JP2019151062A - Image formation method and image formation device - Google Patents

Abstract

To provide an image formation method which controls a dot diameter of ink to improve granularity of an intermediate gradation without giving a damage to a base material.SOLUTION: An image formation method includes: a treatment liquid imparting step of imparting a treatment liquid A containing water, an organic solvent, resin particles and inorganic particles and a treatment liquid B having surface tension lower than that of the treatment liquid A to different regions on a recording medium; and an ink imparting step of imparting ink containing water, an organic solvent and a coloring material to the recording medium to which the treatment liquids A and B are imparted.SELECTED DRAWING: None

Description

  The present invention relates to an image forming method and an image forming apparatus.

  In recent years, a printing method in which a pretreatment liquid is applied before forming an image with ink has been increasing from the viewpoint of bleeding of characters and fixability to a non-permeable substrate. It is also known that the fixing property and the ink dot diameter can be controlled by the drying temperature in the printing process.

  As such a printing method, an image forming method in which image quality such as character bleeding and color bleeding is improved by applying a pretreatment liquid containing a cationic compound has been proposed (for example, see Patent Document 1).

  An object of the present invention is to provide an image forming method capable of improving the granularity of intermediate gradations by controlling the dot diameter of ink without damaging the substrate.

The image forming method of the present invention as a means for solving the above-described problems includes a treatment liquid A containing water, an organic solvent, resin particles, and inorganic particles, and a treatment liquid B having a surface tension lower than that of the treatment liquid A. , A treatment liquid application step for applying to different areas on the recording medium,
An ink application step of applying an ink containing water, an organic solvent, and a coloring material onto the recording medium to which the treatment liquids A and B are applied.

  According to the present invention, it is possible to provide an image forming method capable of improving the granularity of the intermediate gradation by controlling the dot diameter of the ink without damaging the substrate.

FIG. 1 is a perspective explanatory view showing an example of the image forming apparatus of the present invention. FIG. 2 is an explanatory perspective view showing an example of a main tank in the image forming apparatus of the present invention. FIG. 3 is a diagram in which black solid images of 10% gradation and 60% gradation are formed at a resolution of 600 dpi.

(Image forming method and image forming apparatus)
In the image forming method of the present invention, a treatment liquid A containing water, an organic solvent, resin particles, and inorganic particles and a treatment liquid B having a surface tension lower than that of the treatment liquid A are applied to different areas on the recording medium. A treatment liquid applying step,
An ink application step of applying an ink containing water, an organic solvent, and a coloring material onto the recording medium to which the treatment liquids A and B are applied, and further includes other steps as necessary.
In the present invention, “giving to different areas on the recording medium” includes “giving with different patterns”. For example, it is also possible to adopt a mode in which one treatment liquid is adhered to the entire surface by roller coating or the like, and the other treatment liquid is partially adhered by an inkjet method.

The image forming apparatus of the present invention applies a treatment liquid A containing water, an organic solvent, resin particles, and inorganic particles, and a treatment liquid B having a surface tension lower than that of the treatment liquid A to different areas on the recording medium. A treatment liquid applying means,
An ink application unit that applies ink containing water, an organic solvent, and a coloring material onto the recording medium to which the treatment liquids A and B are applied, and further includes other units as necessary.

In the prior art, the spread of characters and fixability are improved by applying the pretreatment liquid, but it is difficult to control the dot diameter of the ink with one kind of pretreatment liquid. In this case, it is possible to control the dot diameter of the ink by adjusting the printing temperature in the drying process, but there is a possibility of causing damage such as deterioration in ejection reliability and discoloration and deformation of the substrate.
Therefore, in the present invention, the treatment liquid A containing water, organic solvent, resin particles, and inorganic particles and the treatment liquid B having a surface tension lower than that of the treatment liquid A are applied to different areas on the recording medium. By including a treatment liquid application step, and an ink application step of applying ink containing water, an organic solvent, and a coloring material onto the recording medium to which the treatment liquids A and B have been applied,
By controlling the dot diameter of the ink without damaging the substrate, it is possible to improve the granularity of the intermediate gradation.

<Processing liquid application process and processing liquid application means>
The treatment liquid applying step is a step of applying a treatment liquid A containing water, an organic solvent, resin particles, and inorganic particles and a treatment liquid B having a surface tension lower than that of the treatment liquid A to different regions on the recording medium. It is carried out by the treatment liquid applying means.

<< Processing liquid A >>
The treatment liquid A contains water, an organic solvent, resin particles, and inorganic particles, and further contains other components as necessary.

<Organic solvent>
The organic solvent used in the present invention is not particularly limited, and a water-soluble organic solvent can be used. Examples thereof include ethers such as polyhydric alcohols, polyhydric alcohol alkyl ethers and polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines and sulfur-containing compounds.
Specific examples of the water-soluble organic solvent include, for example, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butane. Diol, 2,3-butanediol, 3-methyl-1,3-butanediol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol 2,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,3-hexanediol, 2,5-hexanediol, 1,5-hexanediol, Glycerin, 1,2,6-hexanetriol, 2-ethyl-1,3-he Polyhydric alcohols such as sundiol, ethyl-1,2,4-butanetriol, 1,2,3-butanetriol, 2,2,4-trimethyl-1,3-pentanediol, petriol, ethylene glycol mono Polyhydric alcohol alkyl ethers such as ethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monophenyl ether, ethylene glycol mono Polyhydric alcohol aryl ethers such as benzyl ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl- -N-containing heterocyclic compounds such as pyrrolidone, 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, γ-butyrolactone, formamide, N-methylformamide, N, N-dimethylformamide, 3-methoxy-N, Amides such as N-dimethylpropionamide and 3-butoxy-N, N-dimethylpropionamide, amines such as monoethanolamine, diethanolamine and triethylamine, sulfur-containing compounds such as dimethylsulfoxide, sulfolane and thiodiethanol, propylene carbonate, Examples thereof include ethylene carbonate.
In addition to functioning as a wetting agent, it is preferable to use an organic solvent having a boiling point of 250 ° C. or lower because good drying properties can be obtained.

  Among these, 1,2-propanediol, 1,2-butanediol, 2,3-butanediol, 4-methyl-1,2-pentanediol, and 4-methoxy-3-methyl-1-butanol are preferable.

  As content of the said organic solvent, 10 mass% or more and 60 mass% or less are preferable with respect to the process liquid A whole quantity, and 20 mass% or more and 60 mass% or less are more preferable.

-Inorganic particles-
Examples of the inorganic particles include titanium compounds, chromium compounds, copper compounds, cobalt compounds, strontium compounds, barium compounds, iron compounds, aluminum compounds, calcium compounds, magnesium compounds, zinc compounds, nickel compounds, and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, a calcium compound and a magnesium compound are preferable.

There is no restriction | limiting in particular as said calcium compound, According to the objective, it can select suitably, For example, calcium carbonate, calcium nitrate, calcium chloride, calcium acetate, calcium sulfate, calcium silicate, or these hydrates etc. Can be mentioned.
There is no restriction | limiting in particular as said magnesium compound, According to the objective, it can select suitably, For example, magnesium chloride, magnesium acetate, magnesium sulfate, magnesium silicate, or these hydrates etc. are mentioned.
There is no restriction | limiting in particular as said barium compound, According to the objective, it can select suitably, For example, barium sulfate or its hydrate etc. are mentioned.
There is no restriction | limiting in particular as said zinc compound, According to the objective, it can select suitably, For example, zinc sulfide, zinc carbonate, etc. are mentioned.
There is no restriction | limiting in particular as said aluminum compound, According to the objective, it can select suitably, For example, aluminum silicate, aluminum hydroxide, etc. are mentioned.
Among these, calcium carbonate, calcium chloride, and magnesium sulfate are preferable.

  1 mass% or more and 10 mass% or less are preferable with respect to the process liquid A whole quantity, and, as for content of the said inorganic particle, 1 mass% or more and 7 mass% or less are more preferable.

