JP7056241B2 - Image forming method and image forming device - Google Patents

Description

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

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

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

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

The image forming method of the present invention as a means for solving the above-mentioned problems comprises a treatment liquid A containing water, an organic solvent, resin particles, and inorganic particles, and a treatment liquid B having a lower surface tension than the treatment liquid A. , The process of applying the treatment liquid to different areas on the recording medium, and
It includes an ink applying 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 graininess 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 a perspective explanatory view showing an example of a main tank in the image forming apparatus of the present invention. FIG. 3 is a diagram in which a black solid image having 10% gradation and 60% gradation is formed at a resolution of 600 dpi.

(Image forming method and image forming device)
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 lower surface tension than the treatment liquid A are applied to different regions on a recording medium. Processing liquid application process and
It includes an ink applying 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, and further includes other steps as necessary.
In the present invention, "giving to different regions on a recording medium" also includes the case of "giving in different patterns". For example, one of the treatment liquids may be adhered to the entire surface by roller coating or the like, and the other treatment liquid may be 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 lower surface tension than the treatment liquid A to different regions on a recording medium. Means for applying the treatment liquid and
It has 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, and further has other means as needed.

In the prior art, the application of the pretreatment liquid improves the bleeding and fixing property of characters, but it is difficult to control the dot diameter of the ink with one kind of pretreatment liquid. In this case, although the dot diameter of the ink can be controlled by adjusting the printing temperature in the drying process, there is a risk of causing damage such as deterioration of ejection reliability and discoloration and deformation of the base material.
Therefore, in the present invention, the treatment liquid A containing water, the organic solvent, the resin particles, and the inorganic particles and the treatment liquid B having a lower surface tension than the treatment liquid A are applied to different regions 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 are applied.
By controlling the dot diameter of the ink without damaging the base material, the graininess of the intermediate gradation can be improved.

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

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

<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-hexanediol, ethyl-1,2,4-butanetriol, 1,2,3-butanetriol, 2,2,4-trimethyl- Polyhydric alcohols such as 1,3-pentanediol and petriol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl Polyhydric alcohol alkyl ethers such as ethers, polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone. , 1,3-Dimethyl-2-imidazolidinone, ε-caprolactam, γ-butyrolactone and other nitrogen-containing heterocyclic compounds, formamide, N-methylformamide, N, N-dimethylformamide, 3-methoxy-N, N- Amidos such as dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, amines such as monoethanolamine, diethanolamine and triethylamine, sulfur-containing compounds such as dimethylsulfoxide, sulfolane and thiodiethanol, propylene carbonate and ethylene carbonate. And so on.
It is preferable to use an organic solvent having a boiling point of 250 ° C. or lower because it not only functions as a wetting agent but also has good drying properties.

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.

The content of the organic solvent is preferably 10% by mass or more and 60% by mass or less, more preferably 20% by mass or more and 60% by mass or less, based on the total amount of the treatment liquid A.

-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 alone or in combination of two or more. Among these, calcium compounds and magnesium compounds are preferable.

The calcium compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, calcium carbonate, calcium nitrate, calcium chloride, calcium acetate, calcium sulfate, calcium silicate, or hydrates thereof may be used. Can be mentioned.
The magnesium compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include magnesium chloride, magnesium acetate, magnesium sulfate, magnesium silicate, and hydrates thereof.
The barium compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include barium sulfate or a hydrate thereof.
The zinc compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include zinc sulfide and zinc carbonate.
The aluminum compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aluminum silicate and aluminum hydroxide.
Among these, calcium carbonate, calcium chloride and magnesium sulfate are preferable.

The content of the inorganic particles is preferably 1% by mass or more and 10% by mass or less, more preferably 1% by mass or more and 7% by mass or less, based on the total amount of the treatment liquid A.

-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, and styrene. Resin particles, butadiene resin Luci, 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 copolymerization 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.
It is possible to obtain the treatment liquid A by mixing the resin particles with a material such as an organic solvent in the state of a resin emulsion in which water is used as a dispersion medium. As the resin particles, those synthesized as appropriate may be used, or commercially available products may be used.
The volume average particle size of the resin particles is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of obtaining good fixability and high image hardness, 10 nm or more and 1,000 nm or less are preferable. More than 200 nm is more preferable, and 10 nm or more and 100 nm or less is particularly preferable.
The volume average particle size can be measured using, for example, a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrac Bell Co., Ltd.).
The content of the resin particles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1% by mass or more and 30% by mass or less, and 5% by mass or more and 20% by mass with respect to the total amount of the treatment liquid A. % Or less is more preferable.

--water--
Examples of the water include pure water such as ion-exchanged water, ultra-filtered water, reverse osmosis water, and distilled water; ultrapure water and the like. These may be used alone or in combination of two or more.
The water content is preferably 60% by mass or less, more preferably 30% by mass or more and 50% by mass or less, based on the total amount of the treatment liquid A. When the content is 60% by mass or less, it is possible to suppress the increase in viscosity, gelation, precipitation of insoluble matter and the like when the water evaporates.

－－Other ingredients －－
The other components are not particularly limited and may be appropriately selected depending on the intended purpose. For example, a surfactant, a defoaming agent, a pH adjuster, an antibacterial agent, a chelating reagent, a rust inhibitor, and an antioxidant. And so on. These may be used alone or in combination of two or more.

The physical properties of the treatment liquid A are not particularly limited, and the viscosity, surface tension, pH and the like can be appropriately selected depending on the intended purpose.

The viscosity of the treatment liquid A is preferably 0.5 mPa · s or more and 30 mPa · s or less 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. The Wilhelmy method can be measured by reading the force that is generated when the stylus (platinum plate) touches the surface of the liquid and tries to draw the stylus into the liquid.

As the pH of the treatment liquid A, for example, 4 to 12 is preferable, and 4 to 8 is more preferable.

The method of 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 discharge method is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the discharge head drive method includes a piezoelectric element actuator using PZT or the like, a method of applying thermal energy, and static electricity. 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 or the like can be used.

Examples of the coating method include a blade coating method, a gravure coating method, a gravure offset coating method, a wire bar coating method, a bar coating method, a roll coating method, a knife coating method, an air knife coating method, a comma coating method, and a U comma coating method. , AKKU coating method, smoothing coating method, microgravia 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, the wire bar coating method and the roller coating method are particularly preferable.

The treatment liquid A may be applied to a recording medium whose surface is sufficiently dried, or may be applied to a recording medium on which an image is formed and is being dried.

