• 2-Ethyl-1,3-hexanediol ... 2.0% by mass• ZONYL FS-300 ( fluorosurfactant manufactured by DuPont Co.) ... 1.0% by mass• PROXEL LV (manufactured by Avecia) ... 0.2% by mass• 2-Amino-2-ethyl-1,3-propanediol ... 0.3% by mass The composition was adjusted to 100% by mass by adding ion exchange water. (Paint Preparation Example 2)• Cyan Dispersion ... 20.0% by mass• 3-Methyl-1,5-pentanediol ... 10.5% by weight• 3-Methyl-1,3-butanediol . .. 13.0% by mass• Glycerin ... 8.0% by mass• 2,2,4-Trimethyl-1,3-pentanediol ... 2.0% by mass• UNISAFE A-LM (non-surfactant ionic polyether based, manufactured by NOF Corporation) ... 2.0% by mass• PROXEL LV (manufactured by Avecia) ... 0.2% by mass• 2-Amino-2-ethyl-1,3- propanediol ... 0.5% by mass The composition was adjusted to 100% by mass by adding ion exchange water.(Paint Preparation Example 3)• Magenta dispersion ... 20.0% by mass• 1,3-Butanediol ... 22.5% by mass• Glycerin ... 9.0% by mass• 2-Ethyl-1,3-hexanediol ... 2.0% by mass• ZONYL FS-300 (fluorosurfactant manufactured by DuPont Co .) ... 1.0% by mass• PROXEL LV (manufactured by Avecia) ... 0.2% by mass• 2-Amino-2-ethyl-1,3-propanediol ... 0.3% by massThe composition was adjusted to 100% by mass by adding ion exchange water.(Paint Preparation Example 4)• Magen Dispersion ta ... 20.0% by mass • 3-Methyl-1,3-butanediol ... 11.5% by mass • Ethylene glycol ... 5.0% by mass • Glycerin ... 7.0% by mass• 2-Ethyl-1,3-hexanediol ... 2.0% by mass• KF-640 (Polyether Modified Silicone Oil, manufactured by Shin-Etsu Chemical Co., Ltd.) ... 0, 5% by mass• PROXEL LV (manufactured by Avecia) ... 0.2% by mass• 2-Amino-2-ethyl-1,3-propanediol ... 0.3% by massThe composition has been adjusted to 100% by mass adding ion exchange water.(Paint Preparation Example 5)• Yellow dispersion ... 20.0% by mass• 1,6-Hexanediol ... 24.5% by mass• Glycerin ... 8, 0% by mass• 2-Ethyl-1,3-hexanediol ... 2.0% by mass• ZONYL FS-300 (fluorosurfactant manufactured by DuPont Co.) ... 0.2% by mass• 2-Amino- 2-ethyl-1,3-propanediol...0.3% by massThe composition was adjusted to 100% by mass by adding ion exchange water.(Paint Preparation Example 6)• Yellow dispersion... 20.0% by mass • 3-Methyl-1,3-butanediol ... 20.0% by mass • 1,3-Butanediol ... 8.5% by mass • Glycerin ... 7.5% by mass• 2-Ethyl-1,3-hexanediol ... 2.0% by mass• KF-640 (Polyether Modified Silicone Oil, manufactured by Shin-Etsu Chemical Co., Ltd. .) ... 0.5% by mass• PROXEL LV (manufactured by Avecia) ... 0.2% by mass• 1-Methylamino-2,3-propanediol ... 0.1% by massThe composition has been adjusted to 100% by mass by adding ion exchange water.(Ink Preparation Example 7)• Black dispersion... 20.0% by mass• 1,5-Pentanediol...22.5% by weight• Glycerin .. 7.5% by mass• 2-Pyrrolidone ... 2.0% by mass• 2-Ethyl-1,3-hexanediol ... 2.0% by mass• R-(OCH2CH2)nOH (in the formula, R = C12, n = 9, where R can be branched) ... 1.0% by mass• KF-640 (polyether-modified silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.) ... ... 0.1% by mass• PROXEL LV (manufactured by Avecia) ... 0.2% by mass• 2-Amino-2-ethyl-1,3-propanediol ... 0.5% by massThe composition has been adjusted to 100% by mass adding ion exchange water. (Paint Preparation Example 8) • Black dispersion ... 20.0% e m mass• 2-Methyl-2,4-pentanediol ... 11.5% by mass• 3-Methyl-1,3-butanediol ... 13.0% by mass• Glycerin ... 7.5% by mass mass• 2-Pyrrolidone ... 2.0% by mass• UNISAFE A-LM (non-ionic surfactant based on polyether, manufactured by NOF Corporation) ... 2.0% by mass• 2,2,4-Trimethyl -1,3-pentanediol ... 2.0% by mass• PROXEL LV (manufactured by Avecia) ...0.2% by mass• 1-Methylamino-2,3-propanediol ... 0.1% by pasta
    [000178] The composition was adjusted to 100% by mass by adding ion exchange water. (Examples 1 to 6 and Comparative Examples 1 to 4)
    [000179] Pretreatment liquids having compositions indicated in Table 1-1 and Table 1-2 below were respectively applied to a surface of a coating layer of a recording medium (LumiArt gloss paper, manufactured by STORA ENSO; thickness of paper: 170 g/m2) by a roll coating method so that an amount of wet coating was 1.9 ± 0.2 g/m2, and then the recording medium was dried at 90°C for 30 seconds by an oven method. Here, drying time of around 1 second is sufficient in practice, but drying time longer than practice has been adapted for evaluation. Similarly, the heating temperature during drying was set higher than that in the current equipment.