-Resin particles-
The resin particles contained in the treatment liquid A are not particularly limited and may be appropriately selected depending on the intended purpose. For example, urethane resin particles, polyester resin particles, acrylic resin particles, vinyl acetate resin particles, styrene Resin particles, butadiene resin resin, styrene-butadiene resin particles, vinyl chloride resin particles, acrylic styrene resin particles, acrylic silicone resin particles, ethylene-vinyl acetate resin particles, ethylene-vinyl acetate-vinyl chloride copolymer Examples thereof include resin particles and vinyl acetate-acrylic resin particles. These may be used alone or in combination of two or more kinds of resin particles.
The treatment liquid A can be obtained by mixing the resin particles with a material such as an organic solvent in the state of a resin emulsion in which water is dispersed as a dispersion medium. As said resin particle, what was synthesize | combined suitably may be used and a commercial item may be used.
The volume average particle diameter of the resin particles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 nm or more and 1,000 nm or less from the viewpoint of obtaining good fixability and high image hardness. It is more preferably 200 nm or less and particularly preferably 10 nm or more and 100 nm or less.
The volume average particle diameter can be measured using, for example, a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).
There is no restriction | limiting in particular as content of a resin particle, Although it can select suitably according to the objective, 1 to 30 mass% is preferable with respect to the processing liquid A whole quantity, and 5 to 20 mass% is preferable. % Or less is more preferable.

--- Water--
Examples of the water include pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, and distilled water; ultrapure water and the like. These may be used individually by 1 type and may use 2 or more types together.
As content of the said water, 60 mass% or less is preferable with respect to the processing liquid A whole quantity, and 30 mass% or more and 50 mass% or less are more preferable. When the content is 60% by mass or less, it is possible to suppress the occurrence of an increase in viscosity of the treatment liquid, gelation, precipitation of insoluble matters, and the like when water is evaporated.

-Other ingredients-
The other components are not particularly limited and may be appropriately selected depending on the purpose. For example, surfactants, foam suppressors, pH adjusters, antibacterial agents, chelating reagents, rust preventives, antioxidants Etc. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as a physical property of the said processing liquid A, According to the objective, a viscosity, surface tension, pH, etc. can be selected suitably.

  The viscosity of the treatment liquid A is preferably 0.5 mPa · s to 30 mPa · s at 25 ° C. Here, the viscosity can be measured using, for example, a viscometer (device name: RE-550L, manufactured by Toki Sangyo Co., Ltd.).

The surface tension of the treatment liquid A is preferably 20 mN / m or more and 50 mN / m or less, and more preferably 25 mN / m or more and 35 mN / m or less at 25 ° C.
The surface tension was measured by the Wilhelmy method using, for example, AUTOMATIC SUPERFACE TENSIONMETER CBVP-Z manufactured by Kyowa Interface Science Co., Ltd. as a measuring instrument. In the Wilhelmy method, measurement can be performed by reading a force for pulling the measuring element generated when the measuring element (platinum plate) touches the surface of the liquid into the liquid.

  As pH of the said processing liquid A, 4-12 are preferable, for example, and 4-8 are more preferable.

  A method for applying the treatment liquid A to the recording medium is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a liquid discharge method and a coating method.

  The liquid ejection method is not particularly limited and can be appropriately selected according to the purpose. For example, the ejection head driving method includes a piezoelectric element actuator using PZT, a method of applying thermal energy, an electrostatic An on-demand type head using an actuator using force or the like can be used, or a continuous injection type charge control type head can be used.

  Examples of the coating method include blade coating, gravure coating, gravure offset coating, wire bar coating, bar coating, roll coating, knife coating, air knife coating, comma coating, and U comma coating. , AKKU coating method, smoothing coating method, micro gravure coating method, reverse roll coating method, 4 to 5 roll coating method, dip coating method, curtain coating method, slide coating method, die coating method and the like. Among these, a wire bar coating method and a roller coating method are particularly preferable.

  The treatment liquid A may be applied to a recording medium whose surface is sufficiently dried, or the effect can be exerted even if it is applied to a recording medium which has been image-formed and is being dried.

The coating weight of the recording medium of the processing liquid A in the treatment liquid application process, 0.1 g / ^{m 2} or more 30.0 g / ^{m 2} or less is preferable, 0.2 g / ^{m 2} or more 10.0 g / ^{m 2} or less Is more preferable.

<< Processing liquid B >>
The treatment liquid B has a lower surface tension than the treatment liquid A, contains water, an organic solvent, resin particles, and a surfactant, and further contains other components as necessary.

  About the water in the processing liquid B, the organic solvent, and the resin particle, the thing similar to the said processing liquid A can be used.

<Surfactant>
As the surfactant, any of silicone surfactants, fluorine surfactants, amphoteric surfactants, nonionic surfactants and anionic surfactants can be used.
There is no restriction | limiting in particular in silicone type surfactant, According to the objective, it can select suitably. Among them, those that do not decompose even at high pH are preferable, and examples thereof include side chain modified polydimethylsiloxane, both terminal modified polydimethylsiloxane, one terminal modified polydimethylsiloxane, and side chain both terminal modified polydimethylsiloxane. Those having an oxyethylene group or a polyoxyethylene polyoxypropylene group are particularly preferred because they exhibit good properties as an aqueous surfactant. In addition, as the silicone surfactant, a polyether-modified silicone surfactant can be used, and examples thereof include a compound in which a polyalkylene oxide structure is introduced into the side chain of the Si portion of dimethylsiloxane.
Examples of the fluorosurfactant include a perfluoroalkyl sulfonic acid compound, a perfluoroalkyl carboxylic acid compound, a perfluoroalkyl phosphate compound, a perfluoroalkyl ethylene oxide adduct, and a perfluoroalkyl ether group in the side chain. Polyoxyalkylene ether polymer compounds are particularly preferred because of their low foaming properties. Examples of the perfluoroalkyl sulfonic acid compound include perfluoroalkyl sulfonic acid, perfluoroalkyl sulfonate, and the like. Examples of the perfluoroalkylcarboxylic acid compound include perfluoroalkylcarboxylic acid and perfluoroalkylcarboxylate. Examples of the polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain include a sulfate ester salt of a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in the side chain and a perfluoroalkyl ether group in the side chain. Examples thereof include salts of polyoxyalkylene ether polymers. As counter ions of salts in these fluorosurfactants, Li, Na, K, NH ₄ , NH ₃ CH ₂ CH ₂ OH, NH ₂ (CH ₂ CH ₂ OH) ₂ , NH (CH ₂ CH ₂ OH) ₃ etc. are mentioned.
Examples of amphoteric surfactants include lauryl aminopropionate, lauryl dimethyl betaine, stearyl dimethyl betaine, and lauryl dihydroxyethyl betaine.
Nonionic surfactants include, for example, polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkylamine, polyoxyethylene alkylamide, polyoxyethylene propylene block polymer, sorbitan fatty acid ester, polyoxyethylene sorbitan Examples include fatty acid esters and ethylene oxide adducts of acetylene alcohol.
Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, laurate, polyoxyethylene alkyl ether sulfate salt, and the like.
These may be used alone or in combination of two or more.

The silicone surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, side chain modified polydimethylsiloxane, both terminal modified polydimethylsiloxane, one terminal modified polydimethylsiloxane, side Since both ends of the chain are modified with polydimethylsiloxane, a polyether-modified silicone surfactant having a polyoxyethylene group or a polyoxyethylene polyoxypropylene group as a modifying group exhibits good properties as an aqueous surfactant. preferable.
As such a surfactant, an appropriately synthesized product or a commercially available product may be used. Commercially available products can be obtained from, for example, Big Chemie Co., Ltd., Shin-Etsu Chemical Co., Ltd., Toray Dow Corning Silicone Co., Ltd., Nippon Emulsion Co., Ltd., and Kyoeisha Chemical Co., Ltd.
There is no restriction | limiting in particular as said polyether modified silicone surfactant, According to the objective, it can select suitably, For example, the polyalkylene oxide structure represented by a general formula (S-1) type | formula is dimethylpolyethylene. Examples thereof include those introduced into the side chain of Si part of siloxane.
Formula (S-1)
(However, in the formula (S-1), m, n, a, and b each independently represent an integer, R represents an alkylene group, and R ′ represents an alkyl group.)
A commercial item can be used as said polyether modified silicone type surfactant, For example, KF-618, KF-642, KF-643 (Shin-Etsu Chemical Co., Ltd.), EMALEX-SS-5602, SS- 1906EX (Japan Emulsion Co., Ltd.), FZ-2105, FZ-2118, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ-2164 (Toray Dow Corning Silicone Co., Ltd.), BYK-33, BYK-387, 333, 345, 347, 348 (Bic Chemie Co., Ltd.), TSF4440, TSF4452, TSF4453 (Toshiba Silicon Co., Ltd.), etc. are mentioned.

