JP5789878B2 - Inkjet treatment liquid and inkjet recording apparatus - Google Patents

Description

  The present invention relates to a processing liquid for improving fixability and an ink jet recording apparatus including a processing liquid coating apparatus for coating the processing liquid.

  Ink jet recording methods have been rapidly spreading in recent years because they can record color images on plain paper and have low running costs. However, this method has a problem that depending on the combination of the ink and the recording medium, an image defect typified by character bleeding (hereinafter referred to as feathering) is likely to occur, and the image quality is greatly deteriorated. Therefore, attempts have been made to suppress feathering by suppressing ink permeability, but in this case, the drying property of the ink deteriorates, and when touching the recorded matter, the ink is attached to the hand and the image is stained. is there.

In addition, when recording a color image by the ink jet recording method, inks of different colors are stacked one after another, so that the color ink spreads and mixes at the color boundary portion (hereinafter referred to as color bleed), the image There is also a problem that the quality is greatly reduced. Regarding this problem, attempts have been made to suppress color bleeding by increasing the permeability of the ink. In this case, however, the colorant enters the inside of the recording medium, resulting in a decrease in image density. There is a problem in that the ink oozes into the ink so that double-sided printing cannot be performed satisfactorily.
In order to solve these problems at the same time and improve the image quality, an image forming method using a processing liquid and ink has been proposed.

For example, a method of forming a colored portion on a recording medium using a liquid composition in which fine particles having a surface charged with a reverse polarity with respect to a water-based ink are dispersed is proposed (see Patent Document 1). No. 2001-1991151). However, although this method has a certain effect on the aggregation and adsorption of the colorant, a sufficient effect is not obtained in terms of feathering and color bleeding suppression. Further, this proposal using a liquid composition containing fine particles also has a problem in terms of fixability of water-based ink. That is, when the liquid composition and the water-based ink adhere to the recording medium and the vehicle (liquid component or liquid component in the water-based ink) penetrates the recording medium, the mixture of the fine particles and the colorant is formed on the surface of the recording medium. accumulate. Since this deposited layer is mechanically weak and can be easily removed by rubbing with a finger, the ink is soiled by the user's hand, and when the printed materials overlap each other, the rubbing resistance that the printed material becomes dirty on the back surface Insufficient defects occur.
As a further improvement, we contacted an ink containing a coloring material that is ionic in water or an ionic coloring material by adsorption of a member that exhibits ionicity in water, and the coloring material in the ink In order to improve the image quality of inkjet printed images by reacting and aggregating, a cationic member or a member that acidifies water, a nonionic surfactant or an amphoteric surfactant as a foaming agent, and a water-insoluble fatty acid Has previously been proposed (Japanese Patent Application Laid-Open No. 2009-262329 of Patent Document 2).

In order to improve the abrasion resistance of an image formed product, an ink jet recording method is disclosed in which printing is performed by attaching an ink composition and a first liquid containing fine polymer particles to a recording medium (Patent Document). No. 3, WO 00/06390, and Japanese Patent Laid-Open No. 2007-2122. According to this method, it is necessary to add a large amount of polymer fine particles in order to obtain sufficient abrasion resistance. However, when trying to add a large amount of polymer fine particles, side effects such as a decrease in ejection stability and storage stability and a decrease in drying property occur, and the problem has not been solved.
In addition, it has been conventionally known that a treatment liquid containing a cationic group-containing material is deposited on a recording medium and then printed with an inkjet recording ink. For example, a cationic polymer compound and an organic acid are used. A method for improving image density and smear fixing properties by combination is described (see JP 2009-166387 A).

  In addition, a method for improving image density by applying a high-viscosity treatment liquid containing a cationic polymer compound is described (see Japanese Patent Application Laid-Open No. 2007-276387).

Further, a method is described in which the treatment liquid contains an amphoteric polymer compound, and the image density is improved by the difference between the isoelectric point of the amphoteric polymer compound and the pH of the ink (see Patent Document 7). No. 2004-155868).
These well-known vague broadly known technical concepts do not suggest a specific and specific treatment liquid that is particularly suitable for inkjet printing using pigment ink on plain paper without a coating layer. There are problems such as a low density improvement effect or an image density improvement effect but poor offset.

The present invention has been made to solve such problems, and an object of the present invention is to provide an ink jet recording apparatus capable of forming a high-quality image and excellent in fixability and capable of outputting at high speed.
That is, an object of the present invention is to provide an inkjet processing liquid and an inkjet recording apparatus capable of forming a high-quality image and excellent in fixability and capable of outputting at high speed, paying attention to the above-described problems. There is.

  In order to solve the above-described problems, the inkjet processing liquid according to the present invention contains at least a water-soluble amphoteric polymer compound and a fluorosurfactant or a silicone surfactant, and the water-soluble amphoteric polymer compound includes: (A) A cationic structural unit having a configuration having a tertiary ammonium group or a quaternary ammonium group, (B) an anionic structural unit, and (C) a nonionic structural unit. The water-soluble amphoteric polymer compound (A) cationic structural unit is represented by the general formula (I).

一般式（Ｉ）において、Ｒ１は水素原子又はメチル基、Ｒ２は、水素原子、アルキル基、アラルキル基を示し、Ｒ３及びＲ４は、各々アルキル基、アラルキル基を示し、ｎは１〜４の整数を示し、Ｘ−は、ハロゲンイオン、メチル硫酸イオンなどのアニオンを示す。

In the general formula (I), R1 represents a hydrogen atom or a methyl group, R2 represents a hydrogen atom, an alkyl group or an aralkyl group, R3 and R4 each represents an alkyl group or an aralkyl group, and n represents an integer of 1 to 4. And X- represents an anion such as a halogen ion or a methyl sulfate ion.

  As a further feature, the case where the anionic structural unit (B) of the water-soluble amphoteric polymer compound is represented by the general formula (II) is included.

一般式（II）において、Ｒ５は水素原子又はメチル基、Ｍは水素原子、アンモニウムイオン又はアルカリ金属イオンを示す。

In general formula (II), R5 represents a hydrogen atom or a methyl group, and M represents a hydrogen atom, an ammonium ion or an alkali metal ion.

  Furthermore, as a further feature, the (C) nonionic structural unit of the water-soluble amphoteric polymer compound includes a treatment liquid characterized by being represented by the general formulas (III), (IV), and (V).

一般式（III）において、Ｒ６は水素原子又はメチル基を示す。

In general formula (III), R6 represents a hydrogen atom or a methyl group.

一般式（IV）において、Ｒ９は水素原子又はメチル基を示す。

In general formula (IV), R9 represents a hydrogen atom or a methyl group.

一般式（Ｖ）において、Ｒ８は水素原子又はメチル基を示し、Ｒ９はアルキル基、アラルキル基を示す。

In general formula (V), R8 represents a hydrogen atom or a methyl group, and R9 represents an alkyl group or an aralkyl group.

一般式（VI）において、Ｒ１０、Ｒ１１、Ｒ１２は水素原子又はメチル基を示し、ｎは１〜３の整数を示す。

In general formula (VI), R10, R11, and R12 represent a hydrogen atom or a methyl group, and n represents an integer of 1 to 3.

  Furthermore, an inkjet processing apparatus characterized by using the above-described inkjet processing liquid is included.

  As will be apparent from the following detailed and specific description, according to the present invention, various conventional problems can be solved, high-quality images can be formed on plain paper, and the fixing solution has excellent fixability. An extremely excellent effect that an image forming method, an image formed product, and an ink jet recording apparatus can be provided is exhibited.

FIG. 2 is a diagram illustrating an example of a recording apparatus that scans an inkjet recording head and forms an image. It is a figure which shows another specific example of the apparatus for implement | achieving the image recording method of this embodiment.

  Hereinafter, the present invention will be described in more detail with reference to preferred embodiments.

<< Inkjet treatment liquid >>
The inkjet processing liquid of this embodiment contains at least a water-soluble amphoteric polymer compound and a fluorine surfactant or a silicone surfactant, and the water-soluble amphoteric polymer compound is (A) a tertiary ammonium group, or It has a cationic structural unit having a configuration having a quaternary ammonium group, (B) an anionic structural unit, and (C) a nonionic structural unit.

<Water-soluble amphoteric polymer compound>
The water-soluble amphoteric polymer compound contains (A) a cationic structural unit composed of a structural unit having a quaternary ammonium group, (B) an anionic structural unit, and (C) a nonionic structural unit. It can be produced by copolymerizing monomers that form each structural unit.
Examples of the cationic structural unit (A) in the water-soluble amphoteric polymer compound include a cationic unit represented by the general formula (I). The cationic unit represented by the general formula (I) is assumed to also include their addition salts. Examples of the addition salt include hydrochloride, sulfate, nitrate, and the like.

一般式（Ｉ）において、Ｒ１は水素原子又はメチル基、Ｒ２は、水素原子、アルキル基、アラルキル基を示し、Ｒ３及びＲ４は、各々アルキル基、アラルキル基を示し、ｎは１〜４の整数を示し、Ｘ−は、ハロゲンイオン、メチル硫酸イオンなどのアニオンを示す。

In the general formula (I), R1 represents a hydrogen atom or a methyl group, R2 represents a hydrogen atom, an alkyl group or an aralkyl group, R3 and R4 each represents an alkyl group or an aralkyl group, and n represents an integer of 1 to 4. And X- represents an anion such as a halogen ion or a methyl sulfate ion.

Here, examples of the alkyl group include a lower alkyl group such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, examples of the cycloalkyl group include a cyclohexyl group, and examples of the aralkyl group include a benzyl group. .
For example, the monomer having the structural unit of the general formula (I) includes dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dipropylaminoethyl acrylate, dipropylaminoethyl methacrylate, dialkylethyl ( Quaternary of alkyl halides such as (meth) acrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl acrylate, diethylaminopropyl methacrylate, dipropylaminopropyl acrylate, dipropylaminopropyl methacrylate, dialkylpropyl (meth) acrylate, etc. Examples thereof include ammonium salts. Examples of the alkyl halide include methyl chloride, ethyl chloride, methyl iodide, propyl iodide, methyl bromide, propyl bromide, benzyl chloride and the like.