    [000180] Next, the water-based ink including the negatively charged pigment particles dispersed therein as manufactured above was discharged by a single-pass inkjet method at 600dpi, and an image was formed in this way.
    [000181] Note that, granularity was evaluated around green (ie a secondary color of cyan and yellow) where image smears were observed even more significantly. Here, it was a green ink including the cyan ink from Ink Preparation Example 1 and the yellow ink from Ink Preparation Example 6 with a mass ratio of 1.15:1.00, and the ink coating amount was 3.2 x 10-8 g/cm2.
    [000182] Still, as samples for comparison, samples were prepared by forming images without performing the pretreatment liquid application step and the drying step in Examples 1 to 6 and Comparative Examples 1 to 4, and the image quality and granularity were evaluated. Results are shown in Table 2. <Image Quality>
    [000183] Image quality was visually observed and assessed based on the following criteria. [Rating criteria]
    [000184] A: Significantly improved image quality compared to recorded matter where an image was formed without applying pretreatment liquid.
    [000185] B: Improved image quality compared to recorded matter where an image was formed without applying the pretreatment liquid.
    [000186] C: Slightly improved image quality compared to recorded matter where an image was formed without applying the pretreatment liquid.
    [000187] D: No significant change was observed visually compared to a recorded matter in which an image was formed without applying the pretreatment liquid. <Granularity>
    [000188] Granularity is a value that indicates granular random quality due to variations in image density. Using a CCD device (product of Hamamatsu Photonics KK, ORCA-3CCD C7780-20), a density was measured at 40 locations. A square root was obtained as a variation from an average density of the measurements, and the value was taken as granularity. Here, the image density was measured based on the values obtained previously by reading the density data with an X-Rite939 image density measurement device. Table 1-1

    Table 1-2


    [000189] The pretreatment liquid compositions in Table 1-1 and Table 1-2 are explained below. -Cationic Polymer- • “DK6810” is a water-soluble cationic polymer manufactured by Seiko PMC Corporation, and is a copolymer of alkylamine and epichlorohydrin.
    [000190] “SC-506” is a water-soluble cationic polymer manufactured by HYMO Co., Ltd., and is a copolymer of quaternary alkylamine and epichlorohydrin. - Ammonium salt of organic acid -
    [000191] As an ammonium salt of an organic acid, an ammonium lactate salt, an ammonium malate salt and an ammonium citrate salt were used.
    [000192] As the ammonium lactate salt, a product manufactured by Musashino Chemical Laboratory, Ltd. was used.
    [000193] As the malate ammonium salt, a product obtained by neutralizing malic acid manufactured by Fuso Chemical Co., Ltd. with an addition of aqueous ammonia manufactured by Tokyo Chemical Industry Co., Ltd. was used.