The amount of the treatment liquid A adhering to the recording medium in the treatment liquid application step is preferably 0.1 g / m ² or more and 30.0 g / m ² or less, and 0.2 g / m ² or more and 10.0 g / m ² or less. Is more preferable.

<< Treatment 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.

As the water, the organic solvent, and the resin particles in the treatment liquid B, the same ones as those in the treatment liquid A can be used.

<Surfactant>
As the surfactant, any of a silicone-based surfactant, a fluorine-based surfactant, an amphoteric surfactant, a nonionic surfactant, and an anionic surfactant can be used.
The silicone-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Among them, those that do not decompose even at high pH are preferable, and examples thereof include side chain modified polydimethylsiloxane, double-ended modified polydimethylsiloxane, single-ended modified polydimethylsiloxane, side chain double-ended modified polydimethylsiloxane, and the like. Those having an oxyethylene group and a polyoxyethylene polyoxypropylene group are particularly preferable because they exhibit good properties as an aqueous surfactant. Further, as the silicone-based surfactant, a polyether-modified silicone-based surfactant can also be used, and examples thereof include compounds in which a polyalkylene oxide structure is introduced into the Si portion side chain of dimethylsiloxane.
Examples of the fluorine-based surfactant include a perfluoroalkyl sulfonic acid compound, a perfluoroalkyl carboxylic acid compound, a perfluoroalkyl phosphate ester compound, a perfluoroalkyl ethylene oxide adduct, and a perfluoroalkyl ether group in the side chain. Polyoxyalkylene ether polymer compounds are particularly preferred because they have low foaming properties. Examples of the perfluoroalkyl sulfonic acid compound include perfluoroalkyl sulfonic acid and perfluoroalkyl sulfonic acid salt. Examples of the perfluoroalkylcarboxylic acid compound include perfluoroalkylcarboxylic acid and perfluoroalkylcarboxylic acid salt. The polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain includes 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. The counter ions of the salts in these fluorine-based surfactants include Li, Na, K, NH ₄ , NH ₃ CH ₂ CH ₂ OH, NH ₂ (CH ₂ CH ₂ OH) ₂ , and NH (CH ₂ CH ₂ OH). ₃ etc. can be mentioned.
Examples of the amphoteric tenside include laurylaminopropionate, lauryl dimethyl betaine, stearyl dimethyl betaine, and lauryl dihydroxyethyl betaine.
Examples of the nonionic surfactant include polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkyl amine, polyoxyethylene alkyl amide, polyoxyethylene propylene block polymer, sorbitan fatty acid ester, and polyoxyethylene sorbitan. Examples thereof include a fatty acid ester and an ethylene oxide adduct of acetylene alcohol.
Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, lauryl salt, polyoxyethylene alkyl ether sulfate salt and the like.
These may be used alone or in combination of two or more.

一般式（Ｓ－１）
（但し、一般式（Ｓ－１）式中、ｍ、ｎ、ａ、及びｂは、それぞれ独立に、整数を表わし、Ｒは、アルキレン基を表し、Ｒ’は、アルキル基を表す。）
上記のポリエーテル変性シリコーン系界面活性剤としては、市販品を用いることができ、例えば、ＫＦ－６１８、ＫＦ－６４２、ＫＦ－６４３（信越化学工業株式会社）、ＥＭＡＬＥＸ－ＳＳ－５６０２、ＳＳ－１９０６ＥＸ（日本エマルジョン株式会社）、ＦＺ－２１０５、ＦＺ－２１１８、ＦＺ－２１５４、ＦＺ－２１６１、ＦＺ－２１６２、ＦＺ－２１６３、ＦＺ－２１６４（東レ・ダウコーニング・シリコーン株式会社）、ＢＹＫ－３３、ＢＹＫ－３８７、３３３、３４５、３４７、３４８（ビックケミー株式会社）、ＴＳＦ４４４０、ＴＳＦ４４５２、ＴＳＦ４４５３（東芝シリコン株式会社）などが挙げられる。 The silicone-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, side chain-modified polydimethylsiloxane, double-ended modified polydimethylsiloxane, one-ended modified polydimethylsiloxane, side. Examples thereof include polydimethylsiloxane modified at both ends of the chain, and a polyether-modified silicone-based surfactant having a polyoxyethylene group or a polyoxyethylene polyoxypropylene group as a modifying group exhibits good properties as an aqueous surfactant, and is particularly effective. preferable.
As such a surfactant, an appropriately synthesized one may be used, or a commercially available product may be used. As commercially available products, for example, they can be obtained from Big Chemie Co., Ltd., Shin-Etsu Chemical Co., Ltd., Toray Dow Corning Silicone Co., Ltd., Nippon Emulsion Co., Ltd., Kyoeisha Chemical Co., Ltd. and the like.
The above-mentioned polyether-modified silicone-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a polyalkylene oxide structure represented by the general formula (S-1) is dimethylpoly. Examples thereof include those introduced into the Si part side chain of siloxane.

General formula (S-1)
(However, in the general formula (S-1), m, n, a, and b each independently represent an integer, R represents an alkylene group, and R'represents an alkyl group.)
Commercially available products can be used as the above-mentioned polyether-modified silicone-based surfactant, for example, KF-618, KF-642, KF-643 (Shinetsu Chemical Industry Co., Ltd.), EMALEX-SS-5602, SS- 1906EX (Nippon 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 (Big Chemie Co., Ltd.), TSF4440, TSF4452, TSF4453 (Toshiba Silicon Co., Ltd.) and the like can be mentioned.