As the fluorine-based surfactant, a fluorine-substituted compound having 2 to 16 carbon atoms is preferable, and a fluorine-substituted compound having 4 to 16 carbon atoms is more preferable.
Examples of the fluorosurfactant include perfluoroalkyl phosphate compounds, perfluoroalkylethylene oxide adducts, and polyoxyalkylene ether polymer compounds having a perfluoroalkyl ether group in the side chain. Among these, a polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain is preferable because of its low foaming property, and in particular, fluorine-based compounds represented by the general formulas (F-1) and (F-2) A surfactant is preferred.
Formula (F-1)
In the compound represented by the general formula (F-1), m is preferably an integer of 0 to 10 and n is preferably an integer of 0 to 40 in order to impart water solubility.
Formula (F-2)
_{C n F 2n + 1- CH 2} CH (OH) CH 2 -O- (CH 2 CH 2 O) a -Y
In the compound represented by the general formula (F-2), Y is H, or CmF _{2m + 1} , m is an integer of 1 to 6, or CH ₂ CH (OH) CH ₂ —CmF _{2m + 1,} where m is 4 to 6. An integer, or CpH _{2p + 1} , p is an integer of 1-19. n is an integer of 1-6. a is an integer of 4-14.
A commercial item may be used as said fluorosurfactant. As this commercial item, for example, Surflon S-111, S-112, S-113, S-121, S-131, S-132, S-141, S-145 (all manufactured by Asahi Glass Co., Ltd.); Fullrad FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431 (all manufactured by Sumitomo 3M Limited); Megafac F-470, F -1405, F-474 (all manufactured by Dainippon Ink & Chemicals, Inc.); Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, UR, Capstone FS-30, FS-31, FS-3100, FS-34, FS-35 (all manufactured by Chemours); FT-110, FT-250 FT-251, FT-400S, FT-150, FT-400SW (all manufactured by Neos Co., Ltd.), Polyfox PF-136A, PF-156A, PF-151N, PF-154, PF-159 (Omnova) ), Unidyne DSN-403N (manufactured by Daikin Industries, Ltd.) and the like. Among these, from the point that good print quality, particularly color developability, paper permeability, wettability, and leveling are remarkably improved, Chemours. FS-3100, FS-34, FS-300, FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW, polynova manufactured by Omninova PF-151N and Unidyne DSN-403N manufactured by Daikin Industries, Ltd. are particularly preferable.

As the surfactant, a siloxane surfactant (also referred to as a silicone-based surfactant) is preferable from the viewpoint of wettability to a non-penetrating substrate.
0.05 mass% or more is preferable and, as for content in the said processing liquid B of the said siloxane surfactant, 0.8 mass% or more and 5 mass% or less are more preferable.

  There is no restriction | limiting in particular as a physical property of the said process liquid B, According to the objective, a viscosity, surface tension, pH, etc. can be selected suitably.

  The viscosity of the treatment liquid B is preferably 0.5 mPa · s to 30 mPa · s at 25 ° C. Here, the viscosity can be measured using, for example, a viscometer (device name: RE-550L, manufactured by Toki Sangyo Co., Ltd.).

The surface tension of the processing liquid B needs to be lower than the surface tension of the processing liquid A, and the surface tension of the processing liquid B is preferably 5 mN / m or more lower than the surface tension of the processing liquid A.
The surface tension of the treatment liquid B is preferably 10 mN / m or more and 40 mN / m or less, more preferably 15 mN / m or more and 35 mN / m or less at 25 ° C.

  As pH of the said processing liquid B, 4-12 are preferable, for example, and 4-8 are more preferable.

  The method for applying the processing liquid B to the recording medium is the same as the processing liquid A.

The coating weight of the recording medium of the treatment liquid B in the treatment liquid application process, 0.1 g / ^{m 2} or more 30.0 g / ^{m 2} or less is preferable, 0.2 g / ^{m 2} or more 10.0 g / ^{m 2} or less Is more preferable.
Either the treatment liquid A or the treatment liquid B may be applied first, or may be applied simultaneously, but the treatment liquid B having a surface tension lower than that of the treatment liquid A is applied to different areas on the recording medium. It is necessary to apply the same from the viewpoint of controlling the dot diameter of the ink.
Examples of the method of applying the processing liquid A and the processing liquid B to different areas on the recording medium include an ink jet method.
In addition, a drying process can be provided as needed with respect to the recording medium which performed the process liquid provision process. In this case, the recording medium can be dried with a roll heater, a drum heater, or hot air. The drying temperature is preferably 60 ° C. or higher.

<Ink application process and ink application means>
The ink application step is a step of applying ink containing water, an organic solvent, and a color material onto the recording medium to which the treatment liquids A and B are applied, and is performed by an ink application unit.

<< Ink >>
Hereinafter, the organic solvent, water, coloring material, resin, surfactant, additive and the like used in the ink of the present invention will be described.

<Water>
The water content in the ink is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10% by mass or more and 90% by mass or less, and 20% by mass from the viewpoint of ink drying property and ejection reliability. % To 60% by mass is more preferable.

<Organic solvent>
It does not restrict | limit especially as an organic solvent used for this invention, A liquid thing is used under 25 degreeC and 1 atmosphere. Examples thereof include ethers such as polyhydric alcohols, polyhydric alcohol alkyl ethers and polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines and sulfur-containing compounds.
Specific examples of the water-soluble organic solvent include, for example, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butane. Diol, 2,3-butanediol, 3-methyl-1,3-butanediol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol 2,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,3-hexanediol, 2,5-hexanediol, 1,5-hexanediol, Glycerin, 1,2,6-hexanetriol, 2-ethyl-1,3-he Polyhydric alcohols such as sundiol, ethyl-1,2,4-butanetriol, 1,2,3-butanetriol, 2,2,4-trimethyl-1,3-pentanediol, petriol, ethylene glycol mono Polyhydric alcohol alkyl ethers such as ethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monophenyl ether, ethylene glycol mono Polyhydric alcohol aryl ethers such as benzyl ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl- -N-containing heterocyclic compounds such as pyrrolidone, 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, γ-butyrolactone, formamide, N-methylformamide, N, N-dimethylformamide, 3-methoxy-N, Amides such as N-dimethylpropionamide and 3-butoxy-N, N-dimethylpropionamide, amines such as monoethanolamine, diethanolamine and triethylamine, sulfur-containing compounds such as dimethylsulfoxide, sulfolane and thiodiethanol, propylene carbonate, Examples thereof include ethylene carbonate.
In addition to functioning as a wetting agent and compatibilizing agent, it is preferable to use an alcohol having a boiling point of 240 ° C. or lower, and particularly preferably an alcohol having a boiling point of 180 ° C. or lower because good drying properties can be obtained.

A polyol compound having 8 or more carbon atoms and a glycol ether compound are also preferably used. Specific examples of the polyol compound having 8 or more carbon atoms include 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, and the like.
Specific examples of glycol ether compounds include polyhydric alcohol alkyls such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and propylene glycol monoethyl ether. Examples of ethers include polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether.

  A polyol compound having 8 or more carbon atoms and a glycol ether compound can improve ink permeability when paper is used as a recording medium.