    [000194] As ammonium citrate salt, a product obtained by neutralizing citric acid manufactured by Fuso Chemical Co., Ltd. with an addition of aqueous ammonia manufactured by Tokyo Chemical Industry Co., Ltd. - Other components -
    [000195] As other components of the pretreatment liquids, the following components have been included: 5% by mass, 10% by mass or 20% by mass of 3-methyl-1,3-butanediol as a water-soluble organic solvent ; 0% by mass, 0.5% by mass or 2% by mass of a nonionic surfactant EMULGEN LS-106, manufactured by Kao Corporation, as a surfactant; 0% by mass, 0.2% by mass or 1% by mass of 2-ethyl-1,3-hexanediol as a penetration agent; 0% by mass, 0.1% by mass or 0.2% by mass of 2-amino-2-ethyl-1,3-propanediol as a pH adjuster; 0% by mass, 0.01% by mass or 0.05% by mass of 2,4,7,9-tetramethyl-4,7-decanediol as a suds suppressor; 0.1% by mass of 1,2-benzisothiazolin-3-one sodium compound as an antiseptic and fungicide; 0.05% by mass of 1,2,3-benzotriazole as a rust inhibitor; and water as a balance. Table 2


    [000196] From the results in Table 2, it was found that the degradation of granularity due to a drying effect was suppressed in Examples 1 to 6, where the pretreatment liquid was applied to the recording medium with the coating layer and then the pretreatment liquid is dried. On the other hand, it was found that the degradation of granularity was proceeding due to the drying effect in Comparative Examples 1 to 6.
    [000197] It has also been found that the drying step performed after application of the pretreatment liquid in Examples 1 to 6 prevents contamination on the rollers or members of the printing apparatus and allows for continuous imaging.
    [000198] Aspects of the present invention are as follows. - 1> An imaging method including:
    [000199] a pretreatment liquid application step for applying a pretreatment liquid on a recording medium including a substrate and a coating layer disposed on at least one surface of the substrate, wherein the pretreatment liquid treatment is applied to a surface of the recording medium with the coating layer;
    [000200] a drying step to dry the recording medium in which the pretreatment liquid has been applied; and
    [000201] an image formation step to form an image on the recording medium after drying by discharging a water-based ink by the inkjet method,
    [000202] wherein the pretreatment liquid includes a water-soluble cationic polymer, an ammonium salt of an organic acid and water, and
    [000203] wherein the water-based ink includes water and negatively charged colored particles including a colorant.
    [000204] <2> The imaging method according to <1>, wherein a content of the water-soluble cationic polymer in the pretreatment liquid is 10% by mass to 70% by mass, and a content of the ammonium salt of an organic acid in the pretreatment liquid is 1% by mass to 40% by mass.
    [000205] <3> The imaging method according to <2>, wherein a total content of the water-soluble cationic polymer content in the pretreatment liquid and the content of the ammonium salt of an organic acid in the pretreatment liquid is 30% by mass or greater.
    [000206] <4> The imaging method according to any one of <1> to <3>, wherein the water-soluble cationic polymer is a copolymer including an amine monomer and an epihalohydrin.
    [000207] <5> The imaging method according to any one of <1> to <4>, wherein the ammonium salt of an organic acid is ammonium malate, ammonium citrate or ammonium lactate, or any combination of them.
    [000208] <6> The imaging method according to <5>, wherein the ammonium salt of an organic acid is ammonium lactate.
    [000209] <7> The imaging method according to any one of <1> to <6>, wherein the pretreatment liquid includes a non-ionic surfactant.
    [000210] <8> The imaging method according to any one of <1> to <7>, wherein an amount of wet coating of the pretreatment liquid on the recording medium is 0.1 g/m2 at 10.0 g/m2.
    [000211] <9> The imaging method according to any one of <1> to <8>, wherein a drying temperature in the drying step is 80°C to 100°C.
    [000212] <10> An imaging device including:
    [000213] a pretreatment liquid application unit configured to apply a pretreatment liquid on a recording medium including a substrate and a coating layer disposed on at least one surface of the substrate, wherein the pretreatment liquid - treatment is applied to a surface of the recording medium with the coating layer,
    [000214] a drying unit configured to dry the recording medium on which the pretreatment liquid has been applied, and
    [000215] an imaging unit configured to form an image on the recording medium after drying by discharging a water-based ink by the inkjet method,
    [000216] wherein the pretreatment liquid includes a water-soluble cationic polymer, an ammonium salt of an organic acid and water, and
    [000217] wherein the water-based ink includes water and negatively charged colored particles including a colorant.