  Examples of the monomer that forms the anionic structural unit (B) in the water-soluble amphoteric polymer compound include an anionic unit of the general formula (II).

一般式（II）において、Ｒ５は水素原子又はメチル基、Ｍは水素原子、アンモニウムイオン又はアルカリ金属イオンを示す。

In general formula (II), R5 represents a hydrogen atom or a methyl group, and M represents a hydrogen atom, an ammonium ion or an alkali metal ion.

Here, examples of the alkali metal ion include lithium ion and potassium ion.
Examples of the compound of the general formula (II) include, but are not limited to, carboxylic acids having a vinyl group such as acrylic acid, methacrylic acid, and crotonic acid, and salts thereof. These anionic monomers may be used alone or in combination of two or more.

  The monomer forming the (C) nonionic structural unit in the water-soluble amphoteric polymer compound is not particularly limited as long as it is nonionic and can be copolymerized with the cationic monomer and the anionic monomer. However, examples of such nonionic monomers include nonionic units represented by general formulas (III), (IV), (V), and (VI).

一般式（III）において、Ｒ６は水素原子又はメチル基を示す。

In general formula (III), R6 represents a hydrogen atom or a methyl group.

一般式（IV）において、Ｒ９は水素原子又はメチル基を示す。

In general formula (IV), R9 represents a hydrogen atom or a methyl group.

一般式（Ｖ）において、Ｒ８は水素原子又はメチル基を示し、Ｒ９はアルキル基、アラルキル基を示す。アルキル基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基などの低級アルキル基を、シクロアルキル基としては、シクロヘキシル基を、アラルキル基としては、ベンジル基、２−フエニル−エチル基をあげることができる。

In general formula (V), R8 represents a hydrogen atom or a methyl group, and R9 represents an alkyl group or an aralkyl group. The alkyl group is a lower alkyl group such as a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, the cycloalkyl group is a cyclohexyl group, and the aralkyl group is a benzyl group or a 2-phenyl-ethyl group. I can give you.

一般式（VI）において、Ｒ１０、Ｒ１１、Ｒ１２は水素原子又はメチル基を示し、ｎは１〜３の整数を示す。

In general formula (VI), R10, R11, and R12 represent a hydrogen atom or a methyl group, and n represents an integer of 1 to 3.

Examples of the compounds of the general formulas (III) to (VI) include diacetone (meth) acrylamide, N-vinylpyrrolidone, ethyl methacrylate, hydroxyethyl (meth) acrylate and the like.
The method for producing the water-soluble amphoteric polymer compound is not particularly limited, and any method such as ordinary solution polymerization, suspension polymerization, and emulsion polymerization can be used.
For example, in an aqueous medium, at least one of the cationic monomers, at least one of the anionic monomers, and at least one of the nonionic monomers are present in the presence of the polymerization initiator. Usually, it can be produced by copolymerization at a temperature in the range of 10 to 100 ° C., preferably 25 to 70 ° C. for about 10 to 120 hours, preferably 24 to 96 hours.

  Examples of the aqueous medium used in this reaction include water, inorganic salt aqueous solution (aqueous solution of hydrochloric acid, sulfuric acid, phosphoric acid, etc.), organic acid aqueous solution, inorganic acid salt aqueous solution (sodium chloride, zinc chloride, calcium chloride, magnesium chloride). Etc.). Examples of the polymerization initiator include peroxides such as ammonium persulfate, potassium persulfate, hydrogen peroxide, and tert-butyl hydroperoxide, and these peroxides and reducing agents such as metal ions and ascorbic acid. Examples thereof include redox initiators composed of combinations and azo compounds such as 2,2′-azobisisobityronitrile. This polymerization reaction is preferably carried out in an inert gas atmosphere such as nitrogen gas at atmospheric pressure. In the present invention, this water-soluble amphoteric polymer compound may be used singly or in combination of two or more.

In aqueous solution polymerization, ammonium persulfate, potassium persulfate, 2,2-azobis (2-amidinopropane) hydrochloride, etc. are used as polymerization initiators, and a predetermined proportion of each monomer is polymerized under normal polymerization conditions. Can be manufactured.
In the treatment liquid, the water-soluble amphoteric polymer compound includes (A) a cationic structural unit composed of a structural unit having a quaternary ammonium group, (B) an anionic structural unit, and (C) a nonionic structural unit. By containing a water-soluble amphoteric polymer compound obtained by copolymerizing monomers that form each constituent unit, the flocculant does not penetrate deeply into the recording medium on the recording medium. Since the effect of staying in the vicinity of the surface of the medium is enhanced, the image density is improved and the amount of liquid applied is small even when the amount of the flocculant is reduced compared to the case where the medium is not added. Cockling is unlikely to occur. Furthermore, when applying with a roller, the viscosity is low when the treatment liquid is under pressure and the viscosity on the recording medium is high, so that thin film application with a roller is possible and the same application amount regardless of the water absorption of the recording medium Application with is possible. In addition, since it has a cation and an anion at the same time, an attractive force and a repulsion appear on the surface of the recording medium at the same time. Expected to penetrate quickly.

  In the production of the water-soluble amphoteric polymer compound used in the present invention, the monomer (A) is 10 to 35% by weight, the monomer (B) is 5 to 25% by weight, and the monomer (C) is 50 to 75% by weight. It is preferable. If the ratio of one of the monomer (A) and the monomer (B) is reduced, the balance between attractive force and repulsion on the surface of the recording medium is poor, so that the ink permeation rate becomes slow and the drying property becomes poor. Further, when the ratio of the monomer (A) and the monomer (B) is reduced at the same time, the water solubility of the polymer compound is lowered. On the other hand, when the ratio of the monomer (A) to the monomer (B) increases, the stability of the water-soluble amphoteric polymer compound deteriorates, causing problems such as aggregation.

The water-soluble amphoteric polymer compound of the present invention thus obtained has a viscosity average molecular weight of about 50,000 to 200,000, preferably 90000 to 150,000, as a copolymer.
In addition, this viscosity average molecular weight [(eta)] is the following (1) Formula and Polmer Handbook 2nd ED. , Plv-14, and using the constants (K = 0.14, a = 0.06). [Η] = K · M · a

<Surfactant>
As the surfactant used in the inkjet processing liquid, at least one selected from silicone surfactants and fluorine surfactants is suitable. Among these, silicone surfactants and fluorine surfactants are particularly preferable. These surfactants can be used alone or in combination of two or more.
Examples of the fluorosurfactant 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.). ; Fullard FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431, FC-4430 (all manufactured by Sumitomo 3M Limited); -470, F-1405, F-474 (all manufactured by Dainippon Ink & Chemicals, Inc.); Zonyl FS-300, FSN, FSN-100, FSO (all manufactured by DuPont); F-top EF-351, EF -352, EF-801, EF-802 (all manufactured by Gemco) and the like. Among these, Zonyl FS-300, FSN, FSN-100, and FSO (all manufactured by DuPont) which are favorable in terms of reliability and color development are particularly suitable.

  Examples of the silicone surfactant include modified silicones KF-351A, KF-353A, KF354L, KF355A, KF-615A, KF-640, KF-642, KF-643, KF-6011 (all Shin-Etsu Chemical Co., Ltd.) Silicone FZ-77, FZ-2104, FZ-2105, L-7604 (all manufactured by Toray Dow Corning) and the like. Among these, KF-355A, KF-640, KF-642, and Kf-643 (all of which are manufactured by Shin-Etsu Kogyo Co., Ltd.) are particularly suitable for improving reliability and color development.

  The content of the surfactant in the inkjet processing liquid is preferably 0.01 to 3.0% by mass, and more preferably 0.5 to 2% by mass. If the content is less than 0.01% by mass, the effect of adding a surfactant may be lost, and if it exceeds 3.0% by mass, there may be a problem in storage stability.

<Water-soluble organic solvent>
Examples of the water-soluble organic solvent used in this embodiment include polyhydric alcohols, polyhydric alcohol alkyl ethers, polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, and sulfur-containing compounds. , Propylene carbonate, and ethylene carbonate. The water-soluble organic solvent according to the present embodiment flows into the ink jet processing liquid even when the water in the ink jet processing liquid evaporates and reaches an equilibrium state. Gives sex.
As the water-soluble organic solvent, when a water-soluble organic solvent having a high equilibrium water content is used, even when the water in the inkjet processing liquid evaporates and reaches an equilibrium state, the water-soluble organic solvent has a large amount of water. It can be held and an excessive increase in viscosity can be suppressed.

  In the present embodiment, the water-soluble organic solvent having a high equilibrium water content refers to a water-soluble organic solvent having an equilibrium water content in an environment of a temperature of 23 ° C. and a humidity of 80% of 30 wt% or more, preferably 40 wt% or more ( Hereinafter referred to as water-soluble organic solvent A). By using such a water-soluble organic solvent A, the water-soluble organic solvent A can retain a large amount of water and prevent an increase in viscosity even when the water content of the ink evaporates and reaches a water balance. Equilibrium water content means that a mixture of water-soluble organic solvent and water is opened to air at a constant temperature and humidity, and the evaporation of water in the solution and the absorption of water in the ink into the ink are in an equilibrium state. Says the amount of water when it becomes. Specifically, the equilibrium water content is determined by using a saturated aqueous solution of potassium chloride, keeping the temperature and humidity in the desiccator at 23 ± 1 ° C. and 80 ± 3%, and weighing 1 g of each water-soluble organic solvent in the desiccator. The petri dish can be stored for a period until the mass change disappears, and can be obtained by the following formula.