  The content of the organic solvent in the ink is not particularly limited and can be appropriately selected according to the purpose, but is preferably 10% by mass or more and 60% by mass or less from the viewpoint of the drying property and ejection reliability of the ink, 20 mass% or more and 60 mass% or less are more preferable.

<Color material>
The color material is not particularly limited, and pigments and dyes can be used.
An inorganic pigment or an organic pigment can be used as the pigment. These may be used alone or in combination of two or more. A mixed crystal may be used.
As the pigment, for example, a black pigment, a yellow pigment, a magenta pigment, a cyan pigment, a white pigment, a green pigment, an orange pigment, a glossy pigment such as gold or silver, a metallic pigment, or the like can be used.
Carbon black produced by known methods such as contact method, furnace method, thermal method in addition to titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow as inorganic pigments Can be used.
Organic pigments include azo pigments, polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone pigments). Dye chelates (for example, basic dye type chelates, acidic dye type chelates), nitro pigments, nitroso pigments, aniline black, and the like can be used. Of these pigments, those having good affinity with the solvent are preferably used. In addition, resin hollow particles and inorganic hollow particles can also be used.
Specific examples of the pigment include black for carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, or copper, iron (CI pigment black 11). And organic pigments such as metals such as titanium oxide and aniline black (CI Pigment Black 1).
Further, for color use, C.I. I. 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, 138, 150, 153, 155, 180, 185, 213, C.I. I. Pigment orange 5, 13, 16, 17, 36, 43, 51, C.I. I. 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 (Brilliant Carmine 6B), 60: 1, 63: 1, 63: 2, 64: 1, 81, 83, 88, 101 (Bengara), 104, 105, 106, 108 (Cadmium Red), 112, 114, 122 (quinacridone magenta), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 184, 185, 190, 193, 202, 207, 208, 209, 213, 219, 224, 254, 264, C.I. I. Pigment violet 1 (rhodamine lake), 3, 5: 1, 16, 19, 23, 38, C.I. I. Pigment Blue 1, 2, 15 (phthalocyanine blue), 15: 1, 15: 2, 15: 3, 15: 4 (phthalocyanine blue), 16, 17: 1, 56, 60, 63, C.I. I. Pigment Green 1, 4, 7, 8, 10, 17, 18, 36, etc.

The dye is not particularly limited, and an acid dye, a direct dye, a reactive dye, and a basic dye can be used. One kind may be used alone, or two or more kinds may be used in combination.
Examples of the dye include C.I. I. Acid Yellow 17, 23, 42, 44, 79, 142, C.I. I. Acid Red 52, 80, 82, 249, 254, 289, C.I. I. Acid Blue 9, 45, 249, C.I. I. Acid Black 1, 2, 24, 94, C.I. I. Food Black 1, 2, C.I. I. Direct Yellow 1,12,24,33,50,55,58,86,132,142,144,173, C.I. I. Direct Red 1,4,9,80,81,225,227, C.I. I. Direct Blue 1, 2, 15, 71, 86, 87, 98, 165, 199, 202, C.I. I. Directed Black 19, 38, 51, 71, 154, 168, 171, 195, C.I. I. Reactive Red 14, 32, 55, 79, 249, C.I. I. Reactive black 3, 4, 35 etc. are mentioned.

  The content of the color material in the ink is preferably 0.1% by mass or more and 15% by mass or less, and more preferably 1% by mass or more and 10% by mass or less from the viewpoints of improvement in image density, good fixability and ejection stability. preferable.

In order to obtain an ink by dispersing a pigment, a method of introducing a hydrophilic functional group into the pigment to form a self-dispersing pigment, a method of coating the surface of the pigment with a resin and dispersing, a dispersing agent is used. Method, etc.
As a method of introducing a hydrophilic functional group into a pigment to obtain a self-dispersing pigment, for example, a method of making it dispersible in water by adding a functional group such as a sulfone group or a carboxyl group to the pigment (for example, carbon) Is mentioned.
As a method for coating the surface of the pigment with a resin and dispersing it, a method in which the pigment is included in microcapsules and dispersible in water can be mentioned. This can be paraphrased as a resin-coated pigment. In this case, it is not necessary that all pigments blended in the ink are coated with a resin, and within a range where the effects of the present invention are not impaired, uncoated pigments and partially coated pigments are dispersed in the ink. It may be.
Examples of the method of dispersing using a dispersant include a method of dispersing using a known low-molecular type dispersant or high-molecular type dispersant represented by a surfactant.
As the dispersant, for example, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, or the like can be used depending on the pigment.
RT-100 (nonionic surfactant) manufactured by Takemoto Yushi Co., Ltd. and naphthalenesulfonic acid Na formalin condensate can also be suitably used as a dispersant.
A dispersing agent may be used individually by 1 type, or may use 2 or more types together.

<Pigment dispersion>
An ink can be obtained by mixing a material such as water or an organic solvent with a pigment. Further, it is also possible to produce an ink by mixing a pigment, other water, a dispersant, and the like into a pigment dispersion and mixing a material such as water or an organic solvent.
The pigment dispersion is obtained by mixing and dispersing water, a pigment, a pigment dispersant, and other components as necessary, and adjusting the particle size. For dispersion, a disperser may be used.
The particle size of the pigment in the pigment dispersion is not particularly limited, but the maximum frequency is 20 nm or more in terms of maximum number because the pigment dispersion stability is good and the image quality such as ejection stability and image density is also high. 500 nm or less is preferable and 20 nm or more and 150 nm or less are more preferable. The particle size of the pigment can be measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).
The content of the pigment in the pigment dispersion is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of obtaining good ejection stability and increasing the image density, 0.1% by mass. % To 50% by mass is preferable, and 0.1% to 30% by mass is more preferable.
The pigment dispersion is preferably degassed by filtering coarse particles with a filter, a centrifugal separator or the like, if necessary.

<Resin>
The type of resin contained in the ink is not particularly limited and can be appropriately selected according to the purpose. For example, urethane resin, polyester resin, acrylic resin, vinyl acetate resin, styrene resin, butadiene type Examples thereof include resins, styrene-butadiene resins, vinyl chloride resins, acrylic styrene resins, and acrylic silicone resins.
You may use the resin particle which consists of these resin. An ink can be obtained by mixing resin particles with a material such as a colorant or an organic solvent in a resin emulsion state in which water is dispersed as a dispersion medium. As said resin particle, what was synthesize | combined suitably may be used and a commercial item may be used. Moreover, these may be used individually by 1 type, or may be used in combination of 2 or more types of resin particles.
The volume average particle diameter of the resin particles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 nm or more and 1,000 nm or less from the viewpoint of obtaining good fixability and high image hardness. It is more preferably 200 nm or less and particularly preferably 10 nm or more and 100 nm or less.
The volume average particle diameter can be measured using, for example, a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).
The resin content is not particularly limited and may be appropriately selected according to the purpose. However, from the viewpoint of fixability and ink storage stability, the content of the resin is 1% by mass or more and 30% by mass or less. Is preferable, and 5 mass% or more and 20 mass% or less are more preferable.

  The particle size of the solid content in the ink is not particularly limited and can be appropriately selected according to the purpose. From the viewpoint of improving the image quality such as ejection stability and image density, the maximum frequency in terms of the maximum number is converted. Is preferably 20 nm to 1000 nm, and more preferably 20 nm to 150 nm. The solid content includes resin particles, pigment particles, and the like. The particle size can be measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).

<Additives>
If necessary, a surfactant, an antifoaming agent, an antiseptic / antifungal agent, an antirust agent, a pH adjuster, and the like may be added to the ink.