    [000218] <11> A recorded matter, including an image recorded by the imaging method according to any one of <1> to <9>.Reference Signal List101 Recording medium before printing102 Liquid application unit pre-treatment 103 Drying unit104 Print unit105 Recording medium after printing.
    权利要求:
    Claims (7)
    [0001]
    1. A method of imaging comprising: applying a pretreatment liquid onto a recording medium comprising a substrate and a coating layer disposed on at least one surface of the substrate, wherein the pretreatment liquid is applied over a surface of the recording medium with the coating layer; drying the recording medium to which the pretreatment liquid has been applied; and forming an image on the recording medium, after flush-drying a water-based ink by the inkjet method, wherein the pretreatment liquid comprises a water-soluble cationic polymer, an ammonia salt of an organic acid and water, in which the water-based ink comprises water and negatively charged colored particles, including a pigment such as a dye, characterized by the fact that the total content of water-soluble cationic polymer and ammonia salt of an organic acid in The ratio of the total amount of the pretreatment liquid is 40% by mass to 70% by mass, wherein the ammonium salt of an organic acid is selected from ammonium lactate, ammonium propionate, ammonium oxalate, ammonium tartrate. ammonium, ammonium succinate (diammonium succinate), diammonium malonate, ammonium malate, ammonium citrate, diammonium hydrogen citrate, triammonium citrate and ammonium L-glutamate, where the ammonium salt content of an acid organic in rel action to the total amount of the pretreatment liquid is 10% by mass to 40% by mass, and the content of the water-soluble cationic polymer with respect to the total amount of the pretreatment liquid is 10% by mass to 70% in large scale.
    [0002]
    2. Imaging method according to claim 1, characterized in that the water-soluble cationic polymer is a copolymer, including an amine monomer and epihalohydrin.
    [0003]
    3. Imaging method according to claim 1 or 2, characterized in that the ammonium salt of an organic acid is ammonium malate, ammonium citrate or ammonium lactate, or any combination thereof.
    [0004]
    4. Imaging method according to claim 3, characterized in that the ammonium salt of an organic acid is ammonium lactate.
    [0005]
    5. Method for imaging, according to any one of claims 1 to 4, characterized in that the pre-treatment liquid comprises a non-ionic surfactant.
    [0006]
    6. Imaging method according to any one of claims 1 to 5, characterized in that an amount of wet coating of the pre-treatment liquid on the recording medium is 0.1 g/m2 and 10 .0 g/m2.
    [0007]
    7. Imaging method according to any one of claims 1 to 6, characterized in that a drying temperature during drying is 80 °C to 100 °C.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112015000654B1|2021-09-08|IMAGE FORMATION METHOD, IMAGE FORMATION APPARATUS, AND RECORDED MATTER
    BR102013002698B1|2020-11-17|post-treatment liquid for inkjet engraving, imaging method, cartridge and imaging apparatus
    CN103140356B|2015-01-07|Image forming method and image formed matter
    BR102013000712B1|2020-11-17|image formation method
    JP5459573B2|2014-04-02|Ink composition for inkjet recording
    JP5426351B2|2014-02-26|Ink set for inkjet recording
    EP2774771B1|2019-09-04|Pre-treatment liquid and image forming method
    BR112013021183B1|2020-08-11|LIQUID TREATMENT LIQUID AND IMAGE FORMATION METHOD USING TREATMENT LIQUID
    JP2011026564A|2011-02-10|Ink-jet printing ink, and ink-jet printing method using the same, and cartridge filled with the same, and printed matter
    JP6464908B2|2019-02-06|Image forming treatment liquid, image forming method, recorded matter, ink jet recording apparatus