一般式（Ｆ－１）
上記一般式（Ｆ－１）で表される化合物において、水溶性を付与するためにｍは０～１０の整数が好ましく、ｎは０～４０の整数が好ましい。
一般式（Ｆ－２）
Ｃ_ｎＦ_{２ｎ＋１－}ＣＨ_２ＣＨ（ＯＨ）ＣＨ_２－Ｏ－（ＣＨ_２ＣＨ_２Ｏ）_ａ－Ｙ
上記一般式（Ｆ－２）で表される化合物において、ＹはＨ、又はＣｍＦ_２ｍ＋１でｍは１～６の整数、又はＣＨ_２ＣＨ（ＯＨ）ＣＨ_２－ＣｍＦ_２ｍ＋１でｍは４～６の整数、又はＣｐＨ_２ｐ＋１でｐは１～１９の整数である。ｎは１～６の整数である。ａは４～１４の整数である。
上記のフッ素系界面活性剤としては市販品を使用してもよい。この市販品としては、例えば、サーフロンＳ－１１１、Ｓ－１１２、Ｓ－１１３、Ｓ－１２１、Ｓ－１３１、Ｓ－１３２、Ｓ－１４１、Ｓ－１４５（いずれも、旭硝子株式会社製）；フルラードＦＣ－９３、ＦＣ－９５、ＦＣ－９８、ＦＣ－１２９、ＦＣ－１３５、ＦＣ－１７０Ｃ、ＦＣ－４３０、ＦＣ－４３１（いずれも、住友スリーエム株式会社製）；メガファックＦ－４７０、Ｆ－１４０５、Ｆ－４７４（いずれも、大日本インキ化学工業株式会社製）；ゾニール（Ｚｏｎｙｌ）ＴＢＳ、ＦＳＰ、ＦＳＡ、ＦＳＮ－１００、ＦＳＮ、ＦＳＯ－１００、ＦＳＯ、ＦＳ－３００、ＵＲ、キャプストーンＦＳ－３０、ＦＳ－３１、ＦＳ－３１００、ＦＳ－３４、ＦＳ－３５（いずれも、Ｃｈｅｍｏｕｒｓ社製）；ＦＴ－１１０、ＦＴ－２５０、ＦＴ－２５１、ＦＴ－４００Ｓ、ＦＴ－１５０、ＦＴ－４００ＳＷ（いずれも、株式会社ネオス製）、ポリフォックスＰＦ－１３６Ａ，ＰＦ－１５６Ａ、ＰＦ－１５１Ｎ、ＰＦ－１５４、ＰＦ－１５９（オムノバ社製）、ユニダインＤＳＮ－４０３Ｎ（ダイキン工業株式会社製）などが挙げられ、これらの中でも、良好な印字品質、特に発色性、紙に対する浸透性、濡れ性、均染性が著しく向上する点から、Ｃｈｅｍｏｕｒｓ社製のＦＳ－３１００、ＦＳ－３４、ＦＳ－３００、株式会社ネオス製のＦＴ－１１０、ＦＴ－２５０、ＦＴ－２５１、ＦＴ－４００Ｓ、ＦＴ－１５０、ＦＴ－４００ＳＷ、オムノバ社製のポリフォックスＰＦ－１５１Ｎ及びダイキン工業株式会社製のユニダインＤＳＮ－４０３Ｎが特に好ましい。 As the fluorine-based surfactant, a compound having 2 to 16 carbon atoms substituted with fluorine is preferable, and a compound having 4 to 16 carbon atoms substituted with fluorine is more preferable.
Examples of the fluorine-based surfactant include a perfluoroalkyl phosphate ester compound, a perfluoroalkylethylene oxide adduct, and a polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain. Among these, the polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain is preferable because it has less foaming property, and is particularly a fluorine-based compound represented by the general formula (F-1) and the general formula (F-2). Surfactants are preferred.

General 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.
General 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 above general formula (F-2), Y is H or CmF _{2m + 1} and m is an integer of 1 to 6, or CH ₂ CH (OH) CH ₂ -CmF _{2m + 1} and m is 4 to 6. It is an integer, or CpH _{2p + 1} and p is an integer of 1 to 19. n is an integer of 1 to 6. a is an integer of 4 to 14.
Commercially available products may be used as the above-mentioned fluorine-based surfactant. Examples of this commercially available product include Surflon S-111, S-112, S-113, S-121, S-131, S-132, S-141, and S-145 (all manufactured by Asahi Glass Co., Ltd.); Full Lard FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431 (all manufactured by Sumitomo 3M Co., Ltd.); Megafuck F-470, F -1405, F-474 (all manufactured by Dainippon Ink and Chemicals Co., Ltd.); 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 The Chemours Company); 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 (manufactured by Omniova), Unidyne DSN-403N (manufactured by Daikin Industries, Ltd.), etc. Among these, FS-3100, FS-34, and FS-300 manufactured by The Chemours Co., Ltd. are significantly improved in good print quality, particularly color development, permeability to paper, wettability, and leveling property. , FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW manufactured by Neos Co., Ltd., Polyfox PF-151N manufactured by Omninova, and Unidyne DSN-403N manufactured by Daikin Industries Co., Ltd. Is 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.
The content of the siloxane surfactant in the treatment liquid B is preferably 0.05% by mass or more, more preferably 0.8% by mass or more and 5% by mass or less.

The physical properties of the treatment liquid B are not particularly limited, and the viscosity, surface tension, pH and the like can be appropriately selected depending on the intended purpose.

The viscosity of the treatment liquid B is preferably 0.5 mPa · s or more and 30 mPa · s or less 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 B needs to be lower than the surface tension of the treatment liquid A, and the surface tension of the treatment liquid B is preferably 5 mN / m or more lower than the surface tension of the treatment liquid A.
The surface tension of the treatment liquid B is preferably 10 mN / m or more and 40 mN / m or less, and more preferably 15 mN / m or more and 35 mN / m or less at 25 ° C.

As the pH of the treatment liquid B, for example, 4 to 12 is preferable, and 4 to 8 is more preferable.

The method of applying the treatment liquid B to the recording medium is the same as that of the treatment liquid A.

The amount of the treatment liquid B adhering to the recording medium in the treatment liquid application step is preferably 0.1 g / m ² or more and 30.0 g / m ² or less, and 0.2 g / m ² or more and 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 at the same time, but the treatment liquid B having a lower surface tension than the treatment liquid A is applied to different regions on the recording medium. It is necessary to apply the ink from the viewpoint of controlling the dot diameter of the ink.
Examples of the method of applying the treatment liquid A and the treatment liquid B to different regions on the recording medium include an inkjet method.
If necessary, a drying step can be provided on the recording medium that has been subjected to the treatment liquid applying step. In this case, the recording medium can be dried by a roll heater, a drum heater, and warm air. The drying temperature is preferably 60 ° C. or higher.

<Ink applying process and ink applying means>
The ink application step is a 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, and is carried out by the ink application means.

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

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

<Organic solvent>
The organic solvent used in the present invention is not particularly limited, and a liquid solvent at 25 ° C. and 1 atm is 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-hexanediol, ethyl-1,2,4-butanetriol, 1,2,3-butanetriol, 2,2,4-trimethyl- Polyhydric alcohols such as 1,3-pentanediol and petriol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl Polyhydric alcohol alkyl ethers such as ethers, polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone. , 1,3-Dimethyl-2-imidazolidinone, ε-caprolactam, γ-butyrolactone and other nitrogen-containing heterocyclic compounds, formamide, N-methylformamide, N, N-dimethylformamide, 3-methoxy-N, N- Amidos such as dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, amines such as monoethanolamine, diethanolamine and triethylamine, sulfur-containing compounds such as dimethylsulfoxide, sulfolane and thiodiethanol, propylene carbonate and ethylene carbonate. And so on.
It is preferable to use an alcohol having a boiling point of 240 ° C. or lower, and an alcohol having a boiling point of 180 ° C. or lower is particularly preferable, because it not only functions as a wetting agent / compatibilizer but also has good drying properties.

Polyol compounds having 8 or more carbon atoms and glycol ether compounds are also preferably used. Specific examples of the polyol compound having 8 or more carbon atoms include 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol.
Specific examples of the glycol ether compound 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. Ethers; Examples thereof 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 the permeability of ink when paper is used as a recording medium.

The content of the organic solvent 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 60% by mass or less from the viewpoint of ink drying property and ejection reliability. More preferably, it is 20% by mass or more and 60% by mass or less.

<Color material>
The coloring material is not particularly limited, and pigments and dyes can be used.
As the pigment, an inorganic pigment or an organic pigment can be used. These may be used alone or in combination of two or more. Further, 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 color pigment such as gold or silver, a metallic pigment, or the like can be used.
As inorganic pigments, 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, and chrome yellow. Can be used.
Examples of organic pigments include azo pigments and polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments, etc.). , Dye chelate (for example, basic dye type chelate, acid dye type chelate, etc.), nitro pigment, nitroso pigment, aniline black and the like can be used. Among these pigments, those having a good affinity with a solvent are preferably used. In addition, resin hollow particles and inorganic hollow particles can also be used.
As a specific example of the pigment, for black, carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, etc., or copper, iron (CI pigment black 11) , Metals such as titanium oxide, and organic pigments such as aniline black (CI pigment black 1).
Further, for color, 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 Carmin 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 Greens 1, 4, 7, 8, 10, 17, 18, 36, etc.

The dye is not particularly limited, and acid dyes, direct dyes, reactive dyes, and basic dyes can be used, and one type may be used alone or two or more types may be used in combination.
As the dye, for example, 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. Hood 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. Dilekdo 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 and the like can be mentioned.

The content of the coloring material in the ink is preferably 0.1% by mass or more and 15% by mass or less, more preferably 1% by mass or more and 10% by mass or less, from the viewpoint of improving the image density, good fixing property and ejection stability. preferable.

In order to disperse the pigment to obtain an ink, a method of introducing a hydrophilic functional group into the pigment to obtain a self-dispersing pigment, a method of coating the surface of the pigment with a resin and dispersing it, and a method of dispersing using a dispersant are used. The method, etc. can be mentioned.
As a method of introducing a hydrophilic functional group into a pigment to obtain a self-dispersing pigment, for example, a method of adding a functional group such as a sulfone group or a carboxyl group to a pigment (for example, carbon) so that the pigment can be dispersed in water. Can be mentioned.
Examples of the method of coating the surface of the pigment with a resin and dispersing the pigment include a method of encapsulating the pigment in microcapsules so that the pigment can be dispersed in water. This can be rephrased as a resin-coated pigment. In this case, it is not necessary that all the pigments blended in the ink are coated with the resin, and the uncoated pigments and the partially coated pigments are dispersed in the ink as long as the effect of the present invention is not impaired. May be.
Examples of the method of dispersing using a dispersant include a method of dispersing using a known low-molecular-weight dispersant and high-molecular-weight dispersant represented by a surfactant.
As the dispersant, for example, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant and the like can be used depending on the pigment.
RT-100 (nonionic surfactant) manufactured by Takemoto Oil & Fat Co., Ltd. and a naphthalene sulfonic acid Na formalin condensate can also be suitably used as a dispersant.
The dispersant may be used alone or in combination of two or more.

<Pigment dispersion>
It is possible to obtain an ink by mixing a material such as water or an organic solvent with the pigment. It is also possible to produce an ink by mixing a material such as water or an organic solvent with a pigment dispersion obtained by mixing a pigment and other water or a dispersant.
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. A disperser may be used for dispersion.
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 the maximum number because the dispersion stability of the pigment is good and the image quality such as ejection stability and image density is also high. It is preferably 500 nm or less, and more preferably 20 nm or more and 150 nm or less. The particle size of the pigment can be measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrac 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, good ejection stability can be obtained and the image density is increased by 0.1 mass. % Or more and 50% by mass or less are preferable, and 0.1% by mass or more and 30% by mass or less are more preferable.
It is preferable that the pigment dispersion is degassed by filtering coarse particles with a filter, a centrifuge, or the like, if necessary.

<Resin>
The type of resin contained in the ink is not particularly limited and may be appropriately selected depending on the intended purpose. For example, urethane resin, polyester resin, acrylic resin, vinyl acetate resin, styrene resin, butadiene resin, etc. Examples thereof include resins, styrene-butadiene resins, vinyl chloride resins, acrylic styrene resins, and acrylic silicone resins.
Resin particles made of these resins may be used. It is possible to obtain ink by mixing resin particles with a material such as a coloring material or an organic solvent in the state of a resin emulsion in which water is used as a dispersion medium. As the resin particles, those synthesized as appropriate may be used, or commercially available products may be used. Further, these may be used alone or in combination of two or more kinds of resin particles.
The volume average particle size of the resin particles is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of obtaining good fixability and high image hardness, 10 nm or more and 1,000 nm or less are preferable. More than 200 nm is more preferable, and 10 nm or more and 100 nm or less is particularly preferable.
The volume average particle size can be measured using, for example, a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrac Bell Co., Ltd.).
The content of the resin is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of fixability and storage stability of the ink, 1% by mass or more and 30% by mass or less with respect to the total amount of the ink. Is preferable, and 5% by mass or more and 20% by mass or less is 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, but from the viewpoint of improving image quality such as ejection stability and image density, the maximum frequency in terms of the maximum number of inks. Is preferably 20 nm or more and 1000 nm or less, and more preferably 20 nm or more and 150 nm or less. 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 Microtrac Bell Co., Ltd.).

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

<Surfactant>
As the surfactant, any of a silicone-based surfactant, a fluorine-based surfactant, an amphoteric surfactant, a nonionic surfactant, and an anionic surfactant can be used.
The silicone-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Among them, those that do not decompose even at high pH are preferable, and examples thereof include side chain modified polydimethylsiloxane, double-ended modified polydimethylsiloxane, single-ended modified polydimethylsiloxane, side chain double-ended modified polydimethylsiloxane, and the like. Those having an oxyethylene group and a polyoxyethylene polyoxypropylene group are particularly preferable because they exhibit good properties as an aqueous surfactant. Further, as the silicone-based surfactant, a polyether-modified silicone-based surfactant can also be used, and examples thereof include compounds in which a polyalkylene oxide structure is introduced into the Si portion side chain of dimethylsiloxane.
Examples of the fluorine-based surfactant include a perfluoroalkyl sulfonic acid compound, a perfluoroalkyl carboxylic acid compound, a perfluoroalkyl phosphate ester compound, a perfluoroalkyl ethylene oxide adduct, and a perfluoroalkyl ether group in the side chain. Polyoxyalkylene ether polymer compounds are particularly preferred because they have low foaming properties. Examples of the perfluoroalkyl sulfonic acid compound include perfluoroalkyl sulfonic acid and perfluoroalkyl sulfonic acid salt. Examples of the perfluoroalkylcarboxylic acid compound include perfluoroalkylcarboxylic acid and perfluoroalkylcarboxylic acid salt. The polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain includes 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. The counter ions of the salts in these fluorine-based surfactants include Li, Na, K, NH ₄ , NH ₃ CH ₂ CH ₂ OH, NH ₂ (CH ₂ CH ₂ OH) ₂ , and NH (CH ₂ CH ₂ OH). ₃ etc. can be mentioned.
Examples of the amphoteric tenside include laurylaminopropionate, lauryl dimethyl betaine, stearyl dimethyl betaine, and lauryl dihydroxyethyl betaine.
Examples of the nonionic surfactant include polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkyl amine, polyoxyethylene alkyl amide, polyoxyethylene propylene block polymer, sorbitan fatty acid ester, and polyoxyethylene sorbitan. Examples thereof include a fatty acid ester and an ethylene oxide adduct of acetylene alcohol.
Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, lauryl salt, polyoxyethylene alkyl ether sulfate salt and the like.
These may be used alone or in combination of two or more.

一般式（Ｓ－１）
（但し、一般式（Ｓ－１）式中、ｍ、ｎ、ａ、及びｂは、それぞれ独立に、整数を表わし、Ｒは、アルキレン基を表し、Ｒ’は、アルキル基を表す。） The silicone-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, side chain-modified polydimethylsiloxane, double-ended modified polydimethylsiloxane, one-ended modified polydimethylsiloxane, side. Examples thereof include polydimethylsiloxane modified at both ends of the chain, and a polyether-modified silicone-based surfactant having a polyoxyethylene group or a polyoxyethylene polyoxypropylene group as a modifying group exhibits good properties as an aqueous surfactant, and is particularly effective. preferable.
As such a surfactant, an appropriately synthesized one may be used, or a commercially available product may be used. As commercially available products, for example, they can be obtained from Big Chemie Co., Ltd., Shin-Etsu Chemical Co., Ltd., Toray Dow Corning Silicone Co., Ltd., Nippon Emulsion Co., Ltd., Kyoeisha Chemical Co., Ltd. and the like.
The above-mentioned polyether-modified silicone-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a polyalkylene oxide structure represented by the general formula (S-1) is dimethylpoly. Examples thereof include those introduced into the Si part side chain of siloxane.

General formula (S-1)
(However, in the general formula (S-1), m, n, a, and b each independently represent an integer, R represents an alkylene group, and R'represents an alkyl group.)

Commercially available products can be used as the above-mentioned polyether-modified silicone-based surfactant, for example, KF-618, KF-642, KF-643 (Shinetsu Chemical Industry Co., Ltd.), EMALEX-SS-5602, SS- 1906EX (Nippon 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 (Big Chemie Co., Ltd.), TSF4440, TSF4452, TSF4453 (Toshiba Silicon Co., Ltd.) and the like can be mentioned.

一般式（Ｆ－１）
上記一般式（Ｆ－１）で表される化合物において、水溶性を付与するためにｍは０～１０の整数が好ましく、ｎは０～４０の整数が好ましい。
一般式（Ｆ－２）
Ｃ_ｎＦ_{２ｎ＋１－}ＣＨ_２ＣＨ（ＯＨ）ＣＨ_２－Ｏ－（ＣＨ_２ＣＨ_２Ｏ）_ａ－Ｙ
上記一般式（Ｆ－２）で表される化合物において、ＹはＨ、又はＣｎＦ_２ｎ＋１でｎは１～６の整数、又はＣＨ_２ＣＨ（ＯＨ）ＣＨ_２－ＣｎＦ_２ｎ＋１でｎは４～６の整数、又はＣｐＨ_２ｐ＋１でｐは１～１９の整数である。ａは４～１４の整数である。
上記のフッ素系界面活性剤としては市販品を使用してもよい。
この市販品としては、例えば、サーフロンＳ－１１１、Ｓ－１１２、Ｓ－１１３、Ｓ－１２１、Ｓ－１３１、Ｓ－１３２、Ｓ－１４１、Ｓ－１４５（いずれも、旭硝子株式会社製）；フルラードＦＣ－９３、ＦＣ－９５、ＦＣ－９８、ＦＣ－１２９、ＦＣ－１３５、ＦＣ－１７０Ｃ、ＦＣ－４３０、ＦＣ－４３１（いずれも、住友スリーエム株式会社製）；メガファックＦ－４７０、Ｆ－１４０５、Ｆ－４７４（いずれも、大日本インキ化学工業株式会社製）；ゾニール（Ｚｏｎｙｌ）ＴＢＳ、ＦＳＰ、ＦＳＡ、ＦＳＮ－１００、ＦＳＮ、ＦＳＯ－１００、ＦＳＯ、ＦＳ－３００、ＵＲ、キャプストーンＦＳ－３０、ＦＳ－３１、ＦＳ－３１００、ＦＳ－３４、ＦＳ－３５（いずれも、Ｃｈｅｍｏｕｒｓ社製）；ＦＴ－１１０、ＦＴ－２５０、ＦＴ－２５１、ＦＴ－４００Ｓ、ＦＴ－１５０、ＦＴ－４００ＳＷ（いずれも、株式会社ネオス製）、ポリフォックスＰＦ－１３６Ａ，ＰＦ－１５６Ａ、ＰＦ－１５１Ｎ、ＰＦ－１５４、ＰＦ－１５９（オムノバ社製）、ユニダインＤＳＮ－４０３Ｎ（ダイキン工業株式会社製）などが挙げられ、これらの中でも、良好な印字品質、特に発色性、紙に対する浸透性、濡れ性、均染性が著しく向上する点から、Ｃｈｅｍｏｕｒｓ社製のＦＳ－３１００、ＦＳ－３４、ＦＳ－３００、株式会社ネオス製のＦＴ－１１０、ＦＴ－２５０、ＦＴ－２５１、ＦＴ－４００Ｓ、ＦＴ－１５０、ＦＴ－４００ＳＷ、オムノバ社製のポリフォックスＰＦ－１５１Ｎ及びダイキン工業株式会社製のユニダインＤＳＮ－４０３Ｎが特に好ましい。 As the fluorine-based surfactant, a compound having 2 to 16 carbon atoms substituted with fluorine is preferable, and a compound having 4 to 16 carbon atoms substituted with fluorine is more preferable.
Examples of the fluorine-based surfactant include a perfluoroalkyl phosphate ester compound, a perfluoroalkylethylene oxide adduct, and a polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain.
Among these, the polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain is preferable because it has less foaming property, and is particularly a fluorine-based compound represented by the general formula (F-1) and the general formula (F-2). Surfactants are preferred.

General 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.
General 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 above general formula (F-2), Y is H or CnF _{2n + 1} and n is an integer of 1 to 6, or CH ₂ CH (OH) CH ₂ -CnF _{2n + 1} and n is 4 to 6. It is an integer, or CpH _{2p + 1} and p is an integer of 1 to 19. a is an integer of 4 to 14.
Commercially available products may be used as the above-mentioned fluorine-based surfactant.
Examples of this commercially available product include Surflon S-111, S-112, S-113, S-121, S-131, S-132, S-141, and S-145 (all manufactured by Asahi Glass Co., Ltd.); Full Lard FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431 (all manufactured by Sumitomo 3M Co., Ltd.); Megafuck F-470, F -1405, F-474 (all manufactured by Dainippon Ink and Chemicals Co., Ltd.); 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 The Chemours Company); 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 (manufactured by Omniova), Unidyne DSN-403N (manufactured by Daikin Industries, Ltd.), etc. Among these, FS-3100, FS-34, and FS-300 manufactured by The Chemours Co., Ltd. are significantly improved in good print quality, particularly color development, permeability to paper, wettability, and leveling property. , FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW manufactured by Neos Co., Ltd., Polyfox PF-151N manufactured by Omninova, and Unidyne DSN-403N manufactured by Daikin Industries Co., Ltd. Is particularly preferable.

The content of the surfactant in the ink is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of excellent wettability and ejection stability and improvement in image quality, 0.001 mass is used. % Or more and 5% by mass or less are preferable, and 0.05% by mass or more and 5% by mass or less are more preferable.

<Defoamer>
The defoaming agent is not particularly limited, and examples thereof include a silicone-based defoaming agent, a polyether-based defoaming agent, and a fatty acid ester-based defoaming agent. These may be used alone or in combination of two or more. Among these, a silicone-based defoaming agent is preferable because it has an excellent defoaming effect.

<Preservatives and fungicides>
The antiseptic and antifungal agent is not particularly limited, and examples thereof include 1,2-benzisothiazolin-3-one and the like.

<pH adjuster>
The pH adjusting agent 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.

The physical characteristics of the ink are not particularly limited and may be appropriately selected depending on the intended purpose. For example, the viscosity, surface tension, pH and the like are preferably in the following ranges.
The viscosity of the ink at 25 ° C. 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 print density and character quality and obtaining good ejection properties. More preferred. Here, for the viscosity, for example, a rotary viscometer (RE-80L manufactured by Toki Sangyo Co., Ltd.) can be used. As the measurement conditions, it is possible to measure at 25 ° C. with a standard cone rotor (1 ° 34'× R24), a sample liquid volume of 1.2 mL, a rotation speed of 50 rpm, and 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 preferably 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 that comes into contact with the liquid.

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

The polypropylene and polyethylene are not particularly limited, and are, 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, Examples include lighting paper, YUPO building materials paper, YUPO polypropylene, YUPOJET, and metallic YUPO (manufactured by Yupo Corporation).

<Recorded material>
The ink recording material of the present invention comprises an image formed by using the ink of the present invention on a recording medium.
It can be recorded by an inkjet recording device and an inkjet recording method to obtain a recorded material.

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

The liquid discharge method is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the discharge head drive method includes a piezoelectric element actuator using PZT or the like, a method of applying thermal energy, and static electricity. 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 or the like can be used.

Examples of the coating method include a blade coating method, a gravure coating method, a gravure offset coating method, a wire bar coating method, a bar coating method, a roll coating method, a knife coating method, an air knife coating method, a comma coating method, and a U comma coating method. , AKKU coating method, smoothing coating method, microgravia 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, the wire bar coating method and the roller coating method are particularly preferable.

<Recording device, recording method>
The ink of the present invention can be suitably used for various recording devices by an inkjet recording method, for example, a printer, a facsimile device, a copying device, a printer / fax / copier multifunction device, a three-dimensional modeling device, and the like.
In the present invention, the recording device and the recording method are devices capable of ejecting ink, various processing liquids, and the like to a recording medium, and a method for recording using the device. The recording medium means a medium to which ink and various treatment liquids can adhere even temporarily.
This recording device can include not only a head portion for ejecting ink, but also means related to feeding, transporting, and discharging paper of a recording medium, a pretreatment device, a device called a posttreatment device, and the like. ..
The recording device and the recording method may have a heating means used in the heating step and a drying means used in the drying step. The heating means and the drying means include, for example, means for heating and drying the printed surface and the back surface of the recording medium. The heating means and the drying means are not particularly limited, but for example, a hot 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, it is equipped with at least a near-infrared irradiation device.
As a near-infrared irradiation device, a device including a halogen lamp and a reflection mirror is known. A halogen heater is incorporated in a reflection mirror to form a heating unit to realize efficient heating. For example, UH-USC-CL300, UHUSC-CL700, UH-USC-CL1000, UH -USD-CL300, UHUSD-CL700, UH-USD-CL1000, UH-MA1-CL300, UHMA1-CL700, UH-MA1-CL1000 (all manufactured by Ushio, Inc.) and the like.
Further, the recording device and the recording method are not limited to those in which significant images such as characters and figures are visualized by ink. For example, those that form patterns such as geometric patterns and those that form three-dimensional images are also included.
Further, the recording device includes both a serial type device that moves the discharge head and a line type device that does not move the discharge head, unless otherwise specified.
Further, as this recording device, it is possible to use not only a desktop type but also a wide recording device capable of printing on an A0 size recording medium, or, for example, continuous paper wound in a roll shape as a recording medium. A continuous book printer is also included.
An example of the recording device will be described with reference to FIGS. 1 and 2. FIG. 1 is a perspective explanatory view of the device. FIG. 2 is a perspective explanatory view of the main tank. The image forming apparatus 400 as an example of the recording apparatus is a serial type image forming apparatus. A mechanism portion 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), and yellow (Y) is, for example, a package of an aluminum laminated film or the like. It is formed of members. The ink container 411 is housed 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 behind the opening when the cover 401c of the main body of the apparatus is opened. A main tank 410 is detachably attached to the cartridge holder 404. As a result, each ink ejection port 413 of the main tank 410 and the ejection head 434 for each color communicate with each other via the supply tube 436 for each color, and ink can be ejected from the ejection head 434 to the recording medium.

This recording device can include not only a portion for ejecting ink but also a device called a pretreatment device, a posttreatment device, and the like.
As one aspect of the pretreatment apparatus and the posttreatment apparatus, it has a pretreatment liquid and a posttreatment liquid as in the case of inks such as black (K), cyan (C), magenta (M), and yellow (Y). There is an embodiment in which a liquid accommodating portion and a liquid discharge head are added, and a pretreatment liquid or a posttreatment liquid is discharged by an inkjet recording method.
As another aspect of the pretreatment device and the posttreatment device, there is a mode in which a pretreatment device and a posttreatment device by, for example, a blade coating method, a roll coating method, and a spray coating method are provided other than the inkjet recording method.

The method of using the ink is not limited to the inkjet recording method, and can be widely used. In addition to the inkjet recording method, examples thereof include 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, and a spray coating method.

In the present invention, the drying temperature at the time of recording is preferably 50 ° C. or higher in order to improve the drying property and the fixing property to the impermeable substrate. The upper limit of the drying temperature at the time of recording is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 200 ° C. or lower from the viewpoint of thermal deformation of the base material from the viewpoint of safety. The drying temperature before and after recording is not particularly limited and can be appropriately selected according to the purpose.

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

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

<Ink preparation>
<Preparation Example 1 of Black Pigment Dispersion Solution>
After premixing the following raw materials, a black pigment dispersion was obtained by circulating and dispersing for 7 hours in a disc-type bead mill (KDL type of Simmal Enterprises, media: using zirconia balls having a diameter of 0.3 mm).
-Carbon black pigment (trade name: Monarch800, manufactured by Cabot): 15 parts by mass-Anionic surfactant (Pionin A-51-B, manufactured by Takemoto Oil & Fat Co., Ltd.): 2 parts by mass-Ion-exchanged water: 83 parts by mass

<Preparation Example 1 of Cyan Pigment Dispersion Solution>
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 Oil & Fat Co., Ltd.): 2 parts by mass -Ion-exchanged water: 83 parts by mass

(Preparation example of ink a1)
Ion-exchanged water was added to the following formulation so as to have a total volume of 100 parts by mass, and after mixing, the mixture was mixed and stirred, and filtered through a filter having an average pore diameter of 5 μm (Minisalt manufactured by Sartorius) to prepare ink a1.
[Ink prescription]
-Black pigment dispersion (non-volatile content 20% by mass): 20 parts by mass-Superflex 300 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyurethane resin, solid content concentration: 30% by mass): 15 parts by mass-BYK-348 (BYK) Silicone-based surfactant): 1 part by mass ・ 1,2-propanediol: 3 parts by mass ・ 1,3-butanediol: 3 parts by mass ・ Equamid 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 Abyssia, preservative): 0.1% by mass Part ・ Ion exchanged water: Remaining amount

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

(Ink sets a to f)
Next, the prepared inks a1 to f2 were combined with Tables 1 and 2 to prepare ink sets a to f.

(Preparation Example of Ethylene-Vinyl Acetate Copolymerized Resin Emulsion A)
1061 g of PVA-1 (polymerization degree 1,700, saponification degree 88 mol%, manufactured by Kuraray Co., Ltd., PVA-217), ion-exchanged water in an autoclave with a pressure resistance of 50 liters equipped with a nitrogen inlet, a thermometer, and a stirrer. 19,440 g, 12.7 g of L (+) sodium tartrate, 10.6 g of sodium acetate, and 0.4 g of ferrous chloride were charged, completely dissolved at 95 ° C, then cooled to 60 ° C, and subjected to nitrogen substitution. gone.
Next, after charging 22,360 g of vinyl acetate, ethylene was pressurized to 45 kg / cm ² and introduced, and 1,000 g of a 0.4% by mass hydrogen peroxide aqueous solution was press-fitted over 5 hours and emulsified at 60 ° C. Polymerization was performed. When the pH at the initial stage of polymerization was confirmed, it was pH = 5.2.

When the amount of residual vinyl acetate reached 10% by mass, ethylene was released, the ethylene pressure was 20 kg / cm ² , and 50 g of a 3% by mass hydrogen peroxide aqueous solution was press-fitted to continue the polymerization.
Ethylene was released and cooled when the amount of residual vinyl acetate monomer in the emulsion reached 1.5% by mass. After cooling, the pH was confirmed and found to be pH = 4.8.
Then, 20 g of sodium bisulfite was added, and deethyleneation was carried out 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-butylhydroperoxide was added and the mixture was stirred for 2 hours. When the pH at the end of the polymerization was confirmed, the pH was 4.7.

This emulsion was filtered to adjust the solid content to 50% by mass to obtain an ethylene-vinyl acetate copolymer resin emulsion A.
The glass transition point (Tg) of the ethylene-vinyl acetate copolymer resin emulsion A was measured by DSC (Thermo plus EVO2 / DSC manufactured by Rigaku Co., Ltd.) and found to be 0 ° C.

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

450 g of the 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 the silicone-based defoamer SE-21 (manufactured by Wacker Silicon) was dissolved in 15 minutes, and the temperature was 25 ° C. After stirring for 10 minutes, the compound of the following structural formula 1 and ethylenediamine and adipic acid hydrazide were added dropwise to obtain a urethane resin emulsion A.
[Structural formula 1]

The glass transition point (Tg) of the obtained polyurethane resin emulsion A was measured by DSC (Thermo plus EVO2 / DSC manufactured by Rigaku Co., Ltd.) and found to be 20 ° C.

(Preparation example of treatment liquid A1>
After formulating the following formulation, the mixture was mixed and stirred, and filtered through a filter (Minisalt manufactured by Sartorius) having an average pore size of 5 μm to prepare a treatment liquid A1.
[Prescription of treatment liquid]
・ 1,2-Propanediol: 10 parts by mass ・ Emargen LS-106 (surfactant manufactured by Kao Co., Ltd.): 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 (manufactured by Avisia, preservative): 0.1 parts by mass ・ Ion exchanged water: Total remaining amount: 100 parts by mass

(Preparation example of treatment liquids A2 to A5)
In the preparation example of the treatment liquid A1, the 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 was changed to the formulation shown in Table 3.

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

<Surface tension of treatment liquid>
As a measuring instrument, AUTOMATIC SUPERFACE TENSIONMETER CBVP-Z manufactured by Kyowa Interface Science Co., Ltd. was used, and the measurement was performed by the Wilhelmy method. The Wilhelmy method is a method of measuring surface tension by reading the force generated when a stylus (platinum plate) touches the surface of a liquid to draw the stylus into the liquid. It was measured 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: Viniblanc 1225 (Tg: 9 ° C.) manufactured by Nissin Chemical Co., Ltd.

(Preparation example of treatment liquid B1)
After formulating the following formulation, the mixture was mixed and stirred, and filtered through a filter (Minisalt manufactured by Sartorius) having an average pore size of 5 μm to prepare a 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 (manufactured by Abyssia, preservative): 0.1 parts by mass ・ Ion exchanged water: Total remaining amount: 100 parts by mass

(Preparation example of treatment liquids B2 to B7)
In the preparation example of the treatment liquid B1, the 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 was changed to the formulation shown in Table 4.

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

The details of the components in Table 4 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: manufactured by Nissin Chemical Co., Ltd., Viniblanc 1225 (Tg: 9 ° C)
-BYK-333 (Silicone-based surfactant manufactured by BYK)
-BYK-345 (Silicone-based surfactant manufactured by BYK)
-BYK-347 (Silicone-based surfactant manufactured by BYK)
・ FS300 (DuPont, fluorine-based surfactant)

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

<Formation of granularity measurement image>
Inkjet printer (IPSiO GX5000, manufactured by Ricoh Co., Ltd.) is filled with each ink in 410k and 410c of FIG. 1 with a combination of ink sets a to f, treatment liquid A, and treatment liquid B shown in Table 5, and the treatment liquid is used. A is filled in 410 m in FIG. 1 and treatment liquid B is filled in 410y in FIG. 1 to form a polyvinyl chloride film (CPPVWP1300, manufactured by Sakurai Co., Ltd., hereinafter also referred to as “PVC film”) in FIG. As shown, a solid black image with 10% gradation and 60% gradation was formed with a resolution of 600 dpi. The processing liquid A was applied to the 10% gradation image, and the processing liquid B was applied to the 60% gradation image, and black ink was applied thereto to form an image. After forming a solid black image, the printed matter was passed through a hot air drying unit at 70 ° C. for drying and fixing.
Next, a cyan solid image was formed in the same manner as the formation of the black solid image except that cyan ink was used instead of the black ink, and drying and fixing were performed.

<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 that it is B or more in actual use.
[Evaluation criteria]
A: No ink dot particles can be seen even when viewed from a distance of less than 5 cm B: No ink dot particles can be seen even when viewed from a distance of 5 cm or more and less than 30 cm C: No ink dot particles can be seen even when viewed from a distance of 30 cm or more and less than 100 cm No ink dot particles can be seen D: Ink dot particles can be seen even when viewed from a distance of 100 cm or more.

＊なお、ブラックのベタ画像、シアンのベタ画像で、粒状度の評価結果は同一であった。

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

On the other hand, Comparative Example 1 is an example in which the treatment liquid A does not contain inorganic particles, the ink dot diameter on the treatment liquid A is larger than that in the example, and the granularity in the 10% gradation image is high. 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, the ink dot diameter on the treatment liquid B is smaller than that of the example, and the granularity in the 60% gradation image is inferior. 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, and the ink dot diameter is larger than that of Comparative Example 1 and the gradation is 10%. The result was that the graininess in the image was inferior.
Comparative Example 4 is an example in which the treatment liquid A does not contain inorganic particles and the surfactant in the treatment liquid B is not siloxane-based, and has a 10% gradation and a 60% scale as compared with Example 1. The result was that the graininess of the toned image was inferior.
Comparative Example 5 is an example in which the processing liquid B is applied to the 10% gradation image, and the ink dot diameter in the 10% gradation image is larger than that in the example, and the graininess in the 10% gradation image is improved. The result was inferior.

Examples of aspects of the present invention are as follows.
<1> A treatment liquid applying step of applying a treatment liquid A containing water, an organic solvent, resin particles, and inorganic particles and a treatment liquid B having a lower surface tension than the treatment liquid A to different regions on a recording medium. When,
An ink applying 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.
It is an image forming method characterized by including.
<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 treatment 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> A treatment liquid applying means for applying a treatment liquid A containing water, an organic solvent, resin particles, and inorganic particles and a treatment liquid B having a lower surface tension than the treatment liquid A to different regions on a recording medium. When,
An ink applying means for 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.
It is an image forming apparatus characterized by having.
<7> The image forming apparatus according to <6>, wherein the treatment 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 treatment liquid B is a siloxane surfactant.
<9> The image forming apparatus according to <8>, wherein the content of the siloxane surfactant in the treatment 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 according to any one of <1> to <5> and the image forming apparatus according to any one of <6> to <10>, the conventional problems are solved and the present invention is made. The purpose can be achieved.

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

Japanese Unexamined Patent Publication No. 2009-166387

Claims (6)

The treatment liquid A containing water, an organic solvent, resin particles, and inorganic particles and the treatment liquid B having a lower surface tension than the treatment liquid A and containing no inorganic particles are applied to different regions on the recording medium. Treatment liquid application process and
An ink applying 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.
An image forming method comprising. The image forming method according to claim 1, wherein the treatment 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 treatment liquid B is a siloxane surfactant. The image forming method according to claim 3, wherein the content of the siloxane surfactant in the treatment liquid B is 0.05% by mass or more. The image forming method according to any one of claims 1 to 4, wherein the ink further contains resin particles. The treatment liquid A containing water, an organic solvent, resin particles, and inorganic particles and the treatment liquid B having a lower surface tension than the treatment liquid A and containing no inorganic particles are applied to different regions on the recording medium. Treatment liquid application means and
An ink applying means for 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.
An image forming apparatus characterized by having.

Images