<Surfactant>
As the surfactant, any of silicone surfactants, fluorine surfactants, amphoteric surfactants, nonionic surfactants and anionic surfactants can be used.
There is no restriction | limiting in particular in silicone type surfactant, According to the objective, it can select suitably. Among them, those that do not decompose even at high pH are preferable, and examples thereof include side chain modified polydimethylsiloxane, both terminal modified polydimethylsiloxane, one terminal modified polydimethylsiloxane, and side chain both terminal modified polydimethylsiloxane. Those having an oxyethylene group or a polyoxyethylene polyoxypropylene group are particularly preferred because they exhibit good properties as an aqueous surfactant. In addition, as the silicone surfactant, a polyether-modified silicone surfactant can be used, and examples thereof include a compound in which a polyalkylene oxide structure is introduced into the side chain of the Si portion of dimethylsiloxane.
Examples of the fluorosurfactant include a perfluoroalkyl sulfonic acid compound, a perfluoroalkyl carboxylic acid compound, a perfluoroalkyl phosphate compound, a perfluoroalkyl ethylene oxide adduct, and a perfluoroalkyl ether group in the side chain. Polyoxyalkylene ether polymer compounds are particularly preferred because of their low foaming properties. Examples of the perfluoroalkyl sulfonic acid compound include perfluoroalkyl sulfonic acid, perfluoroalkyl sulfonate, and the like. Examples of the perfluoroalkylcarboxylic acid compound include perfluoroalkylcarboxylic acid and perfluoroalkylcarboxylate. Examples of the polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain include a sulfate ester salt of a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in the side chain and a perfluoroalkyl ether group in the side chain. Examples thereof include salts of polyoxyalkylene ether polymers. As counter ions of salts in these fluorosurfactants, Li, Na, K, NH ₄ , NH ₃ CH ₂ CH ₂ OH, NH ₂ (CH ₂ CH ₂ OH) ₂ , NH (CH ₂ CH ₂ OH) ₃ etc. are mentioned.
Examples of amphoteric surfactants include lauryl aminopropionate, lauryl dimethyl betaine, stearyl dimethyl betaine, and lauryl dihydroxyethyl betaine.
Nonionic surfactants include, for example, polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkylamine, polyoxyethylene alkylamide, polyoxyethylene propylene block polymer, sorbitan fatty acid ester, polyoxyethylene sorbitan Examples include fatty acid esters and ethylene oxide adducts of acetylene alcohol.
Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, laurate, polyoxyethylene alkyl ether sulfate salt, and the like.
These may be used alone or in combination of two or more.

The silicone surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, side chain modified polydimethylsiloxane, both terminal modified polydimethylsiloxane, one terminal modified polydimethylsiloxane, side Since both ends of the chain are modified with polydimethylsiloxane, a polyether-modified silicone surfactant having a polyoxyethylene group or a polyoxyethylene polyoxypropylene group as a modifying group exhibits good properties as an aqueous surfactant. preferable.
As such a surfactant, an appropriately synthesized product or a commercially available product may be used. Commercially available products can be obtained from, for example, Big Chemie Co., Ltd., Shin-Etsu Chemical Co., Ltd., Toray Dow Corning Silicone Co., Ltd., Nippon Emulsion Co., Ltd., and Kyoeisha Chemical Co., Ltd.
There is no restriction | limiting in particular as said polyether modified silicone surfactant, According to the objective, it can select suitably, For example, the polyalkylene oxide structure represented by a general formula (S-1) type | formula is dimethylpolyethylene. Examples thereof include those introduced into the side chain of Si part of siloxane.
Formula (S-1)
(However, in the formula (S-1), m, n, a, and b each independently represent an integer, R represents an alkylene group, and R ′ represents an alkyl group.)

  A commercial item can be used as said polyether modified silicone type surfactant, For example, KF-618, KF-642, KF-643 (Shin-Etsu Chemical Co., Ltd.), EMALEX-SS-5602, SS- 1906EX (Japan Emulsion Co., Ltd.), FZ-2105, FZ-2118, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ-2164 (Toray Dow Corning Silicone Co., Ltd.), BYK-33, BYK-387 (Bic Chemie Co., Ltd.), TSF4440, TSF4452, TSF4453 (Toshiba Silicon Co., Ltd.), etc. are mentioned.

As the fluorine-based surfactant, a fluorine-substituted compound having 2 to 16 carbon atoms is preferable, and a fluorine-substituted compound having 4 to 16 carbon atoms is more preferable.
Examples of the fluorosurfactant include perfluoroalkyl phosphate compounds, perfluoroalkylethylene oxide adducts, and polyoxyalkylene ether polymer compounds having a perfluoroalkyl ether group in the side chain.
Among these, a polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain is preferable because of its low foaming property, and in particular, fluorine-based compounds represented by the general formulas (F-1) and (F-2) A surfactant is preferred.
Formula (F-1)
In the compound represented by the general formula (F-1), m is preferably an integer of 0 to 10 and n is preferably an integer of 0 to 40 in order to impart water solubility.
Formula (F-2)
_{C n F 2n + 1- CH 2} CH (OH) CH 2 -O- (CH 2 CH 2 O) a -Y
In the compound represented by the general formula (F-2), Y is H, or CnF _{2n + 1} , n is an integer of 1 to 6, or CH ₂ CH (OH) CH ₂ —CnF _{2n + 1,} where n is 4 to 6. An integer, or CpH _{2p + 1} , p is an integer of 1-19. a is an integer of 4-14.
A commercial item may be used as said fluorosurfactant.
As this commercial item, for example, Surflon S-111, S-112, S-113, S-121, S-131, S-132, S-141, S-145 (all manufactured by Asahi Glass Co., Ltd.); Fullrad FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431 (all manufactured by Sumitomo 3M Limited); Megafac F-470, F -1405, F-474 (all manufactured by Dainippon Ink & Chemicals, Inc.); Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, UR, Capstone FS-30, FS-31, FS-3100, FS-34, FS-35 (all manufactured by Chemours); FT-110, FT-250 FT-251, FT-400S, FT-150, FT-400SW (all manufactured by Neos Co., Ltd.), Polyfox PF-136A, PF-156A, PF-151N, PF-154, PF-159 (Omnova) ), Unidyne DSN-403N (manufactured by Daikin Industries, Ltd.) and the like. Among these, from the point that good print quality, particularly color developability, paper permeability, wettability, and leveling are remarkably improved, Chemours. FS-3100, FS-34, FS-300, FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW, polynova manufactured by Omninova PF-151N and Unidyne DSN-403N manufactured by Daikin Industries, Ltd. are particularly preferable.

  There is no restriction | limiting in particular as content of surfactant in an ink, Although it can select suitably according to the objective, From the point which is excellent in wettability and discharge stability, and image quality improves, it is 0.001 mass. % To 5% by mass is preferable, and 0.05% to 5% by mass is more preferable.

<Antifoaming agent>
There is no restriction | limiting in particular as an antifoamer, For example, a silicone type antifoamer, a polyether type | system | group antifoamer, a fatty-acid ester type | system | group antifoamer etc. are mentioned. These may be used alone or in combination of two or more. Among these, a silicone type antifoaming agent is preferable from the viewpoint of excellent foam breaking effect.

<Antiseptic and antifungal agent>
The antiseptic / antifungal agent is not particularly limited, and examples thereof include 1,2-benzisothiazolin-3-one.

<PH adjuster>
The pH adjuster is not particularly limited as long as the pH can be adjusted to 7 or more, and examples thereof include amines such as diethanolamine and triethanolamine.

There is no restriction | limiting in particular as a physical property of an ink, According to the objective, it can select suitably, For example, it is preferable that a viscosity, surface tension, pH, etc. are the following ranges.
The viscosity at 25 ° C. of the ink is preferably 5 mPa · s or more and 30 mPa · s or less, preferably 5 mPa · s or more and 25 mPa · s or less from the viewpoint of improving the printing density and character quality and obtaining good discharge properties. More preferred. Here, for the viscosity, for example, a rotary viscometer (RE-80L manufactured by Toki Sangyo Co., Ltd.) can be used. Measurement conditions are 25 ° C., standard cone rotor (1 ° 34 ′ × R24), sample liquid amount 1.2 mL, rotation speed 50 rpm, and measurement is possible for 3 minutes.
The surface tension of the ink is preferably 35 mN / m or less and more preferably 32 mN / m or less at 25 ° C. from the viewpoint that the ink is suitably leveled on the recording medium and the drying time of the ink is shortened.
The pH of the ink is preferably 7 to 12 and more preferably 8 to 11 from the viewpoint of preventing corrosion of the metal member in contact with the liquid.