    JP6868217B2|2021-05-12|Liquid composition for surface treatment of printed matter, ink set using it, recording method, recording device, storage container, printed matter
    JPH11228898A|1999-08-24|Ink for ink jet recording and ink jet recording
    TW201311832A|2013-03-16|Perfluoropolyethers as ink additives
    US10676628B2|2020-06-09|Surface treatment liquid composition for substrate, ink set, recording method, recording device, storage container, and printed matter
    EP3584086A1|2019-12-25|Receiving solution, ink set containing this receiving solution, and method for producing printed material with use of ink set
    JP6213735B2|2017-10-18|Maintenance liquid for water-based inkjet recording
    JP4393748B2|2010-01-06|Inkjet ink
    JP6471026B2|2019-02-13|Inkjet recording method
    JP2011137122A|2011-07-14|Aqueous inkjet ink
    JP6443038B2|2018-12-26|Treatment liquid, image forming method, recorded matter, recording apparatus
    JP2001254036A|2001-09-18|Ink and recording method using the same
    EP3584085A1|2019-12-25|Receptive solution, ink set containing said receptive solution and method for producing printed material using ink set
    JP2016120670A|2016-07-07|Image forming method ann ink set
    JP6953697B2|2021-10-27|Water-based inks and ink cartridges for inkjet recording
    JP2011099007A|2011-05-19|Inkjet clear ink, ink set, and inkjet recording method
    同族专利:
    公开号 | 公开日
    EP2872338B1|2017-03-15|
    BR112015000654A2|2017-06-27|
    JP2014015008A|2014-01-30|
    CN104470726B|2016-04-13|
    CN104470726A|2015-03-25|
    US20150283828A1|2015-10-08|
    WO2014010710A1|2014-01-16|
    EP2872338A1|2015-05-20|
    EP2872338A4|2015-08-26|
    RU2015104348A|2016-08-27|
    US9789720B2|2017-10-17|
    RU2606183C2|2017-01-10|
    IN2014KN02941A|2015-05-08|
    JP5910372B2|2016-04-27|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JP3206797B2|1995-04-21|2001-09-10|セイコーエプソン株式会社|Inkjet recording method|
    JP3729310B2|1997-08-01|2005-12-21|リコープリンティングシステムズ株式会社|Hot melt ink composition for inkjet|
    JP4314333B2|1998-08-21|2009-08-12|日本製紙株式会社|Ink jet recording paper and method for producing the same|
    US6899751B2|2000-09-29|2005-05-31|Ricoh Company, Ltd.|Ink for ink jet recording, ink jet recording method, ink cartridge and ink jet recording apparatus|
    US6833008B2|2001-01-16|2004-12-21|Aprion Digital Ltd.|Surface treatment for printing applications using water-based ink|
    JP2004002692A|2002-03-26|2004-01-08|Hymo Corp|Water-soluble polymer having lowered molecular weight, its preparation process, and method of using it|
    CN100448671C|2002-06-24|2009-01-07|株式会社理光|Inkjet recording apparatus and inkjet recording method|
    JP2004090596A|2002-09-04|2004-03-25|Canon Inc|Image forming method and image forming apparatus|
    EP1791917B1|2004-09-13|2011-09-07|Ricoh Company, Ltd.|Recording ink, ink cartridge, ink record, inkjet recording apparatus, and inkjet recording method|
    DE602005018507D1|2004-09-17|2010-02-04|Ricoh Kk|RECORDING INK, INK CARTRIDGE, INK RECORDING, INK RADIATION RECORDING DEVICE, AND INK RADIATION RECORDING METHOD|
    US8044114B2|2005-08-23|2011-10-25|Ricoh Company, Ltd.|Ink for recording, and ink cartridge, ink recorded matter, inkjet recording apparatus and inkjet recording method using the same|
    WO2007049782A1|2005-10-24|2007-05-03|Ricoh Company, Ltd.|Recording ink, recording ink set, records, ink cartridge, recording method, and inkjet recording apparatus|
    KR100980746B1|2005-12-22|2010-09-07|가부시키가이샤 리코|Pigment dispersion, recording ink, ink cartridge, ink-jet recording method and ink-jet recording apparatus|
    US20070197685A1|2006-01-18|2007-08-23|Tamotsu Aruga|Recording ink as well as ink media set, ink cartridge, ink recorded matter, inkjet recording apparatus and inkjet recording method|
    EP1994102B1|2006-03-10|2011-12-28|Ricoh Company, Ltd.|Recording ink, ink cartridge, inkjet recording method, and inkjet recording apparatus|