  Examples of the water-soluble organic solvent A preferably used in the present embodiment include polyhydric alcohols having an equilibrium water content of 30 wt% or more in an environment of a temperature of 23 ° C. and a humidity of 80%. Specific examples of such water-soluble organic solvent A include 1,2,3-butanetriol (bp175 ° C./33 hPa, 38 wt%), 1,2,4-butanetriol (bp190-191 ° C./24 hPa, 41 wt%). ), Glycerin (bp 290 ° C., 49 wt%), diglycerin (bp 270 ° C./20 hPa, 38 wt%), triethylene glycol (bp 285 ° C., 39 wt%), tetraethylene glycol (bp 324-330 ° C., 37 wt%), diethylene glycol (bp 245) C, 43 wt%), 1,3-butanediol (bp203-204 ° C, 35 wt%) and the like. Of these, glycerin and 1,3-butanediol are particularly preferably used for reasons such as lowering the viscosity when water is contained, and keeping the pigment dispersion stable without aggregation. When the water-soluble organic solvent A is used in an amount of 50 wt% or more of the entire water-soluble organic solvent, it is preferable because it is excellent in securing ejection stability and preventing waste ink sticking in a maintenance device of the ink ejection device.

  In addition to the water-soluble organic solvent A, the inkjet processing liquid of this embodiment may be replaced with a part of the water-soluble organic solvent A or in addition to the water-soluble organic solvent A as required. A water-soluble organic solvent (hereinafter referred to as water-soluble organic solvent B) having an equilibrium water content at 80 ° C. of less than 30 wt% can be used in combination. Examples of such water-soluble organic solvents B include polyhydric alcohols, polyhydric alcohol alkyl ethers, polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, sulfur-containing compounds, propylene. Examples include carbonate, ethylene carbonate, and other water-soluble organic solvents.

  Specific examples of the polyhydric alcohols of the water-soluble organic solvent B include, for example, dipropylene glycol (bp 232 ° C), 1,5-pentanediol (bp 242 ° C), 3-methyl-1,3-butanediol (bp 203 ° C). ), Propylene glycol (bp 187 ° C.), 2-methyl-2,4-pentanediol (bp 197 ° C.), ethylene glycol (bp 196-198 ° C.), tripropylene glycol (bp 267 ° C.), hexylene glycol (bp 197 ° C.), polyethylene Glycol (viscous liquid to solid), polypropylene glycol (bp 187 ° C), 1,6-hexanediol (bp253-260 ° C), 1,2,6-hexanetriol (bp178 ° C), trimethylolethane (solid, mp199- 201 ° C), trimethylolpropane Solid, MP61 ° C.), and the like.

  Examples of the polyhydric alcohol alkyl ethers include ethylene glycol monoethyl ether (bp 135 ° C.), ethylene glycol monobutyl ether (bp 171 ° C.), diethylene glycol monomethyl ether (bp 194 ° C.), diethylene glycol monoethyl ether (bp 197 ° C.), and diethylene glycol monoethyl ether. Examples include butyl ether (bp 231 ° C.), ethylene glycol mono-2-ethylhexyl ether (bp 229 ° C.), propylene glycol monoethyl ether (bp 132 ° C.), and the like. Examples of the polyhydric alcohol aryl ethers include ethylene glycol monophenyl ether (bp 237 ° C.) and ethylene glycol monobenzyl ether.

  Examples of the nitrogen-containing heterocyclic compound include 2-pyrrolidone (bp 250 ° C., mp 25.5 ° C., 47-48 wt%), N-methyl-2-pyrrolidone (bp 202 ° C.), 1,3-dimethyl-2-imidazo Lydinone (bp 226 ° C.), ε-caprolactam (bp 270 ° C.), γ-butyrolactone (bp 204-205 ° C.) and the like can be mentioned. Examples of the amides include formamide (bp 210 ° C.), N-methylformamide (bp 199-201 ° C.), N, N-dimethylformamide (bp 153 ° C.), N, N-diethylformamide (bp 176-177 ° C.), and the like. Can be mentioned. Examples of the amines include monoethanolamine (bp 170 ° C), diethanolamine (bp268 ° C), triethanolamine (bp360 ° C), N, N-dimethylmonoethanolamine (bp139 ° C), N-methyldiethanolamine (bp243 ° C). ), N-methylethanolamine (bp159 ° C.), N-phenylethanolamine (bp282-287 ° C), 3-aminopropyldiethylamine (bp169 ° C), and the like. Examples of the sulfur-containing compounds include dimethyl sulfoxide (bp 139 ° C.), sulfolane (bp 285 ° C.), thiodiglycol (bp 282 ° C.), and the like. Other solid water-soluble organic solvents are preferably saccharides.

Examples of the saccharide include monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides), polysaccharides, and the like. Specific examples include glucose, mannose, fructose, ribose, xylose, arabinose, galactose, maltose, cellobiose, lactose, sucrose, trehalose, maltotriose, and the like. Here, the polysaccharide means a saccharide in a broad sense, and is used to include a substance that exists widely in nature such as α-cyclodextrin and cellulose. The derivatives of these saccharides are represented by the reducing sugars of the saccharides described above (for example, sugar alcohol (general formula: HOCH ₂ (CHOH) _n CH ₂ OH (where n represents an integer of 2 to 5)). ), Oxidized sugars (for example, aldonic acid, uronic acid, etc.), amino acids, thioic acids, etc. Among these, sugar alcohols are preferable, and specific examples include maltitol, sorbit, and the like.

  The content of the water-soluble organic solvent agent in the inkjet processing liquid is not particularly limited, but is usually 10 to 80% by mass, preferably 15 to 60% by mass. If it is larger than 80% by mass, there is a possibility of poor drying on the recording medium after treatment depending on the type of the water-soluble organic solvent. If it is smaller than 10% by mass, moisture evaporation occurs in the treatment coating process and the composition of the treatment liquid. May change drastically.

―Other ingredients―
The inkjet processing liquid of the present embodiment preferably contains at least one non-wetting agent polyol compound or glycol ether compound having 8 to 11 carbon atoms as a penetrating agent. These preferably have a solubility of between 0.2 and 5.0% by weight in water at 25 ° C. Among these, 2-ethyl-1,3-hexanediol [solubility: 4.2% (25 ° C.)], 2,2,4-trimethyl-1,3-pentanediol [solubility: 2.0% (25 ° C)] is particularly preferred.

  Examples of other non-wetting agent polyol compounds include aliphatic diols such as 2-ethyl-2-methyl-1,3-propanediol, 3,3-dimethyl-1,2-butanediol, 2,2- Diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2,4-dimethyl-2,4-pentanediol, 2,5-dimethyl-2,5-hexanediol, 5-hexene-1,2-diol and the like.

  Other penetrants that can be used in combination are not particularly limited as long as they can be dissolved in ink and can be prepared to have desired physical properties, and can be appropriately selected according to the purpose. For example, diethylene glycol monophenyl ether, ethylene Glycol monophenyl ether, ethylene glycol monoallyl ether, diethylene glycol monophenyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, alkyl and aryl ethers of polyhydric alcohols such as tetraethylene glycol chlorophenyl ether, lower alcohols such as ethanol, etc. Is mentioned.

  The content of the penetrant in the inkjet processing liquid is preferably 0.1 to 5.0% by mass. When the content is less than 0.1% by mass, the effect of infiltrating the ink-jet ink may be lost. When the content exceeds 5.0% by mass, it is separated from the solvent due to low solubility in the solvent. The effect of improving the permeability may be saturated.

  If necessary, an antiseptic agent, a rust inhibitor, and the like used in the inkjet ink described below may be used in the inkjet processing liquid of the present embodiment.

<Inkjet ink>
The ink jet ink used in the image forming method of the present embodiment contains a water-dispersible colorant, a water-soluble organic solvent, a surfactant, a penetrating agent, and water.

-Water dispersible colorant-
In the inkjet ink, a pigment is mainly used as a water-dispersible colorant from the viewpoint of weather resistance, but a dye may be contained within a range in which the weather resistance is not deteriorated for the purpose of adjusting the color tone. There is no restriction | limiting in particular as said pigment, According to the objective, it can select suitably, For example, the inorganic pigment, organic pigment, etc. for black or color are mentioned. These may be used individually by 1 type and may use 2 or more types together.

  Inorganic pigments include titanium oxide and iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, and chrome yellow, as well as carbon produced by known methods such as the contact method, furnace method, and thermal method. Black can be used.

  Organic pigments include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments), polycyclic pigments (eg, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazines). Pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinofullerone pigments, etc.), 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 water are particularly preferably used.

  Specific examples of pigments that are more preferably used in the above-mentioned pigments 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), metals such as titanium oxide, and organic pigments such as 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 , 408, 109, 110, 117, 120, 128, 138, 150, 151, 153, 183, 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, 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, 185, 190, 193, 209, 219, C.I. I. Pigment violet 1 (rhodamine lake), 3, 5: 1, 16, 19, 23, 38, C.I. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3 (phthalocyanine blue), 16, 17: 1, 56, 60, 63, C.I. I. Pigment green 1, 4, 7, 8, 10, 17, 18, 36, and the like.

The following first and second forms are particularly preferable when the colorant is a pigment.
1) In the first embodiment, the colorant contains a polymer emulsion (an aqueous dispersion of polymer fine particles containing a coloring material) in which a polymer fine particle contains a water-insoluble or poorly water-soluble coloring material.
2) In the second embodiment, the colorant has a surface having at least one hydrophilic group and exhibits water dispersibility in the absence of a dispersant (hereinafter, referred to as “self-dispersible pigment”). ).

In the present invention, in the case of the second embodiment, it is preferable that the following water-dispersible resin is included.
As the water-dispersible colorant of the first form, it is preferable to use a polymer emulsion in which a pigment is contained in polymer fine particles in addition to the pigment. The polymer emulsion in which the pigment is contained in the polymer fine particles is one in which the pigment is encapsulated in the polymer fine particles, or the pigment is adsorbed on the surface of the polymer fine particles. In this case, it is not necessary that all the pigments are encapsulated or adsorbed, and the pigments may be dispersed in the emulsion as long as the effects of the present invention are not impaired. Examples of the polymer forming the polymer emulsion (polymer in the polymer fine particles) include vinyl polymers, polyester polymers, polyurethane polymers, and the like. Particularly preferably used polymers are vinyl polymers and polyester polymers. Polymers disclosed in 2000-53897 and JP 2001-139849 can be used.