<Recording medium>
The recording medium is not particularly limited, and plain paper, glossy paper, special paper, cloth, and the like can be used. Good image formation is possible even with a non-permeable substrate.
The non-permeable base material is a base material having a surface with low water permeability and absorbability, and includes materials that do not open to the outside even if there are many cavities inside, more quantitatively. In the Bristow method, the water absorption amount from the start of contact to 30 msec ^1/2 is 10 mL / m ² or less.
As said non-permeable base material, plastic films, such as a vinyl chloride resin film, a polyethylene terephthalate (PET) film, a polypropylene, polyethylene, a polycarbonate film, can be used conveniently, for example.

  The polypropylene and polyethylene are not particularly limited. For example, AR1025, AR1056, AR1082, EC1082, 1082D, 1073D, 1056D, 1025D, FR1073 (manufactured by Asahi DuPont Flashspan Products Co., Ltd.), P2002, P2102, P2108, P2161, P2171, P2111, P4266, P5767, P3162, P6181, P8121, P1162, P1111, P1128, P1181, P1153, P1157, P1146, P1147, P1171 (manufactured by Toyobo Co., Ltd.), YPI, Aqua Yupo, Super Yupo, Ultra Yupo, New Yupo, Yupo Lighting paper, YUPO building material paper, YUPO high gloss, YUPOJET, metallic YUPO (manufactured by YUPO Corporation) And so on.

<Recorded material>
The ink recorded matter of the present invention has an image formed using the ink of the present invention on a recording medium.
Recording can be performed by recording with an inkjet recording apparatus and an inkjet recording method.

  Examples of a method for applying the ink to the recording medium include a liquid ejection method and a coating method.

  The liquid ejection method is not particularly limited and can be appropriately selected according to the purpose. For example, the ejection head driving method includes a piezoelectric element actuator using PZT, a method of applying thermal energy, an electrostatic An on-demand type head using an actuator using force or the like can be used, or a continuous injection type charge control type head can be used.

  Examples of the coating method include blade coating, gravure coating, gravure offset coating, wire bar coating, bar coating, roll coating, knife coating, air knife coating, comma coating, and U comma coating. , AKKU coating method, smoothing coating method, micro gravure coating method, reverse roll coating method, 4 to 5 roll coating method, dip coating method, curtain coating method, slide coating method, die coating method and the like. Among these, a wire bar coating method and a roller coating method are particularly preferable.

<Recording apparatus and recording method>
The ink of the present invention can be suitably used for various recording apparatuses using an ink jet recording method, such as a printer, a facsimile apparatus, a copying apparatus, a printer / fax / copier complex machine, and a three-dimensional modeling apparatus.
In the present invention, the recording apparatus and the recording method are an apparatus capable of ejecting ink, various treatment liquids, and the like to a recording medium, and a method of performing recording using the apparatus. The recording medium means a medium on which ink or various processing liquids can be temporarily attached.
The recording apparatus can include not only a head portion that ejects ink but also means for feeding, transporting, and discharging a recording medium, and other devices called pre-processing devices and post-processing devices. .
The recording apparatus and the recording method may include a heating unit used in the heating step and a drying unit used in the drying step. The heating means and the drying means include, for example, a means for heating and drying the printing surface and the back surface of the recording medium. Although it does not specifically limit as a heating means and a drying means, For example, a warm air heater and an infrared heater can be used. Heating and drying can be performed before printing, during printing, after printing, and the like.
When an infrared heater is used, at least a near infrared irradiation device is provided.
As the near-infrared irradiation device, a device including a halogen lamp and a reflection mirror is known. Products that are designed to realize efficient heating by incorporating a halogen heater into the reflection mirror and making it into a heating unit have been commercialized, for example, UH-USC-CL300, UHUSC-CL700, UH-USC-CL1000, UH -USD-CL300, UHUD-CL700, UH-USD-CL1000, UH-MA1-CL300, UHMA1-CL700, UH-MA1-CL1000 (all manufactured by Ushio).
Further, the recording apparatus and the recording method are not limited to those in which significant images such as characters and figures are visualized by ink. For example, what forms patterns, such as a geometric pattern, etc. includes what forms a three-dimensional image.
Further, the recording apparatus includes both a serial type apparatus that moves the ejection head and a line type apparatus that does not move the ejection head, unless otherwise specified.
Furthermore, this recording apparatus can use not only a desktop type but also a wide recording apparatus that can print on an A0 size recording medium, for example, a continuous paper wound up in a roll shape as a recording medium. Also included are continuous paper printers.
An example of the recording apparatus will be described with reference to FIGS. FIG. 1 is a perspective view of the apparatus. FIG. 2 is an explanatory perspective view of the main tank. An image forming apparatus 400 as an example of a recording apparatus is a serial type image forming apparatus. A mechanism unit 420 is provided in the exterior 401 of the image forming apparatus 400. Each ink storage portion 411 of the main tank 410 (410k, 410c, 410m, 410y) for each color of black (K), cyan (C), magenta (M), yellow (Y) is packaged, for example, an aluminum laminate film It is formed by a member. The ink storage unit 411 is stored in, for example, a plastic container case 414. As a result, the main tank 410 is used as an ink cartridge for each color.
On the other hand, a cartridge holder 404 is provided on the inner side of the opening when the cover 401c of the apparatus main body is opened. A main tank 410 is detachably attached to the cartridge holder 404. Thus, the ink discharge ports 413 of the main tank 410 and the discharge heads 434 for the respective colors communicate with each other via the supply tubes 436 for the respective colors, and ink can be discharged from the discharge heads 434 to the recording medium.

The recording apparatus can include not only a portion that ejects ink but also a device called a pre-processing device or a post-processing device.
As one mode of the pretreatment device and the posttreatment device, as in the case of inks such as black (K), cyan (C), magenta (M), and yellow (Y), a pretreatment liquid and a posttreatment liquid are included. There is a mode in which a liquid container and a liquid discharge head are added, and a pretreatment liquid and a posttreatment liquid are discharged by an ink jet recording method.
As another aspect of the pretreatment apparatus and the posttreatment apparatus, there is an aspect in which, for example, a pretreatment apparatus or a posttreatment apparatus other than the ink jet recording method is provided by a blade coating method, a roll coating method, or a spray coating method.

  The method of using the ink is not limited to the ink jet recording method, and can be widely used. Besides the ink jet recording method, for example, a blade coating method, a gravure coating method, a bar coating method, a roll coating method, a dip coating method, a curtain coating method, a slide coating method, a die coating method, a spray coating method and the like can be mentioned.

  In the present invention, the drying temperature during recording is preferably 50 ° C. or higher in order to improve the drying property and the fixing property to the non-permeable substrate. The upper limit of the drying temperature at the time of recording is not particularly limited and can be appropriately selected according to the purpose. However, from the viewpoint of thermal deformation of the substrate, 200 ° C. or lower is preferable. The drying temperature before and after recording is not particularly limited and can be appropriately selected according to the purpose.