    JP2007276387A|2006-04-11|2007-10-25|Ricoh Co Ltd|Ink media set and pretreatment liquid cartridge, ink cartridge, ink recording object, inkjet recording method, and inkjet recording device|
    JP5118832B2|2006-08-22|2013-01-16|株式会社リコー|Ink for recording and ink media set, ink cartridge, ink jet recording method and ink jet recording apparatus|
    KR101045624B1|2006-09-15|2011-07-01|가부시키가이샤 리코|Inkjet recording ink, inkjet recording ink set, inkjet recording ink media set, ink cartridge, inkjet recording method and inkjet recording apparatus|
    WO2008032864A1|2006-09-15|2008-03-20|Ricoh Company, Ltd.|Recording ink, inkjet recording method and inkjet recording apparatus|
    CN101379150B|2006-09-19|2012-05-23|株式会社理光|Recording ink, ink media set, ink cartridge, ink recorded matter, inkjet recording apparatus, and inkjet recording method|
    US7919544B2|2006-12-27|2011-04-05|Ricoh Company, Ltd.|Ink-media set, ink composition, ink cartridge, inkjet recording method, inkjet recording apparatus, and ink recorded matter|
    CN101573419A|2006-12-28|2009-11-04|株式会社理光|Refill ink and ink cartridge|
    JP5170508B2|2007-03-16|2013-03-27|株式会社リコー|Ink media set, ink jet recording method, recorded matter, and recording apparatus|
    JP5240501B2|2007-03-19|2013-07-17|株式会社リコー|Ink set, ink cartridge, ink jet recording method, and ink jet recording apparatus|
    EP2136999B1|2007-03-19|2015-02-25|Ricoh Company, Ltd.|Ink-jet recording method|
    JP5263584B2|2007-06-12|2013-08-14|株式会社リコー|Ink jet recording ink, ink media set, ink cartridge, ink jet recording apparatus, and ink jet recording method|
    JP5224092B2|2007-09-14|2013-07-03|株式会社リコー|Ink for recording, ink media set, ink cartridge, ink record, ink jet recording apparatus, and ink jet recording method|
    JP5360455B2|2007-11-26|2013-12-04|株式会社リコー|Inkjet recording ink, inkjet recording ink set, inkjet recording ink-media set, ink cartridge, inkjet recording method, inkjet recording apparatus|
    JP5403310B2|2007-12-26|2014-01-29|株式会社リコー|Ink jet recording ink, ink set for ink jet recording, ink media set for ink jet recording, ink cartridge, ink jet recording method, ink jet recording apparatus|
    JP2009166387A|2008-01-17|2009-07-30|Ricoh Co Ltd|Image formation method and image formation recorded matter|
    JP5415029B2|2008-07-01|2014-02-12|株式会社リコー|UV curable ink jet recording ink and color image forming apparatus|
    JP5621192B2|2008-09-05|2014-11-05|株式会社リコー|Ink jet ink, ink cartridge, ink jet recording apparatus, ink jet recording method, image forming method, and ink recorded matter|
    JP5453750B2|2008-09-17|2014-03-26|株式会社リコー|Ink set for inkjet recording and inkjet recording method|
    JP5381015B2|2008-10-30|2014-01-08|株式会社リコー|Ink set for ink jet recording, ink cartridge, ink jet recording method, and ink jet recording apparatus|
    JP5568900B2|2008-10-30|2014-08-13|株式会社リコー|Ink jet recording ink, ink set, ink cartridge, recording method and recorded matter|
    JP2010158887A|2008-12-09|2010-07-22|Seiko Epson Corp|Image recording method, recorded article, and image recording system|
    JP2010188568A|2009-02-17|2010-09-02|Ricoh Co Ltd|Pretreatment apparatus of recording medium and image forming apparatus equipped with the same|
    JP5564821B2|2009-04-09|2014-08-06|株式会社リコー|Inkjet pretreatment liquid, image forming method, and image formed product|
    JP5776141B2|2009-06-23|2015-09-09|株式会社リコー|Ink jet recording ink, ink jet recording method using the ink, cartridge containing the ink, and recorded matter|
    US8814340B2|2009-08-21|2014-08-26|Ricoh Company, Ltd.|Image forming method, and image formed matter|
    CN102781677B|2010-02-26|2014-07-09|株式会社理光|Inkjet treatment liquid, inkjet recording apparatus, inkjet recording method and image formation|