  The self-dispersing pigment of the second form is a surface modified so that at least one hydrophilic group is bonded to the surface of the pigment directly or via another atomic group. In the surface modification, a specific functional group (a functional group such as a sulfone group or a carboxyl group) is chemically bonded to the surface of the pigment, or at least one of hypohalous acid and a salt thereof is used. A method such as wet oxidation is used. Among these, a form in which a carboxyl group is bonded to the surface of the pigment and dispersed in water is particularly preferable. Since the pigment is thus surface-modified and the carboxyl group is bonded, not only the dispersion stability is improved, but also high-quality print quality is obtained and the water resistance of the recording medium after printing is further improved. improves.

Further, since the ink containing the self-dispersing pigment of the first form is excellent in redispersibility after drying, clogging does not occur even when printing is stopped for a long time and ink moisture near the inkjet head nozzle evaporates. Good printing can be easily performed with a simple cleaning operation. The volume average particle size (D ₅₀ ) of the self-dispersing pigment is preferably 0.01 to 0.16 μm in the ink.

For example, as the self-dispersing carbon black, those having ionicity are preferable, and those having an anionic charge are preferable.
As the anionic hydrophilic group, for _{example, -COOM, -SO 3 M, -PO} 3 HM, -PO 3 M 2, -SO 2 NH 2, -SO 2 NHCOR ( although, M is an alkali metal, ammonium or And R represents an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have a substituent, or a naphthyl group which may have a substituent.
Among these, it is preferable to use those in which —COOM and —SO ₃ M are bonded to the surface of the color pigment.

  Further, “M” in the hydrophilic group includes, for example, lithium, sodium, potassium and the like as an alkali metal. Examples of the organic ammonium include mono to trimethyl ammonium, mono to triethyl ammonium, and mono to trimethanol ammonium. As a method of obtaining the anionically charged color pigment, as a method of introducing —COONa to the color pigment surface, for example, a method of oxidizing the color pigment with sodium hypochlorite, a method of sulfonation, a diazonium salt The method of making it react is mentioned.

The hydrophilic group may be bonded to the surface of carbon black via another atomic group.
Examples of other atomic groups include an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have a substituent, or a naphthyl group which may have a substituent. Specific examples of the case where the hydrophilic group is bonded to the surface of carbon black through another atomic group include, for example, —C ₂ H ₄ COOM (where M represents an alkali metal or quaternary ammonium). ), -PhSO ₃ M (wherein Ph represents a phenyl group, M represents an alkali metal or a quaternary ammonium).

  The content of the colorant in the inkjet ink is preferably 2 to 15% by mass and more preferably 3 to 12% by mass in terms of solid content. If the content is less than 2% by mass, the color developability and image density of the ink may be lowered, and if it exceeds 15% by mass, the ink may be thickened and the dischargeability may be deteriorated. There is not preferable.

―Water-soluble organic solvent―
As the water-soluble organic solvent used in the inkjet ink, a water-soluble organic solvent used in the inkjet processing liquid is preferably used. The mass ratio of the water-dispersible colorant to the water-soluble organic solvent in the inkjet ink affects the ink ejection stability from the head. For example, when the solid content of the water-dispersible colorant is high but the blending amount of the water-soluble organic solvent is small, water evaporation near the ink meniscus of the nozzle may progress and cause ejection failure. The content of the water-soluble organic solvent in the inkjet ink is preferably 20 to 50% by mass, and more preferably 20 to 45% by mass. When the content is less than 20% by mass, there is a possibility that the ejection stability is lowered or the waste ink is fixed by the maintenance device of the ink jet recording apparatus. On the other hand, if it exceeds 50% by mass, the dryness on the paper surface is inferior and the character quality on plain paper may be lowered.

―Surfactant―
The surfactant used in the inkjet ink is preferably an anionic surfactant having a low surface tension, low penetrability, and high leveling property without losing dispersion stability depending on the type of the colorant or the combination of the water-soluble organic solvent. At least one selected from surfactants, nonionic surfactants, silicone surfactants and fluorosurfactants is preferred.
Among these, silicone surfactants and fluorine surfactants are particularly preferable. These surfactants can be used alone or in combination of two or more.
As the surfactant used in the inkjet ink, the surfactant used in the inkjet processing liquid is preferably used.

  The content of the surfactant in the inkjet ink is preferably 0.01 to 3.0% by mass, and more preferably 0.5 to 2% by mass. When the content is less than 0.01% by mass, the effect of adding a surfactant may be lost. When the content exceeds 3.0% by mass, the permeability to a recording medium becomes higher than necessary. There may be a decrease in the image density or a show-through.

―Penetration agent―
As the penetrant used in the ink jet ink, the penetrant used in the ink jet processing liquid is preferably used. The content of the penetrant in the ink-jet ink is preferably 0.1 to 4.0% by mass. When the content is less than 0.1% by mass, quick-drying may not be obtained and a blurred image may be obtained. When the content exceeds 4.0% by mass, the dispersion stability of the colorant is impaired, and the nozzle In some cases, the image density is lowered or the back-through occurs, such as being easily clogged or having an unnecessarily high permeability to the recording medium.

―Water-dispersible resin―
The water-dispersible resin has excellent film-forming properties (image formability), high water repellency, high water resistance, and high weather resistance, and has high water resistance and high image density (high color development). Useful for. For example, a condensation synthetic resin, an addition synthetic resin, a natural polymer compound, and the like can be given.
Examples of the condensed synthetic resin include polyester resin, polyurethane resin, polyepoxy resin, polyamide resin, polyether resin, poly (meth) acrylic resin, acrylic-silicone resin, and fluorine-based resin.

Examples of the addition type synthetic resin include polyolefin resins, polystyrene resins, polyvinyl alcohol resins, polyvinyl ester resins, polyacrylic acid resins, unsaturated carboxylic acid resins, and the like.
Examples of the natural polymer compound include celluloses, rosins, and natural rubber.
Among these, polyurethane resin fine particles, acrylic-silicone resin fine particles, and fluorine-based resin fine particles are particularly preferable. Moreover, it is not a problem to use two or more kinds of the water-dispersible resins in combination.
As the fluororesin, fluororesin fine particles having a fluoroolefin unit are preferred, and among these, fluorine-containing vinyl ether resin fine particles composed of a fluoroolefin unit and a vinyl ether unit are particularly preferred.
As the fluoroolefin unit is not particularly limited and may be appropriately selected depending on the purpose, for example, _{-CF 2 CF 2 -, - CF} 2 CF (CF 3) -, - CF 2 CFCl- like It is done.
There is no restriction | limiting in particular as said vinyl ether unit, Although it can select suitably according to the objective, For example, the compound etc. which are represented with following Structural formula are mentioned.

As the fluorine-containing vinyl ether resin fine particles composed of the fluoroolefin unit and the vinyl ether unit, an alternating copolymer obtained by alternately copolymerizing the fluoroolefin unit and the vinyl ether unit is preferable.
As such fluorine-based resin fine particles, those appropriately synthesized may be used, or commercially available products may be used. Examples of the commercially available products include Fluorate FEM-500, FEM-600, Dickguard F-52S, F-90, F-90M, F-90N, and Aquafuran TE-5A manufactured by Dainippon Ink & Chemicals, Inc .; Asahi Glass Co., Ltd. Lumiflon FE4300, FE4500, FE4400, Asahi Guard AG-7105, AG-950, AG-7600, AG-7000, AG-1100, etc. are mentioned.

  The water-dispersible resin may be used as a homopolymer, may be used as a copolymer and used as a composite resin, and any of a single-phase structure type, a core-shell type, and a power feed type emulsion Can be used.

As the water-dispersible resin, a resin itself having a hydrophilic group and having a self-dispersibility, and a resin itself having no dispersibility and imparted with a surfactant or a resin having a hydrophilic group can be used. .
Among these, an emulsion of resin particles obtained by emulsion and suspension polymerization of an ionomer of a polyester resin or a polyurethane resin or an unsaturated monomer is optimal. In the case of emulsion polymerization of an unsaturated monomer, the resin emulsion is reacted with water to which an unsaturated monomer, a polymerization initiator, a surfactant, a chain transfer agent, a chelating agent, and a pH adjusting agent are added. Therefore, a water-dispersible resin can be easily obtained, and the desired properties can be easily produced because the resin configuration can be easily changed.

Examples of the unsaturated monomer include unsaturated carboxylic acids, monofunctional or polyfunctional (meth) acrylic acid ester monomers, (meth) acrylic acid amide monomers, and aromatic vinyl monomers. , Vinyl cyano compound monomers, vinyl monomers, allyl compound monomers, olefin monomers, diene monomers, oligomers having unsaturated carbon, etc., alone or in combination Can do. By combining these monomers, the properties can be flexibly modified, and the properties of the resin can be modified by performing a polymerization reaction or a graft reaction using an oligomer type polymerization initiator.
Examples of the unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid and the like.

  Examples of the monofunctional (meth) acrylic acid ester monomers include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2 -Ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, methacryloxyethyltrimethylammonium Salt, 3-me Acryloxypropyltrimethoxysilane, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, decyl acrylate , Dodecyl acrylate, octadecyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, dimethylaminoethyl acrylate, acryloxyethyl trimethyl ammonium salt, and the like.

  Examples of the polyfunctional (meth) acrylic acid ester monomers include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1, 4-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, dipropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, polybutylene glycol dimethacrylate, 2,2′-bis (4-methacryloxy) Diethoxyphenyl) propane, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, polyethylene Glycol diacrylate, triethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, 1,9-nonanediol di Acrylate, polypropylene glycol diacrylate, 2,2′-bis (4-acryloxypropyloxyphenyl) propane, 2,2′-bis (4-acryloxydiethoxyphenyl) propane trimethylolpropane triacrylate, trimethylolethanetri Acrylate, tetramethylol methane triacrylate, ditrimethylol tetraacrylate, tetramethylol methane tetraacrylate, pentaerythritol tetraacrylate, Pentaerythritol hexaacrylate, and the like.

  Examples of the (meth) acrylic acid amide monomers include acrylamide, methacrylamide, N, N-dimethylacrylamide, methylenebisacrylamide, 2-acrylamido-2-methylpropanesulfonic acid, and the like.

Examples of the aromatic vinyl monomers include styrene, α-methylstyrene, vinyltoluene, 4-t-butylstyrene, chlorostyrene, vinylanisole, vinylnaphthalene, divinylbenzene, and the like.
Examples of the vinyl cyano compound monomers include acrylonitrile and methacrylonitrile.

  Examples of the vinyl monomers include vinyl acetate, vinylidene chloride, vinyl chloride, vinyl ether, vinyl ketone, vinyl pyrrolidone, vinyl sulfonic acid or salts thereof, vinyl trimethoxysilane, vinyl triethoxysilane, and the like.

  Examples of the allyl compound monomers include allyl sulfonic acid salt thereof, allylamine, allyl chloride, diallylamine, diallyldimethylammonium salt, and the like.

Examples of the olefin monomers include ethylene and propylene.
Examples of the diene monomers include butadiene and chloroprene.

  Examples of the oligomers having unsaturated carbon include styrene oligomers having methacryloyl groups, styrene-acrylonitrile oligomers having methacryloyl groups, methyl methacrylate oligomers having methacryloyl groups, dimethylsiloxane oligomers having methacryloyl groups, and polyesters having acryloyl groups. An oligomer etc. are mentioned.

  The water-dispersible resin has a strong alkalinity and strong acidity, and causes molecular breakage such as dispersion breakage and hydrolysis. Therefore, the pH is preferably 4 to 12, particularly from the viewpoint of miscibility with a water-dispersible colorant. As for pH, 6-11 are more preferable, and 7-9 are still more preferable.

The average particle size (D ₅₀ ) of the water-dispersible resin is related to the viscosity of the dispersion. When the composition is the same, the viscosity at the same solid content increases as the particle size decreases. The average particle diameter (D ₅₀ ) of the water-dispersible resin is preferably 50 nm or more so that the ink does not become excessively high in viscosity. Further, when the particle size is several tens of μm, it becomes larger than the nozzle opening of the ink jet head and cannot be used. If particles having a large particle diameter are present in the ink even if they are smaller than the nozzle opening, the discharge property is deteriorated. Therefore, the average particle diameter (D ₅₀ ) is preferably 200 nm or less, and more preferably 150 nm or less, in order not to inhibit the ink ejection properties.

The water-dispersible resin has a function of fixing the water-dispersed colorant on the paper surface, and is preferably formed into a film at room temperature to improve the fixability of the color material. Therefore, it is preferable that the minimum film-forming temperature (MFT) of the water-dispersible resin is 30 ° C. or less. Further, when the glass transition temperature of the water-dispersible resin is -40 ° C. or lower, the resin film becomes more viscous and the printed matter is tacky. Therefore, the water-dispersible resin has a glass transition temperature of −30 ° C. or higher. It is preferable.
The content of the water-dispersible resin in the inkjet ink is preferably 1 to 15% by mass, more preferably 2 to 7% by mass in terms of solid content.

  Here, the solid content of the inkjet ink can be measured, for example, by a method of separating only the water-dispersible colorant and the water-dispersible resin component from the inkjet ink. Further, when a pigment is used as the water-dispersible colorant, the ratio of the colorant to the water-dispersible resin can be measured by evaluating the mass reduction rate by thermal mass spectrometry. In addition, when the molecular structure of the water-dispersible colorant is clear, the solid content of the colorant can be quantified using NMR for pigments and dyes, and the inorganic pigment contained in the heavy metal atom, molecular skeleton, For the metal-containing organic pigment and the metal-containing dye, the solid content of the colorant can be quantified by using fluorescent X-ray analysis.

―Other ingredients―
The other components are not particularly limited and may be appropriately selected as necessary. For example, pH adjusters, antiseptic / antifungal agents, chelating reagents, rust preventives, antioxidants, ultraviolet absorbers, oxygen An absorber, a light stabilizer, etc. are mentioned.

  The pH adjuster is not particularly limited as long as the pH can be adjusted to 7 to 11 without adversely affecting the ink jet ink to be prepared, and can be appropriately selected according to the purpose. Examples include alcohol amines, alkali metal hydroxides, ammonium hydroxides, phosphonium hydroxides, alkali metal carbonates, and the like. If the pH is less than 7 or more than 11, the amount of the ink jet head or ink supply unit that melts out is large, and problems such as ink deterioration, leakage, and ejection failure may occur.

  Examples of the alcohol amines include diethanolamine, triethanolamine, 2-amino-2-ethyl-1,3-propanediol, and the like.

  Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, and potassium hydroxide.

  Examples of the ammonium hydroxide include ammonium hydroxide, quaternary ammonium hydroxide, quaternary phosphonium hydroxide, and the like.

  Examples of the alkali metal carbonate include lithium carbonate, sodium carbonate, and potassium carbonate.

  Examples of the antiseptic / antifungal agent include sodium dehydroacetate, sodium sorbate, 2-pyridinethiol-1-oxide sodium, sodium benzoate, sodium pentachlorophenol, and the like.

  Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uramil diacetate, and the like.

  Examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.

  Examples of the antioxidant include phenolic antioxidants (including hindered phenolic antioxidants), amine-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and the like.

  Examples of the ultraviolet absorber include a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, a salicylate ultraviolet absorber, a cyanoacrylate ultraviolet absorber, and a nickel complex ultraviolet absorber.

―Inkjet ink manufacturing process―
The ink-jet ink is prepared by dispersing or dissolving a water-dispersible colorant, a water-soluble organic solvent, a surfactant, a penetrating agent and water, and other components in an aqueous medium as necessary, and stirring as necessary. Produced by mixing. The stirring and mixing can be performed by, for example, a sand mill, a homogenizer, a ball mill, a paint shaker, an ultrasonic disperser, and the like. Can be done.

―Inkjet ink properties―
There is no restriction | limiting in particular as a physical property of the said inkjet ink, According to the objective, it can select suitably, For example, it is preferable that a viscosity, surface tension, etc. are the following ranges.

  The viscosity of the inkjet ink at 25 ° C. is preferably 5 to 20 mPa · s. By setting the ink viscosity to 5 mPa · s or more, the effect of improving the printing density and the character quality can be obtained. On the other hand, by suppressing the ink viscosity to 20 mPa · s or less, it is possible to ensure the discharge performance. Here, the said viscosity can be measured at 25 degreeC, for example using a viscometer (RE-550L, Toki Sangyo Co., Ltd. make).

  The static surface tension of the inkjet ink is preferably 20 to 35 mN / m at 25 ° C., more preferably 20 to 30 mN / m or less. When the ink jet ink has a static surface tension of 20 to 35 mN / m, it is highly effective in reducing bleeding by increasing the permeability, and the drying property on plain paper is improved. By being easily wetted with the treatment layer, the color developability is good and white spots are also improved. When the surface tension exceeds 35 mN / m, leveling of the ink on the recording material is difficult to occur and the drying time may be prolonged.

  There is no restriction | limiting in particular as coloring of the said inkjet ink, According to the objective, it can select suitably, Yellow, magenta, cyan, black etc. are mentioned. When recording is performed using an ink set in which two or more of these colorings are used in combination, a multicolor image can be formed. When recording is performed using an ink set in which all colors are combined, a full color image is formed. be able to.

  The ink-jet ink uses an piezoelectric head as a pressure generating means for pressurizing ink in the ink flow path as an ink-jet head, and deforms a diaphragm that forms the wall surface of the ink flow path to change the volume in the ink flow path. A so-called piezo type that discharges ink droplets (refer to Japanese Patent Laid-Open No. 2-51734), or a so-called thermal type that generates bubbles by heating ink in an ink flow path using a heating resistor ( JP, 61-59911, A), the diaphragm which forms the wall surface of an ink channel, and an electrode are arranged opposite, and a diaphragm is deformed by the electrostatic force generated between a diaphragm and an electrode, Mounted with any ink jet head such as an electrostatic type (see JP-A-6-71882) that discharges ink droplets by changing the volume of the ink flow path It can also be successfully used in that printer.

  The ink-jet ink can be used, for example, in a printer having a function of promoting printing and fixing by heating a recording medium and the ink-jet ink at 50 to 200 ° C. at the time of printing or before and after printing.

<Recording media>
As the recording medium, plain paper having no coating layer is preferably used, and plain paper having a sizing degree of 10 S or more and an air permeability of 5 to 50 S, which is generally used as a copy sheet, is preferred.

<Image forming method>
The image forming method of the present embodiment includes a processing step of applying the ink jet processing liquid of the present embodiment to a recording medium, and applying a stimulus to the ink jet ink and applying the processing liquid to the recording medium. An ink flying step of flying an inkjet ink to form an image.

―Processing process―
The treatment step is not particularly limited as long as a coating method for uniformly applying the inkjet treatment liquid onto the surface of the recording medium is used. Examples of such coating methods include blade coating, gravure coating, gravure offset coating, bar coating, roll coating, knife coating, air knife coating, comma coating, U comma coating, and 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.

  The treatment process is effective whether performed on a recording medium whose surface is sufficiently dried or on a recording medium being dried. In addition, a drying process can be provided as needed with respect to the recording medium which processed. In this case, the recording medium can be dried by a roll heater, a drum heater or hot air.

  The treatment liquid application step is performed as a pretreatment step performed before the following ink flying step, and the treatment liquid is preferably used as a pretreatment liquid, but the treatment liquid coating step is performed after the ink flying step. It may be a post-treatment step, and therefore the treatment liquid can be used as a post-treatment liquid. Furthermore, the treatment liquid can be used as a simultaneous treatment liquid, which is performed simultaneously with the ink flying process.

Wet adhesion amount to the recording medium of the inkjet treatment liquid in the treatment step ^is preferably intended to achieve the range of ^{0.1g / m 2 ~30.0g / m 2} , more preferably 0.2 it is a ~10.0g / ^{m 2.} If the adhesion amount is less than 0.1 g / m ² , the image quality (image density, saturation, color bleed, character bleeding and white spot) may hardly be improved, and the amount exceeds 30.0 g / m ² . The texture of plain paper may be impaired, and curling may occur.

―Ink flight process―
The ink flying process in the image forming method of the present embodiment is a process in which stimulation (energy) is applied to the ink-jet ink and the ink-jet ink is ejected onto the recording medium to form an image on the recording medium. is there. As the method for forming the image on the recording medium by flying the ink-jet ink on the recording medium in the ink flying step, any known ink-jet recording method can be applied. Examples of such a method include an ink jet recording method in which a head is scanned, and an ink jet recording method in which an image is recorded on a single sheet of recording medium by using a lined head.

  In the ink flying process, there is no particular limitation on the driving method of the recording head, which is an ink flying means, a piezoelectric element actuator using PZT, a method of applying thermal energy, an on demand using an actuator using electrostatic force, etc. A recording head can be used, and recording can be performed with a continuous ejection type charge control type head. In the method of applying thermal energy, it is difficult to freely control the ejection of droplets, and there is a tendency for variations in the image due to the type of recording media to be large. By adding to the above, these problems are solved, and stable high image quality can be obtained regardless of the type of recording medium.

-apparatus-
An apparatus for applying the inkjet processing liquid of the present embodiment to a recording medium and forming an image with the inkjet ink will be described with reference to a specific example of FIG. The apparatus shown in FIG. 1 is a type of recording apparatus that scans an inkjet recording head to form an image.
In the processing application and ink jet recording apparatus of FIG. 1, the recording medium (6) is fed out by the paper feed roller (7), and the processing liquid for inkjet (1) is recorded by the application roller (4) and the counter roller (5). Uniformly and thinly applied to the working medium (6). The inkjet processing liquid (1) is pumped up by the pumping roller (3), and is uniformly applied to the applying roller (4) by the film thickness control roller (2). The recording medium (6) to which the ink jet processing liquid (1) is applied is sent to a recording scanning unit having the ink jet recording head (20). The length of the paper path from the end portion of the processing liquid application operation (reference (A) portion in FIG. 1) to the recording scanning start portion (reference (B) portion in FIG. 1) is longer than the length in the feeding direction of the recording medium. Since it is set, the application of the treatment liquid can be completely terminated when the recording medium reaches the recording scanning start portion. In this case, since the application of the treatment liquid can be performed before the inkjet recording head (20) starts scanning for printing and the recording medium (6) is intermittently conveyed, the recording medium (6) Can be continuously applied at a constant conveyance speed, and uniform application without unevenness can be achieved. In the apparatus shown in FIG. 1, the recording medium (6) that needs to be processed is supplied from the lower cassette, and the recording medium (17) that is not needed or processed is supplied from the upper cassette. Therefore, it is convenient to provide a long recording medium conveyance path.

FIG. 2 shows another specific example of an apparatus for realizing the image recording method of the present embodiment. The apparatus example of FIG. 2 is also a type of recording apparatus that scans an inkjet recording head to form an image.
This is an example of a compact device configuration compared to the device of FIG. The recording medium (17) is fed out by the paper feed roller (7), and the inkjet processing liquid (1) is uniformly and thinly applied to the recording medium by the applying roller (4) and the counter roller (5). The inkjet processing liquid is pumped by the pumping roller (3), and is uniformly applied to the applying roller (4) by the film thickness control roller (2). The recording medium (17) passes through the recording scanning portion with the inkjet recording head (20) while being applied with the inkjet processing liquid (1), and is sent until the recording medium completes the application of the inkjet processing liquid. When the recording medium completes the application of the inkjet processing liquid, the recording medium head is returned again until the recording scanning start position is reached. Completion of application can be detected, for example, by providing a known recording medium detection means (not shown) in the vicinity of the outlet of the treatment liquid application apparatus.
This detection means is not necessarily required. Information on the length of the recording medium is input to the controller in advance, and the number of rotations of the motor is controlled, so that the feed amount of the outer periphery of the recording medium conveyance roller is determined. A system configuration corresponding to the length may be adopted.

The recording medium (17) to which the inkjet processing liquid (1) is applied is conveyed again to the recording scanning position before the inkjet processing liquid is dried and solidified. In this case, the ink jet recording head is used. In conformity with the scanning of (20), it is conveyed intermittently.
When returning the same path as the path that was sent when returning the recording medium, the trailing edge of the recording medium will reversely enter the processing liquid application device, causing problems such as uneven coating, dirt, and recording media jam. When returning the recording medium, the direction is switched by the recording medium guide (31). That is, when the recording medium is reversely fed after the treatment liquid (1) is applied to the recording medium (17), the recording medium guide (31) is placed at the position of the dotted line in the figure, and a known solenoid or motor is known. Move by means. Thereby, since the recording medium (17) is conveyed to the position of the recording medium return guide (34), it is possible to prevent the recording medium from being soiled or jammed.

The treatment process is preferably performed continuously at a constant linear velocity of 10 to 1000 mm / s.
For this reason, in this example of the apparatus, when a single-sheet recording medium is used and a single-sheet recording medium is viewed, after the step of applying the inkjet processing liquid to the recording medium is completed for the single-sheet The process of recording an image by the ink jet recording method is started.
In this way, in the apparatus, since the ink jet processing liquid application speed and the image recording speed do not coincide in most cases, the ink jet processing liquid is applied at the recording start portion and the recording end portion of the sheet. There is a difference in the time from when the image is recorded to when the image is recorded. Even when this difference becomes considerably large, it contains a large amount of a hydrophilic solvent having a boiling point higher than that of water and a low evaporation rate, and is close to the amount in equilibrium with the moisture in the air in the environment where the printer is used. Inkjet processing liquids prepared to a moisture ratio remarkably suppress water evaporation from the liquid, so at least a visual difference in image quality that occurs between the recording start part and the recording end part of the single-sheet recording medium is visually observed. It can be made below the level that can be observed with.

  As is apparent from the recording medium transporting process in this apparatus, after the ink jet processing liquid is applied, the recording medium to which the ink jet processing liquid is applied is used to form rollers, rollers, guides, and the like. In many cases, it is necessary to transport the recording medium by means of contact with the recording medium. In such a case, if the inkjet processing liquid applied to the recording medium is transferred to the recording medium conveyance member, the conveyance function may be impaired, dirt may accumulate, and image quality may deteriorate. Cause the problem of end. In order to prevent this problem, measures such as making the guide into corrugated plates, rolling rollers into a spur shape, or using a water-repellent material on the surface of the roller are alleviated from the device side. Can do.

  However, it is desirable that the inkjet processing liquid applied to the recording medium is absorbed into the recording medium as quickly as possible and apparently dried. In order to achieve this object, it is effective to set the surface tension of the inkjet processing liquid to 40 mN / m or less so that the liquid can quickly penetrate into the recording medium. “Dry solidification” after the application of the inkjet processing liquid does not mean that the inkjet processing liquid is absorbed into the recording medium and apparently becomes dry as described above. This means that the liquid compound in the treatment liquid evaporates and cannot be maintained in a liquid state and solidifies. By using the recording apparatus in which the inkjet processing liquid application apparatus and the image recording apparatus are combined as described above, the inkjet processing liquid according to the present embodiment is absorbed by the recording medium, and apparently. The ink jet recording can be performed in a state where the ink treatment liquid is not solidified even in a dry state, and the image quality is remarkably improved even when the amount of the ink treatment liquid applied is extremely small. It can be improved.

  In order to control the operation of the apparatus shown in FIGS. 1 and 2, when a print command is received from a host machine such as a personal computer, the inkjet processing liquid application / image forming apparatus performs head cleaning work and inkjet processing liquid coating work. Are started simultaneously, and the recording operation starts when all the preparations are completed. In this case, the image data may be transferred for one scan, for a plurality of scans, or for one page. Head cleaning and ejection check operations are not always necessary. In addition, there is no need to sequentially perform head cleaning, ejection check operation and image data processing / image data transfer, and start application of inkjet processing liquid, head cleaning, ejection check operation and image data processing / image data transfer simultaneously, etc. It is possible to process in parallel. In this way, the throughput of the printing and recording apparatus is almost reduced even when processing liquid application work is performed by performing parallel processing of ink jet processing liquid application, head cleaning, ejection check operation and image data processing / image data transfer. It is possible to record an image without dropping it.

  Examples of the present invention will be described below, but the present invention is not limited to these examples. In the following examples, the treatment liquid is used as the pretreatment liquid, and the coating of the pretreatment liquid is a pretreatment process performed before the ink flying process, and this pretreatment process is performed after the ink flying process, or It can be done at the same time.

(Preparation Example 1)
<Preparation of water-soluble polymer compound>
A monomer aqueous solution prepared at 2.0 mol / liter with the composition shown in the following table was subjected to nitrogen gas bubbling at room temperature for 20 minutes, and 0.01 to 0.20 mol% of potassium persulfate was added to all monomers And polymerized at 40 to 55 ° C. for 6 to 10 hours. Next, the obtained polymer aqueous solution gel was chopped and poured into a large amount of acetone, and then filtered to obtain a powder. Finally, vacuum drying was performed to obtain a white powder polymer.

表２中の略号などは下記の意味を表わす。
ＤＡＤＭ：ジアリルジメチルアンモニウムクロリド（第４級アンモニウム塩）
ＭＡ：マレイン酸
ＤＭ：Ｎ，Ｎ−ジメチルアミノエチルメタクリレート塩化メチル４級塩
ＭＡＡ：メタクリル酸
ＡＡ：アクリル酸
ＤＡＡＭ：ダイアセトンアクリルアミド
ＥＭＡ：エチレンメタクリレート
ＨＥＭＡ：ヒドロキシエチルメタクリレート
ＨＰＡ：ヒドロキシプロピルアクリレート
ＮＶＰ：Ｎ−ビニルピロリドン

Abbreviations in Table 2 have the following meanings.
DADM: diallyldimethylammonium chloride (quaternary ammonium salt)
MA: maleic acid DM: N, N-dimethylaminoethyl methacrylate methyl chloride quaternary salt MAA: methacrylic acid AA: acrylic acid DAAM: diacetone acrylamide EMA: ethylene methacrylate HEMA: hydroxyethyl methacrylate HPA: hydroxypropyl acrylate NVP: N- Vinylpyrrolidone

(Preparation Example 2)
<Preparation of treatment liquid>
Each treatment solution was manufactured according to the following procedure. First, the materials shown in Tables 3 and 4 below are mixed and stirred for 1 hour and mixed uniformly. This treatment liquid was subjected to pressure filtration with a polyvinylidene fluoride membrane filter having an average pore diameter of 5.0 μm to remove coarse particles and dust, thereby producing treatment liquid examples 1 to 19.

表３及び表４中の略号などは下記の意味を表わす。
＊ポリアクリル酸：日本触媒製 アクアリックＡＳ
＊ゼラチン：アルカリ処理品、等電点４．８、キシダ化学（株）製
＊エスレック ＫＷ−１：積水化学製、有効成分２０％、水溶性の変性ポリアセタール樹脂（ブチラール基、アセチル基、水酸基を有する水溶性高分子化合物）
＊ＰＶＡ：ポリビニルアルコール、日本酢ビ・ポバール製、ＪＦ−１７Ｌ
＊ポリビニルピロリドン：日本触媒製 Ｋ−３０ 純度９５％以上
＊ゾニールＦＳ−３００：（フッ素系界面活性剤）ポリオキシエチレンパーフロロアルキルエーテル （Ｄｕｐｏｎｔ社製、有効成分４０質量％）
＊サーフロンＳ−３８６：（フッ素系界面活性剤）パーフロロアルキル化合物 （ＡＧＣセイミケミカル製、有効成分９９％以上）
＊メガファックＦ−４４４：（フッ素系界面活性剤）パーフロロアルキル化合物 （ＤＩＣ製、有効成分９９％以上）
＊シリコーンＦＺ２１０５：（シリコーン系界面活性剤）シリコーン化合物（東レ・ダウコーニング製、有効成分９９％以上）
＊変性シリコーンＫＦ６４０：（シリコーン系界面活性剤）シリコーン化合物（信越化学工業製、有効成分９９％以上）
＊ソフタノールＥＰ−７０２５：（炭化水素系界面活性剤）ポリオキシアルキレンアルキルエーテル （日本触媒株式会社製、成分１００質量％）
＊Ｐｒｏｘｅｌ ＧＸＬ：１，２−ｂｅｎｚｉｓｏｔｈｉａｚｏｌｉｎ−３−ｏｎｅを主成分とした防カビ剤（アビシア社製、成分２０質量％、ジプロピレングリコール含有）

Abbreviations in Table 3 and Table 4 have the following meanings.
* Polyacrylic acid: Aquaric AS manufactured by Nippon Shokubai
* Gelatin: Alkali-treated product, isoelectric point 4.8, manufactured by Kishida Chemical Co., Ltd. * ESREC KW-1: Sekisui Chemical, active ingredient 20%, water-soluble modified polyacetal resin (butyral group, acetyl group, hydroxyl group) Water-soluble polymer compound)
* PVA: polyvinyl alcohol, manufactured by Nippon Vinegar / Poval, JF-17L
* Polyvinylpyrrolidone: Nippon Shokubai K-30 purity 95% or more * Zonyl FS-300: (Fluorosurfactant) Polyoxyethylene perfluoroalkyl ether (Dupont, 40 mass% active ingredient)
* Surflon S-386: (Fluorosurfactant) Perfluoroalkyl compound (AGC Seimi Chemical, active ingredient 99% or more)
* MegaFuck F-444: (Fluorosurfactant) Perfluoroalkyl compound (manufactured by DIC, 99% or more active ingredient)
* Silicone FZ2105: (Silicone-based surfactant) Silicone compound (Toray Dow Corning, active ingredient 99% or more)
* Modified silicone KF640: (silicone surfactant) silicone compound (manufactured by Shin-Etsu Chemical Co., Ltd., 99% or more active ingredient)
* Softanol EP-7025: (hydrocarbon surfactant) polyoxyalkylene alkyl ether (manufactured by Nippon Shokubai Co., Ltd., 100 mass% component)
* Proxel GXL: Antifungal agent based on 1,2-benzisothiazolin-3-one (Avicia, 20% by mass, containing dipropylene glycol)

(Preparation Example 3)
<Preparation of pigment-containing polymer fine particle dispersion>
-Preparation of polymer solution A-
After sufficiently replacing the inside of a 1 L flask equipped with a mechanical stirrer, thermometer, nitrogen gas inlet tube, reflux tube, and dropping funnel, 11.2 g of styrene, 2.8 g of acrylic acid, 12.0 g of lauryl methacrylate Then, 4.0 g of polyethylene glycol methacrylate, 4.0 g of styrene macromer, and 0.4 g of mercaptoethanol were mixed and heated to 65 ° C.
Next, 100.8 g of styrene, 25.2 g of acrylic acid, 108.0 g of lauryl methacrylate, 36.0 g of polyethylene glycol methacrylate, 60.0 g of hydroxylethyl methacrylate, 36.0 g of styrene macromer, 3.6 g of mercaptoethanol, azobismethylvalero A mixed solution of 2.4 g of nitrile and 18 g of methyl ethyl ketone was dropped into the flask over 2.5 hours. After dropping, a mixed solution of 0.8 g of azobismethylvaleronitrile and 18 g of methyl ethyl ketone was dropped into the flask over 0.5 hours.
After aging at 65 ° C. for 1 hour, 0.8 g of azobismethylvaleronitrile was added and further aging was performed for 1 hour. After completion of the reaction, 364 g of methyl ethyl ketone was added to the flask to obtain 800 g of a polymer solution A having a concentration of 50% by mass.

-Preparation of pigment-containing polymer fine particle dispersion-
28 g of the polymer solution A, 42 g of the coloring material shown in Table 5, 13.6 g of a 1 mol / L potassium hydroxide aqueous solution, 20 g of methyl ethyl ketone, and 13.6 g of ion-exchanged water were sufficiently stirred and then kneaded using a roll mill. did. The obtained paste was put into 200 g of pure water and stirred sufficiently, and then methyl ethyl ketone and water were distilled off using an evaporator, and this dispersion was further removed with polyvinylidene fluoride having an average pore size of 5.0 μm to remove coarse particles. By pressure filtration with a membrane filter, a pigment-containing polymer fine particle dispersion having a pigment content of 15% by mass and a solid content of 20% by mass was obtained. The average particle diameter (D ₅₀ ) of the polymer fine particles in the obtained pigment-containing polymer fine particle dispersion was measured and shown in Table 5. The average particle diameter (D ₅₀ ) was measured using a particle size distribution measuring device (Nikkiso Co., Ltd., Nanotrac UPA-EX150).

(Preparation Example 4)
<Preparation of inkjet ink>
Each inkjet ink was produced according to the following procedure. First, a water-soluble organic solvent (wetting agent), a penetrating agent, a surfactant, an antifungal agent, and water shown in Table 6 below are mixed and stirred uniformly for 1 hour. Further, depending on the liquid mixture, a water-dispersible resin is added and stirred for 1 hour, and a pigment dispersion, an antifoaming agent, and a pH adjuster are added and stirred for 1 hour. This dispersion was subjected to pressure filtration with a polyvinylidene fluoride membrane filter having an average pore size of 5.0 μm to remove coarse particles and dust, and ink jet inks of Ink Preparation Examples 1 to 8 were produced.

表６中の略号などは下記の意味を表わす。
＊マゼンタ顔料含有ポリマー微粒子分散液（表５）
＊シアン顔料含有ポリマー微粒子分散液（表５）
＊イエロー顔料含有ポリマー微粒子分散液（表５）
＊ブラック顔料含有ポリマー微粒子分散液（表５）
＊ＣＡＢ−Ｏ−ＪＥＴ ２６０：ＣＡＢＯＴ製、顔料固形分１１％、マゼンタ自己分散顔料
＊ＣＡＢ−Ｏ−ＪＥＴ ２５０：ＣＡＢＯＴ製、顔料固形分１１％、シアン自己分散顔料
＊ＣＡＢ−Ｏ−ＪＥＴ ２７０：ＣＡＢＯＴ製、顔料固形分１１％、イエロー自己分散顔料
＊ＣＡＢ−Ｏ−ＪＥＴ ３００：ＣＡＢＯＴ製、顔料固形分１５％、ブラック自己分散顔料
＊フッ素樹脂エマルジョン：旭硝子株式会社製、ルミフロンＦＥ４５００、固形分５２質量％、平均粒子径１３６ｎｍ、最低造膜温度（ＭＦＴ）＝２８℃
＊アクリル−シリコーン樹脂エマルジョン：昭和高分子株式会社製、ポリゾールＲＯＹ６３１２、固形分４０質量％、平均粒子径１７１ｎｍ、最低造膜温度（ＭＦＴ）＝２０℃
＊ＫＦ−６４０：ポリエーテル変性シリコーン系界面活性剤（信越化学工業株式会社製、成分１００質量％）
＊ソフタノールＥＰ−７０２５：ポリオキシアルキレンアルキルエーテル（日本触媒株式会社製、成分１００質量％）
＊Ｐｒｏｘｅｌ ＧＸＬ：１，２−ｂｅｎｚｉｓｏｔｈｉａｚｏｌｉｎ−３−ｏｎｅを主成分とした防カビ剤（アビシア社製、成分２０質量％、ジプロピレングリコール含有）
＊ＫＭ−７２Ｆ：自己乳化型シリコーン消泡剤（信越シリコーン株式会社製、成分１００質量％）

Abbreviations in Table 6 have the following meanings.
* Magenta pigment-containing polymer fine particle dispersion (Table 5)
* Cyan pigment-containing polymer fine particle dispersion (Table 5)
* Yellow pigment-containing polymer fine particle dispersion (Table 5)
* Black pigment-containing polymer fine particle dispersion (Table 5)
* CAB-O-JET 260: manufactured by CABOT, pigment solid content 11%, magenta self-dispersing pigment * CAB-O-JET 250: manufactured by CABOT, pigment solid content 11%, cyan self-dispersed pigment * CAB-O-JET 270: CABOT, pigment solid content 11%, yellow self-dispersion pigment * CAB-O-JET 300: CABOT, pigment solid content 15%, black self-dispersion pigment * Fluorine resin emulsion: Asahi Glass Co., Ltd., Lumiflon FE4500, solid content 52 Mass%, average particle diameter 136 nm, minimum film forming temperature (MFT) = 28 ° C.
* Acrylic-silicone resin emulsion: manufactured by Showa Polymer Co., Ltd., Polysol ROY6312, solid content 40% by mass, average particle diameter 171 nm, minimum film-forming temperature (MFT) = 20 ° C.
* KF-640: polyether-modified silicone surfactant (manufactured by Shin-Etsu Chemical Co., Ltd., component 100% by mass)
* Softanol EP-7025: polyoxyalkylene alkyl ether (manufactured by Nippon Shokubai Co., Ltd., component 100% by mass)
* Proxel GXL: Antifungal agent based on 1,2-benzisothiazolin-3-one (Avicia, 20% by mass, containing dipropylene glycol)
* KM-72F: Self-emulsifying silicone defoaming agent (manufactured by Shin-Etsu Silicone Co., Ltd., 100% by mass)

<Image formation>
On the recording medium, the treatment liquids of Preparation Examples 21 to 28 are coated and hot-air dried by the wire bar coating method, or are coated and naturally dried by the apparatus of FIG. 1 or FIG. After the treatment, in an environment adjusted to a temperature of 23 ± 0.5 ° C. and 50 ± 5% RH, an ink jet printer (IPSiO GX5000, manufactured by Ricoh Co., Ltd.) was used, and the piezo element was adjusted so that the amount of ink discharged was uniform. The drive voltage was varied, and settings were made so that the same amount of ink was applied to the recording medium.

実施例及び比較例で用いた記録用メディアの詳細を示す。
＊Ｍｙ＿ｐａｐｅｒ：（株）リコー製（上質紙）坪量６９．６ｇ／ｍ^２，サイズ度２３．２秒，透気度２１秒、

Details of the recording media used in Examples and Comparative Examples are shown.
* My_paper: Ricoh Co., Ltd. (quality paper) basis weight 69.6 g / m ² , size 23.2 seconds, air permeability 21 seconds,

<Image density>
A chart with 64 point characters “■” created by Microsoft Word 2000 was printed on a recording medium, and the “■” portion of the printed surface was measured with X-Rite 938, and judged according to the following evaluation criteria. The print mode was printed with “plain paper-standard fast” mode color matching off with the driver attached to the printer.

[Color specification for "■" part]
Black: (R) 0, (G) 0, (B) 0
Yellow: (R) 255, (G) 255, (B) 0
Magenta: (R) 255, (G) 0, (B) 255
Cyan: (R) 0, (G) 0, (B) 255

〔Evaluation criteria〕
A: Black: 1.3 or more,
Yellow: 0.85 or more
Magenta: 1.05 or more,
Cyan: 1.1 or more ○: Black: 1.2 or more and less than 1.3
Yellow: 0.8 or more and less than 0.85,
Magenta: 1.0 or more and less than 1.05,
Cyan: 1.0 or more and less than 1.1 Δ: Black: 1.15 or more and less than 1.2
Yellow: 0.75 or more and less than 0.8,
Magenta: 0.95 or more and less than 1.0,
Cyan: 0.95 or more and less than 1.0 ×: Black: less than 1.15
Yellow: less than 0.75,
Magenta: less than 0.95,
Cyan: Less than 0.95

<Image saturation>
Similar to the image density, a chart was printed on a recording medium, and the “■” portion of the printed surface was measured by X-Rite 938, and judged according to the following evaluation criteria. The print mode was printed with “plain paper-standard fast” mode color matching off with the driver attached to the printer.
The ratio of the saturation value of the standard color (Japan color ver. 2) to the measured saturation value (Yellow: 91.34, Magenta: 74.55, Cyan: 62.82) was calculated, and the following evaluation was performed. Judgment was made according to criteria.
〔Evaluation criteria〕
◎: 0.85 or more ○: 0.8 or more and less than 0.85 Δ: 0.75 or more and less than 0.8 ×: Less than 0.75

<Offset>
As with image density, a chart is printed on a recording medium, and a polyethylene cylindrical roller with a diameter of 40 mm is applied to the “■” portion of 40 mm length on the printing surface within 5 seconds after printing, and the strength is 5N. The portion where the ink was re-transferred from the cylindrical roller to the recording medium was measured by X-Rite 938, and judged according to the following evaluation criteria. The print mode was printed with “plain paper-standard clean” mode color matching off with a driver attached to the printer.
〔Evaluation criteria〕
◎: Less than 0.1 ○: 0.1 or more and less than 0.15,
Δ: 0.15 or more and less than 0.2,
X: 0.2 or more

<Fixability>
A chart with a 3cm x 3cm mono black solid image created by Microsoft Word 2000 was ejected onto a recording medium and dried at a temperature of 23 ± 1 ° C and a humidity of 50 ± 10% for 24 hours. -1 type clock meter attached with double-sided tape JIS L 0803 Cotton 3 was reciprocated 5 times so that it touches the printed part, and then the ink adhesion stain on the cotton cloth was measured with X-Rite 938. By subtracting, the density of the soiled part was determined according to the following evaluation criteria.
〔Evaluation criteria〕
◎: Less than 0.05 ○: 0.05 or more and less than 0.1 Δ: 0.1 or more and less than 0.2 ×: 0.2 or more

<Storage stability>
The treatment liquids of Preparation Examples 13 to 28 were prepared in the same manner as when image evaluation was performed, and left in a 70 ° C. constant temperature bath for 2 weeks, and the viscosity change rate of the treatment liquid before and after being left in the constant temperature bath was measured. did. The viscosity of the treatment liquid was measured in the same manner as the ink viscosity.
A: Less than 5% viscosity change B: Less than 10% viscosity change B: Less than 20% viscosity change X: More than 20 viscosity change

  The results are shown in Table 8, and the evaluation was performed for each color based on the evaluation criteria. Therefore, each image quality result describes the judgment with the highest evaluation in the result. In the case of the same number of evaluation judgments, the better one is described in the result. “Abrasion resistance” in the table is synonymous with fixability.

  The inkjet processing liquid of the present invention can be applied to various types of recording by the inkjet recording method, and is particularly preferably applied to, for example, an inkjet recording printer, a facsimile apparatus, a copying apparatus, a printer / fax / copier multifunction machine, and the like. be able to.

DESCRIPTION OF SYMBOLS 1 Inkjet processing liquid 2 Film thickness control roller 3 Pumping roller 4 Applying roller 5 Counter roller 6 Recording medium 7 Paper feed roller 8 Paper feed tray 10 Paper feed rollers 11-16 Recording media feed roller 17 Recording media 18 Paper feed roller 20 Recording head 21 Ink cartridge 22 Carriage shaft 23 Carriage 31 Recording media guides 32, 33 Recording media feed roller 34 Recording media return guide 35 Paper feed guide

JP 2001-199151 A JP 2009-262329 A WO 00/06390 Publication JP 2007-2122 A JP 2009-166387 A JP 2007-276387 A JP 2004-155868 A

Claims (4)

At least a water-soluble amphoteric polymeric compounds, fluorine surfactants or contain silicone surfactant, water-soluble amphoteric polymer compound, (A) the following general formula (I) in the indicated Ru cationic structural unit, (B) An anionic structural unit and (C) a nonionic structural unit, a processing liquid used for ink jet recording.

In the general formula (I), R1 represents a hydrogen atom or a methyl group, R2 represents a hydrogen atom, an alkyl group or an aralkyl group, R3 and R4 each represents an alkyl group or an aralkyl group, and n represents an integer of 1 to 4. And X- represents an anion such as a halogen ion or a methyl sulfate ion. R3 and R4 each represent an alkyl group or an aralkyl group, n represents an integer of 1 to 4, and X- represents an anion such as a halogen ion or a methyl sulfate ion. The treatment liquid according to claim 1, wherein the (B) anionic structural unit of the water-soluble amphoteric polymer compound is represented by the general formula (II).

In general formula (II), R5 represents a hydrogen atom or a methyl group, and M represents a hydrogen atom, an ammonium ion or an alkali metal ion. The treatment according to claim 1 or 2, wherein the (C) nonionic structural unit of the water-soluble amphoteric polymer compound is represented by the general formula (III), (IV), (V), or (VI). liquid.

In general formula (III), R6 represents a hydrogen atom or a methyl group.

In general formula (IV), R9 represents a hydrogen atom or a methyl group.

In general formula (V), R8 represents a hydrogen atom or a methyl group, and R9 represents an alkyl group or an aralkyl group.

In general formula (VI), R10, R11, and R12 represent a hydrogen atom or a methyl group, and n represents an integer of 1 to 3. Inkjet processing apparatus characterized by using the ink jet treatment liquid according to any one of claims 1 to 3.

Images