  Further, the terms “image formation”, “recording”, “printing”, “printing”, etc. in the terms of the present invention are all synonymous.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

<Preparation of ink>
<Preparation Example 1 of Black Pigment Dispersion>
The following raw materials were premixed and then circulated and dispersed in a disk type bead mill (Shinmaru Enterprises KDL type, media: 0.3 mm diameter zirconia ball used) for 7 hours to obtain a black pigment dispersion.
-Carbon black pigment (trade name: Monarch 800, manufactured by Cabot Corporation): 15 parts by mass-Anionic surfactant (Pionin A-51-B, manufactured by Takemoto Yushi Co., Ltd.): 2 parts by mass-Ion exchange water: 83 parts by mass

<Preparation Example 1 of Cyan Pigment Dispersion>
A cyan pigment dispersion was prepared in the same manner as in Preparation Example 1 of the black pigment dispersion except that the following raw materials were used in Preparation Example 1 of the black pigment dispersion.
Pigment Blue 15: 3 (trade name: LIONOL BLUE FG-7351, manufactured by Toyo Ink Co., Ltd.): 15 parts by mass Anionic surfactant (Pionin A-51-B, manufactured by Takemoto Yushi Co., Ltd.): 2 parts by mass・ Ion exchange water: 83 parts by mass

(Preparation example of ink a1)
Ion exchange water was added to the following formulation so that the total amount was 100 parts by mass, and after mixing, the mixture was stirred and filtered through a filter having a mean pore size of 5 μm (manufactured by Sartorius, Mini-Salto) to prepare ink a1.
[Ink prescription]
Black pigment dispersion (nonvolatile content 20% by mass): 20 parts by mass Superflex 300 (Daiichi Kogyo Seiyaku Co., Ltd., polyurethane resin, solid content concentration: 30% by mass): 15 parts by mass BYK-348 (BYK Silicone surfactant): 1 part by mass • 1,2-propanediol: 3 parts by mass • 1,3-butanediol: 3 parts by mass • Examide M100 (3-methoxy-N, N-dimethylpropionamide) , Idemitsu Kosan Co., Ltd.): 10 parts by mass Dipropylene glycol monomethyl ether: 10 parts by mass 3-methoxy-3-methylbutanol: 4 parts by mass Proxel LV (manufactured by Avicia, antiseptic): 0.1 mass・ Ion exchange water: Remaining amount

(Preparation example of ink a2 to ink f2)
Inks a2 to f2 were prepared in the same manner as in Preparation Example 1 of Ink a1, except that the ink formulation in Ink a1 was changed to the ink formulations shown in Tables 1 and 2.

(Ink sets a to f)
Next, ink sets a to f were prepared by combining the prepared inks a1 to f2 in Tables 1 and 2.

(Preparation example of ethylene-vinyl acetate copolymer resin emulsion A)
1061 g of PVA-1 (polymerization degree 1,700, saponification degree 88 mol%, manufactured by Kuraray Co., Ltd., PVA-217) in a 50 liter autoclave equipped with a nitrogen inlet, a thermometer, and a stirrer, ion-exchanged water 19,440 g, L (+) sodium tartrate 12.7 g, sodium acetate 10.6 g, and ferrous chloride 0.4 g were charged and completely dissolved at 95 ° C., then cooled to 60 ° C. went.
Next, after charging 22,360 g of vinyl acetate, ethylene was pressurized to 45 kg / cm ² and introduced, and 1,000 g of 0.4 mass% hydrogen peroxide aqueous solution was injected over 5 hours and emulsified at 60 ° C. Polymerization was performed. The pH at the initial stage of polymerization was confirmed to be pH = 5.2.

When the amount of residual vinyl acetate reached 10% by mass, ethylene was released, the ethylene pressure was adjusted to 20 kg / cm ^2, and 50 g of 3% by mass hydrogen peroxide aqueous solution was injected to continue the polymerization.
When the amount of residual vinyl acetate monomer in the emulsion reached 1.5% by mass, ethylene was released and cooled. After cooling, the pH was confirmed to be pH = 4.8.
Next, 20 g of sodium bisulfite was added, and deethylenation was performed at 30 ° C. under a reduced pressure of 100 mmHg for 1 hour.
After returning the system to atmospheric pressure with nitrogen, 10 g of t-butyl hydroperoxide was added and stirred for 2 hours. When pH at the time of completion | finish of superposition | polymerization was confirmed, it was pH = 4.7.

This emulsion was filtered, solid content was adjusted to 50% by mass, and an ethylene-vinyl acetate copolymer resin emulsion A was obtained.
It was 0 degreeC when the glass transition point (Tg) of the ethylene-vinyl acetate copolymer resin emulsion A was measured by DSC (The Rigaku company make, Thermo plus EVO2 / DSC).

(Preparation example of urethane resin emulsion A)
Polyethylene glycol monomethyl ether having a molecular weight of 1,000 per 1 mol of 1,6-hexanediol and 1.4 mol of dicyclohexylmethane diisocyanate and 1 mol of isocyanurate trimer of 1,6-hexamethylene diisocyanate 0.1 mol of the diisocyanate compound reacted for 3 mol and 15% by mass of N-methyl-2-pyrrolidone of the total mass were charged into a reaction flask and reacted at 90 ° C. for 2 hours under a nitrogen stream to obtain a prepolymer. .

450 g of a prepolymer composition having a solid content of 85% by mass obtained above was added dropwise to 600 g of water in which 0.2 g of a silicone-based antifoaming agent SE-21 (manufactured by Wacker Silicone) was dissolved, at 25 ° C. After stirring for 10 minutes, a compound of the following structural formula 1, ethylenediamine, and adipic acid hydrazide were added dropwise to obtain a urethane resin emulsion A.
[Structural Formula 1]

  It was 20 degreeC when the glass transition point (Tg) of the obtained polyurethane resin emulsion A was measured by DSC (The Rigaku company make, Thermo plus EVO2 / DSC).

(Preparation example of treatment liquid A1>
After the following formulation was prepared, the mixture was stirred and filtered with a filter having a mean pore size of 5 μm (manufactured by Sartorius, Mini Sarto) to prepare treatment liquid A1.
[Prescription of treatment liquid]
-1,2-propanediol: 10 parts by mass-Emulgen LS-106 (manufactured by Kao Corporation, surfactant): 0.3 parts by mass-Calcium acetate monohydrate: 1.76 parts by mass-Ethylene-vinyl acetate Copolymer resin emulsion A (as solid content): 10 parts by mass Proxel LV (Abyssia, preservative): 0.1 parts by mass Ion exchange water: remaining amount Total: 100 parts by mass

(Preparation examples of treatment liquids A2 to A5)
In the preparation examples of the treatment liquid A1, treatment liquids A2 to A5 were prepared in the same manner as in the preparation example of the treatment liquid A1, except that the formulation shown in Table 3 was changed.

  Next, the surface tension of each treatment liquid obtained was measured as follows. The results are shown in Table 3.

<Surface tension of treatment liquid>
The measurement was performed by the Wilhelmy method using an AUTOMATIC SUPERFACE TENSIONMETER CBVP-Z manufactured by Kyowa Interface Science Co., Ltd. The Wilhelmy method is a method for measuring the surface tension by reading the force to pull the measuring element generated when the measuring element (platinum plate) touches the surface of the liquid into the liquid. Measurement was performed at a temperature of 25 ° C.

The details of the components in Table 3 are as follows.
-Ethylene-vinyl acetate copolymer resin B: Sumikaflex 951HQ (Tg: -25 ° C) manufactured by Sumika Chemtex Co., Ltd.
-Ethylene-vinyl acetate-vinyl chloride copolymer resin A: Sumikaflex 808HQ (Tg: 25 ° C) manufactured by Sumika Chemtex Co., Ltd.
・ Vinyl acetate-acrylic copolymer resin A: Nibun Chemical Co., Ltd. vinyl blanc 1225 (Tg: 9 ° C.)

(Preparation example of treatment liquid B1)
After the following formulation was prepared, the mixture was stirred and filtered with a filter having a mean pore size of 5 μm (manufactured by Sartorius, Mini-Salto) to prepare treatment liquid B1.
[Prescription of treatment liquid]
1,2-propanediol: 10 parts by mass BYK-345 (manufactured by BYK, surfactant): 2 parts by mass Ethylene-vinyl acetate-vinyl chloride copolymer resin A (as solid content): 9 parts by mass Proxel LV (Abyssia, preservative): 0.1 parts by mass Ion exchange water: remaining amount: 100 parts by mass

(Preparation examples of treatment liquids B2 to B7)
In the preparation examples of the treatment liquid B1, treatment liquids B2 to B7 were prepared in the same manner as in the preparation example of the treatment liquid B1, except that the formulation shown in Table 4 was changed.

  Next, the surface tension of each treatment liquid B obtained was measured in the same manner as the treatment liquid A. The results are shown in Table 4.