    JP5672065B2|2010-03-02|2015-02-18|株式会社リコー|Ink jet recording ink, ink set for ink jet recording, ink cartridge, ink jet recording method, ink jet recording apparatus, and ink recorded matter|
    JP5398607B2|2010-03-17|2014-01-29|富士フイルム株式会社|Image forming method|
    JP5579476B2|2010-03-26|2014-08-27|富士フイルム株式会社|Inkjet ink set and image forming method|
    JP5990868B2|2010-04-09|2016-09-14|株式会社リコー|Film production method and film by ink jet method|
    US8807731B2|2010-06-02|2014-08-19|Ricoh Company, Ltd.|Inkjet image forming apparatus and inkjet image forming method|
    JP2012000893A|2010-06-17|2012-01-05|Ricoh Co Ltd|Inkjet recording treatment liquid, inkjet cartridge, inkjet recording ink set, and inkjet recording method|
    JP5549422B2|2010-06-29|2014-07-16|株式会社リコー|Liquid composition, recording method, and recorded matter|
    JP5601075B2|2010-08-04|2014-10-08|株式会社リコー|Ink jet ink, ink cartridge, ink jet recording method, ink jet recording apparatus, and ink recorded matter|
    JP5793840B2|2010-08-19|2015-10-14|株式会社リコー|Liquid composition, recording method, and recorded matter|
    JP5879875B2|2010-09-30|2016-03-08|株式会社リコー|Image forming method|
    JP5843215B2|2010-10-08|2016-01-13|株式会社リコー|Inkjet recording method|
    JP5594089B2|2010-11-24|2014-09-24|株式会社リコー|Inkjet pretreatment liquid, inkjet recording method and inkjet recorded matter|
    JP5737141B2|2010-12-14|2015-06-17|株式会社リコー|Active energy ray-curable ink for inkjet, ink container, image forming apparatus and image forming method|
    JP2012140550A|2011-01-04|2012-07-26|Ricoh Co Ltd|Ultraviolet-curable ink and inkjet recording method|
    JP5879689B2|2011-02-07|2016-03-08|株式会社リコー|Photopolymerizable inkjet black ink, ink cartridge, inkjet printer, printed matter, and manufacturing method|
    JP5768394B2|2011-02-10|2015-08-26|株式会社リコー|Ink set for ink jet recording, ink jet recording method using the ink set, and recorded matter|
    JP5919901B2|2011-03-15|2016-05-18|株式会社リコー|Ink jet recording ink, ink jet recording method, and ink recorded matter|
    JP5966482B2|2011-03-25|2016-08-10|株式会社リコー|Ink jet recording method and ink jet recording apparatus|
    JP5874194B2|2011-05-16|2016-03-02|株式会社リコー|Photopolymerizable inkjet ink, ink cartridge, printer|
    JP5888589B2|2011-06-28|2016-03-22|株式会社リコー|Ink for inkjet recording-Media set for recording and inkjet recording method|
    JP2013067162A|2011-09-08|2013-04-18|Ricoh Co Ltd|Inkjet recording apparatus, method for forming inkjet image, and inkjet ink|
    JP5942708B2|2011-09-13|2016-06-29|株式会社リコー|Ink jet ink, ink jet recording method, ink jet recording apparatus, and ink recorded matter|
    JP6051695B2|2011-09-15|2016-12-27|株式会社リコー|Image forming method and inkjet image forming apparatus for carrying out the image forming method|
    JP6031903B2|2011-09-16|2016-11-24|株式会社リコー|Ink composition for ink jet recording and ink jet recording method|
    JP5810883B2|2011-12-14|2015-11-11|株式会社リコー|Image forming method|
    EP2614964B1|2012-01-10|2017-01-04|Ricoh Company, Ltd.|Image forming method|
    JP2013155322A|2012-01-31|2013-08-15|Ricoh Co Ltd|Ink|
    JP6051530B2|2012-02-01|2016-12-27|株式会社リコー|Inkjet recording method|
    JP5957915B2|2012-02-01|2016-07-27|株式会社リコー|Cleaning liquid / filling liquid, cartridge containing the cleaning liquid / filling liquid, and method for cleaning, filling, and storing an inkjet recording apparatus using the cleaning liquid / filling liquid|
    JP6051531B2|2012-02-01|2016-12-27|株式会社リコー|Inkjet recording method|
    US9321921B2|2012-02-02|2016-04-26|Ricoh Company, Ltd.|Post-treatment liquid for inkjet recording, image forming method, cartridge and image forming apparatus|EP3141656B1|2014-05-08|2019-05-22|Konica Minolta, Inc.|Inkjet printing method and inkjet printing apparatus|
    JP6443038B2|2014-06-19|2018-12-26|株式会社リコー|Treatment liquid, image forming method, recorded matter, recording apparatus|
    US10280321B2|2015-01-29|2019-05-07|Ricoh Company, Ltd.|Ink, ink container, inkjet recording device, and recorded matter|
    DE102015101858A1|2015-02-10|2016-10-20|Océ Printing Systems GmbH & Co. KG|Method for controlling a substrate temperature and printing arrangement for printing on a substrate|
    JP6464908B2|2015-04-23|2019-02-06|株式会社リコー|Image forming treatment liquid, image forming method, recorded matter, ink jet recording apparatus|
    US10190007B2|2015-05-14|2019-01-29|Ricoh Company, Ltd.|Ink, ink container, image forming method, image forming apparatus, and image formed matter|
    US10131805B2|2015-06-23|2018-11-20|Ricoh Company, Ltd.|Ink, ink stored container, inkjet recording apparatus, and printed matter|
    US9873809B2|2015-07-07|2018-01-23|Ricoh Company, Ltd.|Ink, image forming method, image forming apparatus, and recorded matter|
    US9938421B2|2015-07-24|2018-04-10|Ricoh Company, Ltd.|Set of ink and print medium, inkjet printing method, inkjet printing apparatus, printed matter, ink, and ink stored container|
    JP2017082043A|2015-10-23|2017-05-18|株式会社リコー|Ink, image formation method and image formation device|
    US9937715B2|2015-11-30|2018-04-10|Ricoh Company, Ltd.|Inkjet recording method and inkjet recording device|
    JP6801179B2|2015-12-04|2020-12-16|株式会社リコー|Ink, ink container, image forming method, liquid ejection device, and image|
    US9873252B2|2015-12-25|2018-01-23|Ricoh Company, Ltd.|Printing device and printing method|
    JP2017149042A|2016-02-25|2017-08-31|セイコーエプソン株式会社|Image formation apparatus and image formation method|
    US10233345B2|2016-03-17|2019-03-19|Ricoh Company, Ltd.|Ink set, recording device, and method of recording|
    WO2017196365A1|2016-05-13|2017-11-16|Hewlett-Packard Development Company, L.P.|Pre-treatment coating compositions|
    CN107674499B|2016-08-01|2021-07-13|株式会社理光|Ink, ink container, liquid discharging apparatus, image forming method and apparatus|
    JP2018069715A|2016-11-04|2018-05-10|セイコーエプソン株式会社|Printer and printing method|
    EP3494186B1|2017-01-31|2020-04-15|Hewlett-Packard Development Company, L.P.|Inkjet ink composition|
    WO2018143962A1|2017-01-31|2018-08-09|Hewlett-Packard Development Company, L.P.|Method of inkjet printing and fixing composition|
    CN109844042A|2017-01-31|2019-06-04|惠普发展公司，有限责任合伙企业|Ink-jet print system|
    EP3494183B1|2017-01-31|2022-01-26|Hewlett-Packard Development Company, L.P.|Inkjet ink composition and inkjet cartridge|
    US11208570B2|2017-04-13|2021-12-28|Hewlett-Packard Development Company, L.P.|White inks|
    JP2019081303A|2017-10-31|2019-05-30|セイコーエプソン株式会社|Inkjet recording method and recording device|
    JP2019155903A|2018-03-06|2019-09-19|株式会社リコー|Liquid composition, liquid composition adding device, image formation device, and image formation method|
    JP2020037252A|2018-09-03|2020-03-12|株式会社リコー|Liquid discharge device|
    WO2020122935A1|2018-12-14|2020-06-18|Hewlett-Packard Development Company, L.P.|Fluid sets|
    WO2020131008A1|2018-12-17|2020-06-25|Hewlett-Packard Development Company, L.P.|Fluid sets|
    US20210163774A1|2019-01-09|2021-06-03|Hewlett-Packard Development Company, L.P.|Fluid sets|
    EP3888927A1|2020-03-31|2021-10-06|Canon Production Printing Holding B.V.|Method for applying an image onto a recording medium and corresponding printing apparatus|
    法律状态:
    2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |
    2019-10-01| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-03-09| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-07-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-09-08| 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 05/07/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2012155193A|JP5910372B2|2012-07-11|2012-07-11|Image forming method|
    JP2012-155193|2012-07-11|
    PCT/JP2013/069072|WO2014010710A1|2012-07-11|2013-07-05|Image forming method, image forming apparatus, and recorded matter|
    [返回顶部]