Details of the components in Table 4 are as follows.
-Ethylene-vinyl acetate copolymer resin B: Sumika Flex 951HQ (Tg: -25 ° C) manufactured by Sumika Chemtex Co., Ltd.
-Ethylene-vinyl acetate-vinyl chloride copolymer resin A: Sumika Flex 808HQ (Tg: 25 ° C.) manufactured by Sumika Chemtex Co., Ltd.
Vinyl acetate-acrylic copolymer resin A: manufactured by Nissin Chemical Co., Ltd., Viniblanc 1225 (Tg: 9 ° C.)
・ BYK-333 (manufactured by BYK, silicone surfactant)
・ BYK-345 (manufactured by BYK, silicone surfactant)
・ BYK-347 (manufactured by BYK, silicone surfactant)
・ FS300 (manufactured by DuPont, fluorine-based surfactant)

(Examples 1-6 and Comparative Examples 1-5)
Next, as shown in Table 5, the ink set, the treatment liquid A, and the treatment liquid B were combined and image formation was performed as follows, and “granularity” was evaluated for each of the obtained images. The results are shown in Table 5.

<Formation of granularity measurement image>
Ink jet printers (IPSiO GX5000, manufactured by Ricoh Co., Ltd.) are filled with inks 410k and 410c in FIG. 1 using combinations of ink sets a to f, processing liquid A, and processing liquid B shown in Table 5, and the processing liquid A is filled in 410 m of FIG. 1 and treatment liquid B is filled in 410 y of FIG. 1, and a polyvinyl chloride film (CPPVWP1300, manufactured by Sakurai Co., Ltd., hereinafter also referred to as “PVC film”) is shown in FIG. As shown, black solid images of 10% gradation and 60% gradation were formed at a resolution of 600 dpi. Processing liquid A was applied to the 10% gradation image, and processing liquid B was applied to the 60% gradation image, and black ink was applied thereon to form an image. After the black solid image was formed, the printed material was passed through a hot air drying unit at 70 ° C., followed by drying and fixing.
Next, a cyan solid image was formed, dried and fixed in the same manner as the black solid image except that cyan ink was used instead of black ink.

<Granularity>
The black gradation solid image and the cyan gradation solid image formed on the obtained PVC film recording medium were visually observed, and the granularity was evaluated according to the following criteria. In addition, it is desirable in practical use that it is B or more.
[Evaluation criteria]
A: No ink dot particles are seen from a distance of less than 5 cm B: No ink dot particles are seen from a distance of from 5 cm to less than 30 cm C: Even from a distance of from 30 cm to less than 100 cm Ink dot particles are not seen D: Ink dot particles are seen from a distance of 100 cm or more

* Note that the evaluation results of the granularity were the same for the black solid image and the cyan solid image.

From the results in Table 5, it was found that Examples 1 and 2 are preferred embodiments of the present invention, and the granularity of the image printed on the recording medium is good.
Example 3 is an example in which the resin does not contain resin particles, and the ink dot diameter on the treatment liquid is larger than in Examples 1 and 2, resulting in a slightly inferior granularity of the 10% gradation image. It was.
Example 4 is an example in which the amount of the surfactant in the processing liquid B is small, and the ink dot diameter on the processing liquid B is smaller than those in Examples 1 and 2, and the granularity of the 60% gradation image is slightly higher. The result was inferior.
Example 5 is an example in which the surfactant in the processing liquid B is not siloxane-based, and the ink dot diameter on the processing liquid B is smaller than in Examples 1 and 2, and the granularity of the 60% gradation image is high. The results were slightly inferior.
Example 6 is an example in which the treatment liquid B does not contain a surfactant, and the ink dot diameter on the treatment liquid B is smaller than those in Examples 1 and 2, and the granularity of a 60% gradation image is obtained. The results were slightly inferior.

On the other hand, Comparative Example 1 is an example in which inorganic particles are not contained in the processing liquid A, and the ink dot diameter on the processing liquid A is larger than in the example, and the granularity in a 10% gradation image is increased. The result was inferior.
Comparative Example 2 is an example in which the surface tension of the treatment liquid B is larger than that of the treatment liquid A, and the ink dot diameter on the treatment liquid B is smaller than in the example, resulting in inferior granularity in a 60% gradation image. It became.
Comparative Example 3 is an example in which the treatment liquid A does not contain inorganic particles, and the ink does not contain resin particles. The ink dot diameter is larger than that of Comparative Example 1, and the gradation is 10%. The granularity in the image was inferior.
Comparative Example 4 is an example in which the treatment liquid A contains no inorganic particles, and the surfactant in the treatment liquid B is not siloxane-based, and has a 10% gradation and 60% floor compared to Example 1. The granularity of the toned image was inferior.
Comparative Example 5 is an example in which the treatment liquid B is applied to a 10% gradation image, and the ink dot diameter in the 10% gradation image is larger than in the example, and the graininess in the 10% gradation image is increased. The result was inferior.

As an aspect of this invention, it is as follows, for example.
<1> Treatment liquid application step of applying treatment liquid A containing water, organic solvent, resin particles, and inorganic particles and treatment liquid B having a surface tension lower than that of treatment liquid A to different regions on the recording medium. When,
An ink application step of applying ink containing water, an organic solvent, and a coloring material onto the recording medium to which the treatment liquids A and B are applied;
An image forming method comprising:
<2> The image forming method according to <1>, wherein the treatment liquid B contains water, an organic solvent, resin particles, and a surfactant.
<3> The image forming method according to <2>, wherein the surfactant contained in the treatment liquid B is a siloxane surfactant.
<4> The image forming method according to <3>, wherein the content of the siloxane surfactant in the processing liquid B is 0.05% by mass or more.
<5> The image forming method according to any one of <1> to <4>, wherein the ink further contains resin particles.
<6> Treatment liquid application means for applying treatment liquid A containing water, organic solvent, resin particles, and inorganic particles, and treatment liquid B having a surface tension lower than that of treatment liquid A to different areas on the recording medium. When,
An ink applying means for applying an ink containing water, an organic solvent, and a coloring material on the recording medium to which the treatment liquids A and B are applied;
An image forming apparatus comprising:
<7> The image forming apparatus according to <6>, wherein the processing liquid B contains water, an organic solvent, resin particles, and a surfactant.
<8> The image forming apparatus according to <7>, wherein the surfactant contained in the processing liquid B is a siloxane surfactant.
<9> The image forming apparatus according to <8>, wherein the content of the siloxane surfactant in the processing liquid B is 0.05% by mass or more.
<10> The image forming apparatus according to any one of <6> to <9>, wherein the ink further contains resin particles.

  According to the image forming method described in any one of <1> to <5> and the image forming apparatus described in any one of <6> to <10>, the conventional problems are solved, and Aim can be achieved.

400 Image forming apparatus 401 Exterior 401c Cover 404 Cartridge holder 410, 410k, 410c, 410m, 410y Main tank 411 Ink storage section 413 Ink discharge port 414 Storage container case 420 Mechanism section 434 Discharge head 436 Supply tube L Ink storage container

JP 2009-166387 A

Claims (6)

A treatment liquid application step of applying a treatment liquid A containing water, an organic solvent, resin particles, and inorganic particles, and a treatment liquid B having a surface tension lower than that of the treatment liquid A to different regions on the recording medium;
An ink application step of applying ink containing water, an organic solvent, and a coloring material onto the recording medium to which the treatment liquids A and B are applied;
An image forming method comprising:   The image forming method according to claim 1, wherein the processing liquid B contains water, an organic solvent, resin particles, and a surfactant.   The image forming method according to claim 2, wherein the surfactant contained in the processing liquid B is a siloxane surfactant.   The image forming method according to claim 3, wherein the content of the siloxane surfactant in the processing liquid B is 0.05% by mass or more.   The image forming method according to claim 1, wherein the ink further contains resin particles. Treatment liquid application means for applying treatment liquid A containing water, organic solvent, resin particles, and inorganic particles, and treatment liquid B having a surface tension lower than that of treatment liquid A to different areas on the recording medium,
An ink applying means for applying an ink containing water, an organic solvent, and a coloring material on the recording medium to which the treatment liquids A and B are applied;
An image forming apparatus comprising: