JP2008013605A - Inkjet recording ink composition, method for preparing lithographic printing plate and lithographic printing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an ink composition for inkjet recording excellent in fixability to ink receptors and redispersibility of the ink composition (colored organic fine particles) to a dispersion medium and provide a method for preparing a lithographic printing plate using the ink composition for inkjet recording and the lithographic printing plate prepared by the method. <P>SOLUTION: The ink composition for inkjet recording comprises (A) colored organic fine particles having ≥0.8 μm volume average particle size, (B) colored organic fine particles having ≤0.7 μm and (C) the dispersion medium. The method for preparing the lithographic printing plate using the ink composition for inkjet recording and the lithographic printing plate are provided. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an ink composition for inkjet recording, a method for preparing a lithographic printing plate using the ink composition, and a lithographic printing plate.

A conventional lithographic printing plate is obtained as follows.
A lithographic printing plate precursor having an oleophilic photosensitive resin layer (image recording layer) provided on a hydrophilic support is exposed through an original image such as a lith film, and the image recording layer in the image area remains. Then, the image recording layer in the non-image part is dissolved and removed with an alkaline developer or an organic solvent to remove the surface of the hydrophilic support, whereby a lithographic printing plate is obtained.
However, in the conventional plate making process of a lithographic printing plate precursor, a step of dissolving and removing the non-image area with a developer or the like is necessary after exposure. Disposal of waste liquids has become a major issue for the entire industry, and there is an increasing demand for solutions to the above issues.

In recent years, as an image recording method for forming an image on a recording medium such as paper based on an image data signal created by a computer or the like, an electrophotographic method, a sublimation type and a melt type thermal transfer method, an ink jet method, etc. have been used so far. Are known. Among these, the electrophotographic system requires a process of forming an electrostatic latent image on a photosensitive drum by charging and exposure, so that the system is complicated and the apparatus is expensive. The thermal transfer method is less expensive than the electrophotographic method, but has problems such as high running costs and waste materials due to the use of an ink ribbon. On the other hand, the ink jet method is an inexpensive apparatus and ejects ink only to a required image portion to form an image directly on a recording medium. Therefore, the ink can be used efficiently and the running cost is low. Furthermore, there is little noise and it is excellent as an image recording method. Therefore, it is a recording method that is rapidly spreading recently.
As such an ink jet recording method, a so-called electrostatic method in which ink is ejected using electrostatic attraction, or a so-called drop-on-demand method (piezoelectric) in which ink is ejected using the vibration pressure of a piezo element. Various methods such as a so-called bubble (thermal) jet method that ejects ink using pressure generated by forming and growing bubbles by high heat have been proposed. Can be obtained.
An ink jet recording type CTP is produced by directly forming an image on a support such as an aluminum plate or a plastic film by using the above ink jet recording method, and printing is performed by attaching it to a cylinder of a printing press without performing wet processing. Is known (see, for example, Patent Documents 1 to 6). CTP means that digitized print information is directly output as a printed matter.
Among such inks for ink jet recording type CTP, oil-based inks are generally used (Patent Documents 4 to 6).
JP 2002-86667 A JP 2001-88269 A JP 2001-150652 A Japanese Patent Laid-Open No. 10-298473 JP-A-10-259336 Japanese Patent Laid-Open No. 10-273614

  An object of the present invention is to provide a method for preparing a lithographic printing plate excellent in fixability to an ink receptor, redispersibility in a dispersion medium of an ink composition (colored organic fine particles), and excellent in printing durability, and obtained thereby. To provide a lithographic printing plate.

  As a result of extensive research, the inventor uses (A) colored organic fine particles having a volume average particle diameter of 0.8 μm or more and (B) colored organic fine particles having a volume average particle diameter of 0.7 μm or less in combination. Thus, the present inventors have found that the above problems can be solved, and have completed the present invention.

That is, the ink composition for inkjet recording of the present invention comprises (A) colored organic fine particles having a volume average particle size of 0.8 μm or more, (B) colored organic fine particles having a volume average particle size of 0.7 μm or less, ( C) A dispersion medium is contained.
The mass ratio of (A) colored organic fine particles having a volume average particle diameter of 0.8 μm or more and (B) colored organic fine particles having a volume average particle diameter of 0.7 μm or less is (A) :( B) = 1: 9 to 9: 1 is preferable.
Furthermore, at least one of (A) colored organic fine particles having a volume average particle size of 0.8 m or more and (B) colored organic fine particles having a volume average particle size of 0.7 μm or less has absorption in the visible region. It is preferable.
The ink composition for ink jet recording of the present invention is preferably used for an electrostatic ink jet recording system.

The lithographic printing plate production method of the present invention includes (a) a step of ejecting the ink composition for inkjet recording of the present invention onto an ink receptor, and (b) a step of fixing the ejected ink composition. It is characterized by including these.
Furthermore, the lithographic printing plate of the present invention is produced by the method for producing a lithographic printing plate of the present invention.

  According to the present invention, a method for preparing a lithographic printing plate excellent in fixability to an ink receptor, redispersibility in a dispersion medium of an ink composition (colored organic fine particles), and excellent in printing durability, and obtained thereby. A lithographic printing plate can be provided.

The present invention will be described below.
<Ink composition for inkjet recording>
First, the ink composition for ink jet recording of the present invention (hereinafter sometimes simply referred to as “ink composition”) will be described.
The ink composition of the present invention comprises (A) colored organic fine particles having a volume average particle size of 0.8 μm or more, (B) colored organic fine particles having a volume average particle size of 0.7 μm or less, and (C) a dispersion medium. It is characterized by containing.
In the present invention, by using colored organic fine particles, the dispersion stability is excellent and the image forming property is good. Further, the colored organic fine particles having a volume average particle diameter of 0.7 μm or less are closely packed between the colored organic fine particles having a volume average particle diameter of 0.8 μm or more. By binding between particles of 8 μm or more, fixability to a recording medium can be improved. On the other hand, the colored organic fine particles having a volume average particle size of 0.8 μm or more are fixed on the recording medium in such a manner that the colored organic fine particles having a volume average particle size of 0.7 μm or less are coated during fixing. It is considered that the uniformity of the film can be imparted and the strength of the image of the lithographic printing plate can be improved and the printing durability can be improved.
Hereinafter, components constituting the ink composition of the present invention will be described in detail.

The colored organic fine particles, which are the most important components in the present invention, will be described.
[(A) Colored organic fine particles having a volume average particle size of 0.8 μm or more]
The colored organic fine particles used in the present invention preferably have a volume average particle size in the range of 0.8 to 2.8 μm, from 0.83 to 2.5 μm, from the viewpoint of image formability and redispersibility. A range is more preferable.
[(B) Colored organic fine particles having a volume average particle size of 0.7 μm or less]
The colored organic fine particles used in the present invention preferably have a volume average particle size in the range of 0.32 to 0.70 μm, from 0.35 to 0.68 μm, from the viewpoint of image formability and redispersibility A range is more preferable.
In the present invention, the volume average particle diameter is an average particle diameter weighted by the particle volume, and in a set of particles, the sum of the diameter of each particle multiplied by the volume of the particle is divided by the total volume of the particle. Is. The volume average particle diameter can be determined by CAPA-500 (trade name, manufactured by Horiba, Ltd.).
The mass ratio of (A) to (B) is (A) :( B) = 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. When the volume average particle diameters are different from each other in this way, (A) and (B) are mixed, whereby the colored organic fine particles can be brought into close contact with the recording medium, and the fixability is improved. . In addition, since the large particles are fixed to the recording medium in such a state that the small particles cover the small particles, the uniformity of the film can be imparted, thereby improving the image area strength of the lithographic printing plate and increasing the printing durability. Obtainable.

[Colored organic fine particles]
As the colored organic fine particles in the present invention, those obtained by coloring organic fine particles produced by a polymerization granulation method or a wet dispersion method are preferably used as described below.
In addition, in this invention, coloring shall include what has absorption by the area | region of an ultraviolet-ray and infrared rays besides what has absorption in visible light. In addition, by controlling the particle size of the organic fine particles that are not colored, the organic fine particles that appear white by reflection of light are also included in the colored organic fine particles of the present invention.
When producing colored organic fine particles using this polymerization granulation method or wet dispersion method, the glass transition temperature (Tg) can be controlled by selecting the monomer to be used and adjusting the polymerization conditions. It is.
In the polymerization granulation method, the particle size can be controlled in the polymerization process of the organic fine particles. In the wet dispersion method, the particle size can be controlled when the polymer forming the particles is mechanically dispersed.
Comparing the polymerization granulation method and the wet dispersion method, the polymerization granulation method can easily control the region where the particle size of the particle is small, and the wet dispersion method can easily control the region where the particle size is large.
The colored organic fine particles obtained by these methods are appropriately mixed at a desired ratio and dispersed in a dispersion medium, whereby the ink composition of the present invention can be obtained.
In this polymerization granulation method and wet dispersion method, the organic fine particles are obtained in a dispersed state in a non-aqueous solvent. Therefore, the ink composition of the present invention can also be obtained by appropriately mixing the dispersion liquid in which the organic fine particles are dispersed at a desired ratio.

-Preparation of colored organic fine particles by polymerization granulation method-
First, a method for producing organic fine particles by the polymerization granulation method in the present invention will be described.
In the polymerization granulation method, at least one monofunctional monomer is polymerized in a non-aqueous solvent in the presence of a dispersion stabilizing resin (hereinafter sometimes referred to as a dispersant), thereby forming organic fine particles. It is a method of manufacturing. By coloring the organic fine particles produced by this method, the colored organic fine particles in the present invention can be obtained. The coloring in the present invention includes controlling the particle size of the organic fine particles when producing the organic fine particles, in addition to the case where the organic fine particles are colored, or when the organic fine particles are mixed with the colorant in advance. In this case, it is also possible to make it look white by reflection of light.
Hereinafter, components used in the polymerization granulation method will be described.

(Non-aqueous solvent)
Here, the non-aqueous solvent is a linear or branched aliphatic hydrocarbon, alicyclic hydrocarbon, or aromatic hydrocarbon, and halogen-substituted products (halogenated hydrocarbons) of these hydrocarbons. Can be mentioned. Specifically, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, Isopar E, Isopar G, Isopar H, Isopar L (Isopar; Exxon product name), Shellsol 70, Shellzol 71 (Shellsol; Shell Oil product name), Amsco OMS, Amsco 460 solvent (Amsco; Spirits product name), methylene dichloride, chloroform, carbon tetrachloride , Dichloroethane, methyl chloroform and the like can be used alone or in combination.

  In addition to the above hydrocarbon compounds and their halogen-substituted products, the following non-hydrocarbon compounds can also be mixed and used. Examples of compounds that can be mixed include alcohols (for example, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, and fluorinated alcohol), ketones (for example, acetone, methyl ethyl ketone, cyclohexanone, and the like), and carboxylic acid esters (for example, acetic acid). Methyl, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, etc.), ethers (eg, diethyl ether, dipropyl ether, tetrahydrofuran, dioxane, etc.), halogenated hydrocarbons (eg, methylene dichloride, Chloroform, carbon tetrachloride, dichloroethane, methyl chloroform and the like).

  In the present invention, in order to omit steps such as substitution with a dispersion medium, which will be described later, which is a preferred component constituting the ink composition, the same non-aqueous solvent as the dispersion medium is usually used in the granulation stage of the organic fine particles. It is preferable to use it.

  The amount of these nonaqueous solvents used is preferably in the range of 80 to 0.01% by mass with respect to the total mass of the mixed solution used in the synthesis, that is, the solid content in the mixed solution is 20%. It is preferable to be in the range of ˜99.99%. Moreover, it is more preferable that it is the range of 70-0.1 mass%, and it is still more preferable that it is the range of 60-1 mass%.

(Monofunctional monomer)
The monofunctional monomer in the present invention (hereinafter sometimes simply referred to as “monomer”) is soluble in a non-aqueous solvent, but is insolubilized by polymerization. If it is, it will not specifically limit. Specific examples include monomers represented by the following general formula (I).

In the general formula ^(I), T 1 _{is, -COO -, - OCO -,} - CH 2 OCO -, - CH 2 COO -, - O -, - CONHCOO -, - CONHOCO -, - SO 2 -, - CON (W ¹ ) —, —SO ₂ N (W ¹ ) —, or a phenylene group (hereinafter, the phenylene group is referred to as “—Ph—”. The phenylene group includes 1,2-, 1,3- And 1,4-phenylene group). Here, W ¹ represents a hydrogen atom or an optionally substituted aliphatic group having 1 to 20 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-bromoethyl group, 2 -Cyanoethyl group, 2-hydroxyethyl group, benzyl group, chlorobenzyl group, methylbenzyl group, methoxybenzyl group, phenethyl group, 3-phenylpropyl group, dimethylbenzyl group, fluorobenzyl group, 2-methoxyethyl group, 3- Methoxypropyl group and the like).

D ¹ represents a hydrogen atom, a halogen atom, or an optionally substituted aliphatic group having 1 to 20 carbon atoms. Examples of the aliphatic group include a methyl group, an ethyl group, a propyl group, a butyl group, a 2-chloroethyl group, a 2,2-dichloroethyl group, a 2,2,2-trifluoroethyl group, a 2-bromoethyl group, 2-glycidylethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 2,3-dihydroxypropyl group, 2-hydroxy-3-chloropropyl group, 2-cyanoethyl group, 3-cyanopropyl group, 2-nitroethyl Group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2-ethoxyethyl group, N, N-dimethylaminoethyl group, N, N-diethylaminoethyl group, trimethoxysilylpropyl group, 3-bromopropyl group, 4-hydroxybutyl group, 2-furfurylethyl group, 2-thienylethyl group, 2-pyridylethyl group, 2-mol Linoethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2-phosphoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, 2-carboxyamidoethyl group, 3-sulfoamidopropyl group 2-N-methylcarboxamidoethyl group, cyclopentyl group, chlorocyclohexyl group, dichlorohexyl group and the like.

d ¹ and d ² may be the same or different from each other, and are a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, —COO—Z ¹ , or a hydrocarbon group having 1 to 20 carbon atoms. -COO-Z ¹ through the formula [wherein Z ¹ represents a hydrocarbon group having 1 to 22 carbon atoms].

Specific monofunctional monomers include, for example, vinyl esters or allyl esters of aliphatic carboxylic acids having 1 to 20 carbon atoms (acetic acid, propionic acid, butyric acid, monochloroacetic acid, trifluoropropionic acid, etc.); C1-C10 optionally substituted alkyl esters or amides of unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid (alkyl groups include, for example, methyl group, ethyl Group, propyl group, butyl group, 2-chloroethyl group, 2-bromoethyl group, 2-fluoroethyl group, trifluoroethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-nitroethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2-benzenesulfonylethyl group, 2- (N, N-dimethylamino) ethyl 2- (N, N-diethylamino) ethyl group, 2-carboxyethyl group, 2-phosphoethyl group, 4-carboxybutyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3-chloropropyl group, 2-hydroxy- 3-chloropropyl group, 2-furfurylethyl group, 2-pyridinylethyl group, 2-thienylethyl group, trimethoxysilylpropyl group, 2-carboxyamidoethyl group, etc.); styrene derivatives (for example, styrene, vinyltoluene, α -Methylstyrene, vinylnaphthalene, chlorostyrene, dichlorostyrene, bromostyrene, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, chloromethylstyrene, hydroxymethylstyrene, methoxymethylstyrene, N, N-dimethylaminomethylstyrene, vinylbenzenecarbo Xylamide, vinylbenzenesulfoamide, etc.); unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid; cyclic anhydrides of maleic acid and itaconic acid; acrylonitrile; methacrylonitrile; Heterocyclic compounds containing a heavy bond group (specifically, compounds described in, for example, “Polymer Data Handbook -Basic Edition” edited by Polymer Society of Japan, p 175-184, Kaoru Baifu (1986)), for example, N- Vinyl pyridine, N-vinyl imidazole, N-vinyl pyrrolidone, vinyl thiophene, vinyl tetrahydrofuran, vinyl oxazoline, vinyl thiazole, N-vinyl morpholine, etc.).
These monofunctional monomers may be used alone or in combination of two or more.

The amount of these monofunctional monomers used is preferably 10% by mass or more, more preferably 15% by mass or more, based on the total solid content in the mixed solution used in the synthesis. More preferably, it is 20% by mass or more. In addition, the upper limit of the amount of the (b) monofunctional monomer used is preferably 99% by mass or less and 95% by mass or less from the viewpoint of monodispersity and dispersion stability of the organic fine particles obtained. It is more preferable.
When the content of the monofunctional monomer is less than 10% by mass, the organic fine particles are hardly precipitated from the non-aqueous solvent, so that the synthesis becomes difficult. Moreover, monodispersity also falls.

(Dispersion stabilizing resin (dispersant))
The dispersion stabilizing resin (dispersant) used when granulating the organic fine particles in the present invention will be described.
This dispersant is used for polymerizing a monofunctional monomer in a non-aqueous solvent and making a polymer insoluble in the non-aqueous solvent into a stable resin dispersion.
In the present invention, the dispersion stabilizing resin (dispersant) is preferably used in an amount of 1 to 50% by mass, more preferably 5 to 40%, based on the monofunctional monomer used for the synthesis of organic fine particles. % By mass.

Examples of the dispersant in the present invention include a random copolymer, comb-type copolymer, star-type copolymer, partially cross-linked copolymer, and cross-linkable group-containing copolymer that are soluble in the above-described dispersion medium. Conventionally known dispersion stabilizers can be used.
Hereinafter, the dispersant suitable for the present invention will be described.

(Random copolymer)
Specific examples of the random copolymer in the present invention include alkyl chains and alkenyl chains having 6 to 32 carbon atoms (these aliphatic groups contain a substituent such as a halogen atom, a hydroxy group, an amino group, and an alkoxy group). Or a heterocarbon atom such as an oxygen atom, a sulfur atom, or a nitrogen atom, and a carbon-carbon bond in the main chain may be interposed therebetween)) of acrylic acid, methacrylic acid, or crotonic acid Esters; higher fatty acid vinyls; alkyl vinyl ethers; olefins such as butadiene, isoprene and diisoprene; polymers obtained by polymerizing monomers, or a combination of two or more of these monomers The copolymer which consists of is mentioned.
Furthermore, the following monomers can be used at a ratio of a monomer that forms a polymer that is soluble in a non-aqueous solvent as described above and a copolymer that can be obtained in a non-aqueous solvent. A copolymer obtained by copolymerizing at least one of the above can also be used.

  Monomers that can be copolymerized with the above monomers include, for example, vinyl acetate, allyl acetate, acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, methyl, ethyl, or propyl esters; styrene derivatives (For example, styrene, vinyltoluene, α-methylstyrene, etc.); unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid or anhydrides thereof; hydroxyethyl methacrylate, hydroxyethyl acrylate, Hydroxy group, amino group, amide group, cyano group, sulfonic acid group, carboxyl group, such as diethylaminoethyl methacrylate, N-vinylpyrrolidone, acrylamide, acrylonitrile, 2-chloroethyl methacrylate, 2,2,2-trifluoroethyl methacrylate ,Halo Monomers containing emissions atoms, various polar groups of the heterocycle and the like; and the like.

  Furthermore, natural resins such as alkyd resins, alkyd resins modified with various fatty acids, linseed oil, and modified polyurethane resins can be used as the random copolymer in the present invention.

The weight average molecular weight of the random copolymer in the present invention is preferably in the range of 3,000 to 200,000, and more preferably in the range of 5,000 to 150,000.
When the molecular weight is less than 3,000, the dispersibility is lowered, and thus redispersibility and storage stability may be lowered. On the other hand, if the molecular weight is larger than 200,000, (a) the solubility in a non-aqueous solvent is lowered, and in this case also, the dispersibility is lowered, and redispersibility and storage stability may be lowered.

(Comb-type copolymer)
The comb-type copolymer in the present invention has the following structure, and has at least one macromonomer (MM) having a weight average molecular weight of 1 × 10 ^{3 to} 5 × 10 ⁴ as a copolymerization component. It is a copolymer.
First, this macromonomer will be described in detail. The macromonomer used to obtain the comb-type copolymer is a polymer represented by the following general formula (III) only at one terminal of the polymer main chain having a repeating unit represented by the following general formula (II). Has a structure formed by bonding a double bond group.

In the general formula (II), a ¹ and a ² may be the same or different from each other, and are a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, etc.), a cyano group, or a carbon number of 1 to 4. -COO-Z ¹ through a hydrocarbon group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.), -COO-Z ¹ or a hydrocarbon group. Here, examples of the hydrocarbon group in the —COO—Z ¹ group via a hydrocarbon group include a methylene group, an ethylene group, and a propylene group. Z ¹ is preferably a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, an alicyclic group, or an aryl group.
These groups may further have a substituent if possible.

In the general formula (II), X ⁰ represents —COO—, —OCO—, —CH ₂ OCO—, —CH ₂ COC—, —O—, —SO ₂ —, —CO—, —CONR ¹¹ —. , —SO ₂ NR ¹¹ —, or —Ph (phenylene group) —. Here, as R ¹¹ , a hydrogen atom, an alkyl group having 1 to 22 carbon atoms which may be substituted (for example, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group, decyl group) Group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group Etc.), an optionally substituted alkenyl group having 4 to 18 carbon atoms (for example, 2-methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1- A pentenyl group, a 1-hexenyl group, a 2-hexenyl group, a 4-methyl-2-hexenyl group, etc.), which may be substituted with 7 to 12 carbon atoms. Aralkyl groups (for example, benzyl, phenethyl, 3-phenylpropyl, naphthylmethyl, 2-naphthylethyl, chlorobenzyl, bromobenzyl, methylbenzyl, ethylbenzyl, methoxybenzyl, dimethylbenzyl) Group, dimethoxybenzyl group, etc.), C5-C8 optionally substituted alicyclic group (e.g., cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.), C6-C12 Aromatic groups which may be substituted (for example, phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl Group, decyloxyphenyl group, chlorophenyl group, dic A rophenyl group, a bromophenyl group, a cyanophenyl group, an acetylphenyl group, a methoxycarbonylphenyl group, an ethoxycarbonylphenyl group, a butoxycarbonylphenyl group, an acetamidophenyl group, a propioamidophenyl group, a dodecylylamidophenyl group). It is done.

Incidentally, X ⁰ is the case of -Ph- (phenylene group), on the ring may have a substituent. Examples of the substituent that can be introduced include a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, chloromethyl group, methoxymethyl group, etc.), alkoxy group (For example, a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, etc.) etc. are mentioned.

In the general formula (II), Q ¹ represents an alkyl group having 10 to 22 carbon atoms or an alkenyl group having 10 to 22 carbon atoms.

  Next, the polymerizable double bond group represented by the following general formula (III) will be described.

In the general formula (III), b ¹ and b ² may be the same as or different from each other, and represent the same contents as a ¹ and a ² in the general formula (II).
Moreover, ^{X 1} is represents the same content as ^{X 0} in formula (II), preferably, -COO -, - OCO -, - O -, - CH 2 OCO-, or _-CH 2 COO- in is there.

Specific examples of the polymerizable double bond group represented by the general formula (III) include CH ₂ ═CH—COO—, CH ₂ ═C (CH ₃ ) —COO—, and CH ₃ —CH═CH—COO—. _{, CH 2 = C (CH 2} COOCH 3) -COO-, CH 2 = C (CH 2 COOH) -COO-, CH 2 = CH-CONH-, CH 2 = C (CH 3) -CONH-, CH 3 _{-CH = CH-CONH-, CH 2} = CH-OCO-, CH 2 = CH-CH 2 -OCO-, CH 2 = CH-O-, CH 2 = C (COOH) -CH 2 -COO-, CH _{2 = C (COOCH 3) -CH} 2 -COO-, CH 2 = CH-Ph- , and the like.

Such a polymerizable double bond group may be directly bonded to one end of the polymer main chain represented by the general formula (II) or may be bonded via a linking group. Examples of the linking group used herein include carbon-carbon bonds (single bonds or double bonds), carbon-heteroatom bonds (hetero atoms include oxygen atoms, sulfur atoms, nitrogen atoms, silicon atoms, etc.), hetero It is composed of any combination of atom-heteroatom bond atomic groups.
Specific examples of the linking group include —CR ⁷ R ⁸ — [wherein R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group. , A hydroxyl group, an alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.) and the like. ], - (CH = CH) - , - C 5 H 10 - ( i.e., cyclohexylene group), - Ph (phenylene) -, - O -, - S -, - CO -, - NR 5 -, - COO—, —SO ₂ —, —CONR ⁹ —, —SO ₂ NR ⁹ —, —NHCOO—, —NHCONH—, —SiR ⁹ R ¹⁰ — [wherein R ⁹ and R ¹⁰ are each independently hydrogen An atom and a hydrocarbon group such as an aliphatic group represented by D ¹ in the general formula (I) are shown. ] Or a linking group formed by combining two or more of these linking groups.

  The macromonomer as described above can be produced by a conventionally known synthesis method. For example, 1) a method of introducing a polymerizable double bond group by reacting various reagents at the end of a living polymer obtained by anionic polymerization or cationic polymerization, and 2) a carboxyl group, hydroxy group in the molecule A polymerization initiator containing a reactive group such as an amino group or an amino group and / or a chain transfer agent, and reacting an oligomer of a terminal reactive group bond obtained by radical polymerization with various reagents to form a polymerizable duplex. Incorporating a linking group by a radical polymerization method, 3) By introducing a polymerizable double bond group into an oligomer obtained by a polyaddition or polycondensation reaction in the same manner as the radical polymerization method, by a polyaddition condensation method Methods and the like.

  More specifically, P.I. Dryfuss & R.D. P. Quirk, Encycl. Polym. Sci. Eng. 7,551 (1987), P.F. Rempp & E.M. Franta, Adv. Polym. Sci. 58, 1 (1984), V.S. Percec, Appl. Polym. Sci. , 285, 95 (1984), R.A. Asami, M .; TakaRi, Makvamol. Chem. Suppl. , 12, 163 (1985), p. Rempp et al, Makvamol. Chem. Suppl. 8, 3 (1984), Yusuke Kawakami “Chemical Industry” 38, 56 (1987), Yuya Yamashita “Polymer” 31, 988 (1982), Shiro Kobayashi “Polymer” 30, 625 (1981), Satoshi Higashimura Nobu "Japan Adhesion Association Journal" 18,536 (1982), Ito Koichi "Polymer Processing" 35,262 (1986), Toki Shiro, Tsuda Takashi "Functional Materials" 1987, No. It can be synthesized according to the methods described in the reviews such as 10, 5 and the literatures and patents cited therein.

  Examples of the polymerization initiator containing a reactive group in the molecule used in the method 2) include 4,4′-azobis (4-cyanovaleric acid), 4,4′-azobis (4-cyano). Valeric acid chloride), 2,2′-azobis (2-cyanopropanol), 2,2′-azobis (2-cyanopentanol), 2,2′-azobis [2- (5-hydroxy-3,4, 5,6-tetrahydropyrimidin-2-yl) propane], 2,2′-azobis (2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propioamide), 2,2 ′ -Azobis {2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propioamide}, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propioamide], 2,2 -Azobis (2-amidinopropane), 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) -propioamide], 2,2'-azobis [2- (5-methyl-2-imidazoline- 2-yl) propane], 2,2′-azobis [2- (4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl) propane], 2,2′-azobis [2 -(3,4,5,6-tetrahydropyrimidin-2-yl) propane], 2,2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane}, 2,2′-azobis [N- (2-hydroxyethyl) -2-methyl-propionamidine], 2,2′-azobis [N- (4-aminophenyl) -2-methylpropionamidine] and the like Compound And the like.

  Examples of the chain transfer agent containing a reactive group in the molecule include, for example, the reactive group or a mercapto compound containing a substituent that can be derived from the reactive group (for example, thioglycolic acid, thiomalic acid, thiosalicylic acid). 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercapto Ethanol, 3-mercapto-1,2-propanediol, 1-mer Pt-2-propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol, etc.), or the reactive group or the reactive group Examples thereof include iodinated alkyl compounds containing substituents (for example, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, and the like). Preferably, a mercapto compound is used.

  The amount of these polymerization initiators or chain transfer agents used is 0.1 to 10% by mass, preferably 0.5 to 100% by mass with respect to 100% by mass of the total monomers used in radical polymerization. 5% by mass.

The weight average molecular weight of the macromonomer (MM) thus obtained is in the range of 1 × 10 ^{3 to} 5 × 10 ⁴ in order to control the molecular weight of the comb-type copolymer to the range described later. In short, it is preferably 3 × 10 ^{3 to} 3 × 10 ⁴ .

The comb-type copolymer in the present invention preferably contains 10 to 90% by mass of the macromonomer having the structure as described above, and more preferably contains 20 to 80% by mass.
By including the macromonomer within this range, the average particle diameter of the organic fine particles obtained by polymerization granulation is evenly arranged, and the redispersibility of the obtained organic fine particles is remarkably improved.

The weight average molecular weight of the comb-type copolymer in the present invention is preferably in the range of 5 × 10 ^{3 to} 5 × 10 ⁵ from the viewpoint of storage stability, redispersibility, and dispersion stability, and 1 × 10 ^4. More preferably, it is in the range of ˜2 × 10 ⁵ .

(Star copolymer)
The star-type copolymer in the present invention is a weight average molecular weight of 1 × 10 ⁴ to 1 formed by binding at least three polymer chains of an AB type block copolymer to a central organic molecule. × 10 ⁶ copolymer.

  Here, the order of arrangement of the block A and the block B in the polymer chain is formed by bonding to an organic molecule at one end opposite to the end bonded to the block B of the polymer main chain of the block A. The structure is schematically shown as the following formula (IV).

  In the above formula (IV), X represents an organic molecule, [A] represents block A, [B] represents block B, and [A]-[B] represents a polymer chain.

  The weight composition ratio of each copolymerization of the block A and the block B in the star copolymer in the present invention is 1 to 50/99 to 50, preferably 5 to 40/95 to 60.

Hereinafter, first, the block A constituting the polymer chain of the AB type block copolymer bonded to the organic molecule will be described.
The block A includes a phosphono group, a carboxyl group, a sulfo group, a hydroxyl group, a formyl group, an amino group, —P (═O) (OH) R ¹ group, —CONR ³ R ⁴ group, —SO ₂ NR ³ R ⁴ , And a polymerization component containing at least one polar group selected from the group consisting of cyclic acid anhydride-containing groups, and / or at least one polymerization component corresponding to the aforementioned (b) monofunctional monomer. Consists of containing.

That is, the block A is composed of a polymerization component corresponding to the monofunctional monomer (b) and / or a polymerization component containing the specific polar group described above.
Among the specific polar groups, in the -P (= O) (OH) R ¹ group, R ¹ represents a -R ² group or a -OR ² group, and R ² represents a hydrocarbon group having 1 to 10 carbon atoms. . The hydrocarbon group for R ² is preferably an aliphatic group having 1 to 8 carbon atoms which may be substituted (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, butenyl group, pentenyl group). Group, hexenyl group, 2-chloroethyl group, 2-cyanoethyl group, cyclopentyl group, cyclohexyl group, benzyl group, phenethyl group, chlorobenzyl group, bromobenzyl group), and optionally substituted aromatic group (for example, Phenyl group, tolyl group, xylyl group, mesityl group, chlorophenyl group, bromophenyl group, methoxyphenyl group, cyanophenyl group, etc.).

Further, in the specific polar group, in the —CONR ³ R ⁴ group and —SO ₂ NR ³ R ⁴ group, R ³ and R ⁴ are each independently a hydrogen atom or a hydrocarbon group (having 1 to 10 carbon atoms, preferably Represents an optionally substituted hydrocarbon group having 1 to 8 carbon atoms. Specific examples of the hydrocarbon group represented by R ³ and R ⁴ include the same hydrocarbon groups as those represented by R ² .

The cyclic anhydride-containing group in the specific polar group is a group containing at least one cyclic acid anhydride, and examples of the cyclic acid anhydride contained include aliphatic dicarboxylic acid anhydrides and aromatic dicarboxylic acid anhydrides. Is mentioned.
Examples of aliphatic dicarboxylic acid anhydrides include succinic acid anhydride, glutaconic acid anhydride, maleic acid anhydride, cyclopentane-1,2-dicarboxylic acid anhydride, cyclohexane-1,2-dicarboxylic acid anhydride, 2 , 3-bicyclo [2,2,2] octane dicarboxylic acid anhydride, etc., and these aliphatic dicarboxylic acid anhydrides include, for example, halogen atoms such as chlorine atom and bromine atom, methyl group, ethyl group, butyl Group and an alkyl group such as a hexyl group.
Examples of the aromatic dicarboxylic acid anhydride include phthalic acid anhydride, naphthalene-dicarboxylic acid anhydride, pyridine-dicarboxylic acid anhydride, thiophene-dicarboxylic acid anhydride, etc., and these aromatic dicarboxylic acid anhydrides. The product is, for example, a halogen atom such as a chlorine atom or a bromine atom, an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, a hydroxyl group, a cyano group, a nitro group, an alkoxycarbonyl group ( A methoxy group, an ethoxy group, and the like).

Further, in the specific polar group, the amino group represents —NH ₂ , —NHR ⁵ , or —NR ⁵ R ⁶ . R ⁵ and R ⁶ each independently represents a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms. More preferably, it represents a hydrocarbon group having 1 to 7 carbon atoms, and specifically, the same hydrocarbon groups as those represented by R ² can be mentioned.

As the hydrocarbon group represented by R ² , R ³ , R ⁴ , R ⁵ and R ⁶ , still more preferably, an optionally substituted alkyl group having 1 to 4 carbon atoms, which may be substituted. Examples thereof include a benzyl group or an optionally substituted phenyl group.

  The monomer corresponding to the polymerization component containing the specific polar group described above may be any monofunctional monomer containing at least one specific polar group. For example, it is described in “Polymer Data Handbook, Fundamentals” edited by the Society of Polymer Science, Japan, published in 1986. Specifically, acrylic acid, α and / or β-substituted acrylic acid (for example, α-acetoxy, α-acetoxymethyl, α- (2-amino) methyl, α-chloro, α-bromo, α-fluoro, α-tributylsilyl, α-cyano, β-chloro, β-bromo, α-chloro-β-methoxy, α, β-dichloro, etc.), methacrylic acid, itaconic acid, Itaconic acid half esters, itaconic acid half amides, crotonic acid, 2-alkenyl carboxylic acids (eg, 2-pentenoic acid, 2-methyl-2-hexenoic acid, 2-octenoic acid, 4-methyl-2-hexenoic acid) 4-ethyl-2-octenoic acid), maleic acid, maleic acid half esters, maleic acid half amides, vinyl benzene carboxylic acid, vinyl benzene sulfonic acid, vinyl sulfonic acid, vinyl phosphonic acid, Vinyl or carboxylic acids half esters derivatives of allyl group and in the substituent of the ester derivatives or amide derivatives of these carboxylic acids or sulfonic acids, compounds, and the like containing the polar group.

Specific examples of such compounds include the following. However, in the following examples [(P-1) to (P-20)], “e” represents —H, —CH ₃ , —Cl, —Br, —CN, or —CH ₂ COOCH ₃ . , “F” represents —H or —CH ₃ , “n” represents an integer of 2 to 10, “m” represents an integer of 1 to 10, and “p” represents an integer of 1 to 4. Represents. X ³ represents —COOH, —O—P (═O) (OH) ₂ , —SO ₃ H, —OH, —NR ^a R ^b , —CHO, or —O—P (═O) (OH ) Represents ^Ra . Here, R ^<a> , R ^<b > represents a C1-C4 alkyl group each independently. Furthermore, ^{X 4} represents -COOH, or -OH.

The specific polar group-containing polymerization component contained in the block A is preferably 1 to 30% by mass, more preferably 1 to 15% by mass in 100% by mass of the star copolymer.
Further, when there is no specific polar group-containing polymerization component in the block A, the polymer component corresponding to the functional monomer (A) is preferably 5 to 50% by mass in 100% by mass of the dispersant. More preferably, it is 10-40 mass%.

Next, the block B constituting the polymer chain of the AB type block copolymer bonded to the organic molecule will be described.
The block B is constituted by containing at least one polymer component composed of a repeating unit represented by the following general formula (V).

In the general formula (V), X ¹ preferably represents —COO—, —OCO—, or —O—.
Y ¹ preferably represents an alkyl group or an alkenyl group having 10 or more carbon atoms, and these may be linear or branched. Specific examples include decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, eicosanyl, docosanyl, decenyl, dodecenyl, tridecenyl, hexadecenyl, octadecenyl, linolel, and the like. .
a ¹ and a ² may be the same or different from each other, and are preferably a hydrogen atom, a halogen atom (eg, a chlorine atom or a bromine atom), a cyano group, or an alkyl group having 1 to 3 carbon atoms (eg, a methyl group). , Ethyl group, propyl group, etc.), -COO-Z ¹ , or -CH ₂ COO-Z ¹ [Z ¹ is a hydrogen atom or an optionally substituted hydrocarbon group having 22 or less carbon atoms (eg, alkyl Group, alkenyl group, aralkyl group, alicyclic group, aryl group and the like.

Specifically, the Z ¹ is preferably a hydrogen atom, or a preferred hydrocarbon atom having an alkyl group having 1 to 22 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group). , Heptyl, hexyl, octyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, eicosanyl, docosanyl, 2-chloroethyl, 2-bromoethyl, 2- A cyanoethyl group, a 2-methoxycarbonylethyl group, a 2-methoxyethyl group, a 3-bromopropyl group, etc.), an optionally substituted alkenyl group having 4 to 18 carbon atoms (for example, a 2-methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl Group, 4-methyl-2-hexenyl group, decenyl group, dodecenyl group, tridecenyl group, hexadecenyl group, octadecenyl group, linolel group, etc.), C 7-12 optionally substituted aralkyl group (for example, benzyl) Group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.) , An optionally substituted alicyclic group having 5 to 8 carbon atoms (for example, cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.), and optionally substituted 6 to 12 carbon atoms. Aromatic groups (eg, phenyl, naphthyl, tolyl, xylyl, propylphenyl) , Butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl, decyloxyphenyl, chlorophenyl, dichlorophenyl, bromophenyl, cyanophenyl, acetylphenyl, methoxycarbonyl Phenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodeciloylamidophenyl group, etc.).

In the block B, two or more repeating units represented by the general formula (V) may be used in combination.
Furthermore, in the block B, you may contain another repeating unit as a copolymerization component with the repeating unit shown by general formula (V). The other copolymer component may be any compound as long as it is composed of a monomer copolymerizable with a monomer corresponding to the repeating unit of the general formula (V). The other copolymerization component is used in a range not exceeding 20% by mass with respect to 100% by mass of block B at most. When it exceeds 20 mass%, the dispersibility of the organic fine particles in the present invention is deteriorated.

  The polymerization component represented by the general formula (V) contained in the block B is preferably 50 to 99% by mass, more preferably 60 to 95% by mass in 100% by mass of the star copolymer.

  In the present invention, the star copolymer is less than the above-described predetermined abundance ratio (that is, the abundance ratio of the block A and the block B and the abundance ratio of the polymerization component represented by the general formula (V) contained in the block B). In some cases, the redispersion stability of the organic fine particles may be lowered. On the other hand, when it exceeds a predetermined abundance ratio, the monodispersity of the particle distribution of the organic fine particles is lowered.

  The organic molecules that bind at least three polymer chains of the AB type block copolymer as described above are not particularly limited as long as the weight average molecular weight is 1,000 or less. . For example, the following trivalent or higher valent hydrocarbon residues may be mentioned. However, specific examples of the organic molecule according to the present invention are not limited thereto.

Here, in the above example, r ³ ~r ⁶ each represent a hydrogen atom or a hydrocarbon group. However, at least one of r ³ and r ⁴ and at least one of r ⁵ and r ⁶ are each linked to a polymer chain of an AB type block copolymer.

The organic molecule is composed of the above hydrocarbon residues alone or in any combination thereof. For ^{combinations, -O -, - S -,} - N (r 9) -, - COO -, - CON (r 9) -, - SO 2 -, or ^{_{-SO 2 N (r 9) -}} ( wherein And r ⁹ represents a hydrogen atom or a hydrocarbon group), —NHCOO—, —NHCONH—, an oxygen atom, a sulfur atom, a heteroatom-containing heterocycle containing a nitrogen atom (eg, a thiophene ring, a pyridine ring, a pyran ring) , An imidazole ring, a benzimidazole ring, a furan ring, a piperidine ring, a pyrazine ring, a pyrrole ring, a piperazine ring, and the like). In addition, these bond units may be used alone or in combination.

  Examples of organic molecules other than those mentioned above include those composed of combinations of the following linking groups and the above binding units. However, specific examples of the organic molecule according to the present invention are not limited thereto.

  The star-type dispersant in the present invention can be synthesized by utilizing a conventionally known method for synthesizing a star-type polymer containing a polar group and having a polymerizable double bond group. For example, one of them is a polymerization reaction using carbanion as an initiator. Specifically, M.M. Morton, T.M. E. Helminiak et al "J. Polym. Sci." 57, 471 (1962), B.R. Gordon III, M, Blumenthal, J.M. E. Loftus et al “Polym. Bull.” 11, 349 (1984), R.A. B. Bates, W. A. It can be synthesized according to the method described in Beavers et al "J. Org. Chem." 44, 3800 (1979).

  However, when the above reaction is used, the above-mentioned “specific polar group” is polymerized by using it as a protected functional group, and then the protecting group is removed. Such protection of a specific polar group with a protecting group and removal of the protecting group (deprotection reaction) can be easily performed using conventionally known knowledge. For example, various references are described in the above cited references describing synthesis methods, and further, Yoshio Iwakura and Keisuke Kurita “Reactive Polymers” (Kodansha) (1977), T.A. W. Green "Protective Groups in Organic Synthesis" (JohnWiley & Sons, 1981), J. MoI. F. W. A method described in detail in a review such as “McOmic” Protective Groups in Organic Chemistry ”(Plenum Press, 1973) can be selected as appropriate.

  In addition, as another synthesis method, a monomer that does not protect the above-mentioned “specific functional group” is used, and a compound containing a dithiocarbamate group and / or a compound containing a xanthate group is used as an initiator. It can also be synthesized by carrying out a polymerization reaction under light irradiation. For example, Takayuki Otsu “Polymer” 37, 248 (1988), Shunichi Sasamori, Ryuichi Otsu “polym. Rep. Jap.” 37, 3508 (1988), JP-A 64-11, JP-A 64-26619 No., Toshinyuki et al. “Polymer Preprints, Japan” 36 (6), 1511 (1987), M. et al. Niwa, N .; It can be synthesized according to the synthesis method described in Higashi et al "J. Macromol. Sci. Chem." A24 (5), 567 (1987) and the like.

The weight average molecular weight (Mw) of the star-type dispersant in the present invention is 1 × 10 ⁴ to 1 × 10 ⁶ , preferably 2 × 10 ⁴ to ⁶ from the viewpoints of storage stability, redispersibility, and dispersion stability. 5 × 10 ⁵ .

(Partially crosslinked copolymer)
The partially crosslinked copolymer in the present invention is a copolymer containing at least one repeating unit represented by the following general formula (VI), wherein a part of the polymer main chain is crosslinked, a) A resin that is soluble in a non-aqueous solvent.

In the general formula (VI), ^{X 1} is _{preferably, -COO -, - OCO -,} - CH 2 OCO -, - CH 2 COO- or an -O-, more preferably, -COO -, - CH ₂ COO— or —O— is represented.
Y ¹ preferably represents an alkyl group, an alkenyl group or an aralkyl group, which may be substituted with 10 to 22. The substituent that may be introduced to, for example, a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, ^{etc.), - O-Z 2,} -COO-Z 2, or ^{--OCO-Z 2} (wherein, Z ² represents an alkyl group having 6 to 22 carbon atoms, and examples thereof include a hexyl group, an octyl group, a decyl group, a dodecyl group, a hexadecyl group, and an octadecyl group. More preferably, ^{Y 1} represents an alkyl or alkenyl group having 10 to 22 carbon atoms. Specific examples include a decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, docosanyl group, eicosanyl group, decenyl group, dodecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group and the like.

b ¹ and b ² may be the same as or different from each other, and preferably a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms, —COO—Z ¹ , or a carbon number. ^{-COO-Z 1 [Z 1} here represents a hydrocarbon group having 1 to 22 carbon atoms] via a hydrocarbon group of 1 to 8 representing the.
Specifically, a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, an alkyl group having 1 to 3 carbon atoms, —COO—Z ³ , or —CH ₂ COO—Z ³ (Here, Z ³ represents an aliphatic group having 1 to 22 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group) Hexadecyl group, octadecyl group, docosanyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, decenyl group, dodecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group, etc. ¹ may have the same substituent as that represented by ¹ ).

The partially crosslinked copolymer of the present invention contains at least one monomer corresponding to the repeating unit represented by the general formula (VI), and a polymer in which a part of the polymer main chain is crosslinked. It is.
Thus, as a method for introducing a crosslinked structure into the polymer main chain, a conventionally known method can be used. That is, 1) a polymerization method in which a polyfunctional monomer is allowed to coexist in a monomer polymerization reaction, or 2) a polymer containing a functional group that undergoes a crosslinking reaction is crosslinked by a polymer reaction. Is the method.

The partially crosslinked copolymer of the present invention has a simple production method (for example, it requires a long reaction, the reaction is not quantitative, and impurities are mixed in by using a reaction accelerator, etc.). From the above, the method 1) is effective.
In the method 1), preferably, a monomer having two or more polymerizable functional groups is polymerized together with a monomer corresponding to the repeating unit represented by the general formula (VI) to form a polymer chain. This is a method of cross-linking.

Specific examples of polymerizable functional groups include CH ₂ ═CH—, CH ₂ ═CH—CH ₂ —, CH ₂ ═CH—CO—O—, CH ₂ ═C (CH ₃ ) —CO—O—, CH. _{3 -CH = CH-CO-O-} , CH 2 = CH-CONH-, CH 2 = C (CH 3) -CONH-, CH 2 = C (CH 3) -CONHCOO-, CH 2 = C (CH 3 _{) -CONHCONH-, CH 3 -CH = CH} -CONH-, CH 2 = CH-O-CO-, CH 2 = C (CH 3) -O-CO-, CH 2 = CH-CH 2 -O-CO _{-, CH 2 = CH-NHCO-} , CH 2 = CH-CH 2 -NHCO-, CH 2 = CH-SO 2 -, CH 2 = CH-CO-, CH 2 = CH-O-, CH 2 = CH -S- and the like, but two or more of the above polymerizable functional groups To the monomer may be any of these polymerizable functional groups those same or different monomer having two or more things.

  Specific examples of the monomer having two or more polymerizable functional groups include, for example, styrene derivatives such as divinylbenzene and trivinylbenzene; polyhydric alcohols (for example, monomers having the same polymerizable functional group) , Ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol # 200, # 400, # 600, 1,3-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol ), Or methacrylic acid, acrylic acid or crotonic acid esters, vinyl ethers or allyl ethers of polyhydroxyphenols (eg hydroquinone, resorcin, catechol and derivatives thereof); dibasic acids ( For example, vinyl esters, allyl esters, vinyl amides or allyl amides of malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, itaconic acid, etc .; polyamines (for example, ethylenediamine, 1, 3-propylenediamine, 1,4-butylenediamine, etc.) and a carboxylic acid having a vinyl group (for example, methacrylic acid, acrylic acid, crotonic acid, allyl acid, etc.);

Further, as monomers having different polymerizable functional groups, for example, carboxylic acids having a vinyl group [for example, methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloyl propionic acid, acryloyl propionic acid, itaconyl yl acetic acid, itaconi Roylpropionic acid, a reactant of a carboxylic anhydride and an alcohol or amine (eg, allyloxycarbonylpropionic acid, allyloxycarbonylacetic acid, 2-allyloxycarbonylbenzoic acid, allylaminocarbonylpropionic acid, etc.) The ester derivative or amide derivative contained, specifically, vinyl methacrylate, vinyl acrylate, vinyl itaconate, allyl methacrylate, allyl acrylate, allyl itaconate, methacryloyl vinyl acetate, methacrylate Vinyl ilpropionate, vinyl methacryloyl propionate, allyl methacryloyl propionate, vinyloxycarbonylmethyl ester methacrylate, vinyloxycarbonylmethyloxycarbonyl ethylene ester, N-allylacrylamide, N-acrylmethacrylamide, N-allylitaconic acid Amide, methacryloylpropionic acid allylamide, etc .;
Condensates of amino alcohols (for example, aminoethanol, 1-aminopropanol, 1-aminobutanol, 1-aminohexanol, 2-aminobutanol, etc.) and a carboxylic acid containing a vinyl group;

  The monomer having two or more polymerizable functional groups described above is polymerized using 10% by mass or less, preferably 8% by mass or less of the total monomer, and (a) a partial crosslinkable soluble in a non-aqueous solvent. A mold copolymer is formed.

  Specifically, the partially crosslinked dispersant used in the present invention includes a monomer corresponding to the repeating unit represented by the general formula (VI), which is a known method, and the polyfunctional monomer described above. A method of polymerizing with a polymerization initiator (for example, azobis compound, peroxide, etc.) in the presence of at least coexist is simple and preferable. The polymerization initiator used here is 0.1 to 15% by mass, preferably 0.5 to 10% by mass, based on 100% by mass of the total monomers.

The weight average molecular weight of the partially crosslinked dispersant of the present invention is 5 × from the viewpoint of adjusting the particle size distribution of organic fine particles obtained by polymerization granulation and (a) solubility in a non-aqueous medium. The range of 10 ³ to 1 × 10 ⁶ is preferable, and the range of 1 × 10 ⁴ to 2 × 10 ⁵ is more preferable.

(Crosslinkable group-containing copolymer)
The crosslinkable group-containing copolymer in the present invention is, as shown by the following general formula (VII), a copolymer component (X component) that is soluble in at least a non-aqueous solvent, and a polymer structure at the end of the side chain. It is a random copolymer containing the organic fine particle obtained by a particle | grain and the copolymerization component (Y component) which has a polymerizable double bond group copolymerizable. For this reason, this crosslinkable group-containing copolymer is a resin that is soluble in a non-aqueous solvent.
Here, X component in general formula (VII) may be comprised from the single copolymerization component, and may be comprised from 2 or more types of copolymerization components. The same applies to the Y component.

In the general formula (VII), R ¹ represents an alkyl group or alkenyl group having 10 to 32 carbon atoms, and these may be linear or branched. Specifically, decyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, octadecyl group, eicosanyl group, docosanyl group, decenyl group, dodecenyl group, tridecenyl group, hexadecenyl group, octadecenyl group, eicosenyl group, A dococenyl group, a linoleyl group, etc. are mentioned.
b ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (methyl group, ethyl group, propyl group, butyl group), preferably a hydrogen atom or a methyl group.
X ¹ and X ² are each independently a single bond, —COO—, —CONH—, —CON (E ² ) — [wherein E ² is preferably an aliphatic group having 1 to 22 carbon atoms (aliphatic group). Represents an alkyl group, an alkenyl group, an aralkyl group, or the like. _{], -OCO -, - CH 2 OCO-} , or an -O-. More preferably -COO -, - CONH- or -CON ^{(E 2)} - represents a.

In the general formula (VII), d ¹ , d ² , e ¹ , and e ² each independently represent a hydrogen atom, a halogen atom, a cyano group, or an alkyl group. Specific examples of the alkyl group include specific examples of the aliphatic group which may be substituted having 1 to 20 carbon atoms and represented by D ¹ in the general formula (I).

W represents a linking group containing a carbon atom and / or a hetero atom. Here, examples of the hetero atom include an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom.
Examples of the linking group include those composed of any combination of carbon-carbon bond (single bond or double bond), carbon-heteroatom bond, heteroatom-heteroatom bond atomic group, heterocyclic group and the like. Specific examples include the divalent groups listed below.

In the above divalent group examples, r ^{1 to} r ⁴ are each a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, a hydroxyl group, or an alkyl group (for example, Methyl group, ethyl group, propyl group, etc.).
r ^{5 to} r ⁷ each independently represent a hydrogen atom, an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, or the like).
r ^{8 to} r ⁹ are each independently a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, benzyl group, phenethyl group, Phenyl group, tolyl group, etc.), or -Or ¹⁰ (r ¹⁰ represents the same content as the hydrocarbon group in r ⁸ ).

  Heterocyclic groups that can form W include heterocycles containing heteroatoms such as oxygen, sulfur, and nitrogen (eg, thiophene ring, pyridine ring, pyran ring, imidazole ring, benzimidazole ring, furan ring, piperidine Ring, pyrazine ring, pyrrole ring, piperazine ring, etc.).

Further, the connecting chain composed of [—X ¹ —W—X ² —] in the Y component of the general formula (VII) is preferably composed of 8 or more atoms in total. As the number of atoms of the connecting main chain in this connecting chain, for example, when X ¹ represents —COO— or —CONH—, an oxo group (═O group) or a hydrogen atom is not included as the number of atoms. Carbon atoms, ether type oxygen atoms, and nitrogen atoms constituting the chain are included as the number of atoms. Therefore, -COO- and -CONH- are counted as 2 atoms.

Although the specific example [(Y-1)-(Y-12)] about the copolymerization component (Y component) which has a polymerizable double bond group is shown below, this invention is not limited to these. .
In the following formula, each symbol represents the following contents.

The crosslinkable group-containing copolymer in the present invention can be easily synthesized by a conventionally known synthesis method. That is, as a method for introducing a copolymer component (Y component) having a polymerizable double bond group into a resin, a “specific reactive group” (for example, —OH, —COOH, —SO ₃ ) is used in advance. H, —NH ₂ , —SH, —PO ₃ H ₂ , —NCO, —NCS, —COCl, —SO ₂ Cl, an epoxy group, and the like) are used as the X component in the general formula (VII). A method of introducing a polymerizable reactive group by a polymer reaction after reacting a reactive reagent containing a polymerizable double bond group after the polymerization reaction with the corresponding monomer is mentioned.
Specifically, P.I. Dryfuss & R.D. P. Quirk, Encycl. Polym. Sci, Eng. 7.551 (1987), Yoshiki Nakajo, Yuya Yamashita “Dyes and Drugs”, 30.232 (1985), Akira Ueda, Susumu Nagai, “Chemical and Industrial”, 60.57 (1986), P.A. F. Rempp & E.M. Franta, Advances in Polymer Science, 58.1 (1984), Koichi Ito “Polymer Processing”, 35.262 (1986), V. A polymerizable double bond group can be introduced according to a method described in a review article such as Percec, Applied Polymer Science, 285.97 (1984) and literatures cited therein.

  In addition, as another method, a bifunctional monomer having different copolymerization reactivity in a radical polymerization reaction is used, and a polymerization reaction is performed together with a monomer corresponding to the X component. Examples thereof include a method described in JP-A No. 60-185962 for synthesizing a copolymer represented by the formula (VII).

  In the resin represented by the general formula (VII), the ratio of the X component and the Y component suppresses gelation of the reaction mixture during the polymerization granulation reaction or the coarsening of the organic fine particles to be generated, and From the viewpoint of dispersion stability and redispersibility of the fine particles, the polymerization ratio is 60/40 to 99/1, and preferably 85/15 to 98/2 by weight.

In the crosslinkable group-containing copolymer used in the present invention, other repeating units may be contained as a copolymerization component together with each repeating unit represented by the general formula (VII). The other copolymer component may be any compound as long as it is composed of a monomer copolymerizable with a monomer corresponding to each repeating unit of the general formula (VII).
The other copolymerization component is used in a range not exceeding 20% by mass with respect to 100% by mass of all the polymerization components. When it exceeds 20 mass%, the dispersibility of the organic fine particles in the present invention is deteriorated.

The weight average molecular weight (Mw) of the crosslinkable group-containing copolymer of the present invention is 5 × 10 ³ to 10 × 10 ⁶ from the viewpoint of storage stability, redispersibility, and dispersion stability, and preferably 1 ×. 10 ^{4 to} 2 × 10 ⁵ .

(Chain transfer agent)
When granulating organic fine particles in the polymerization granulation method, it is preferable to use a chain transfer agent in order to control the molecular weight and to give a specific function.
The chain transfer agent used here can be used without particular limitation as long as it is a substance that moves the active site of the reaction by a chain transfer reaction in the polymerization reaction.
Moreover, a functional group can be introduce | transduced into the terminal of the polymer chain which forms particle | grains by synthesize | combining specific particles using a chain transfer agent. For example, by using mercaptopropionic acid, a COOH group can be introduced at the end of the polymer chain forming the particle. By introducing such a group, the adhesion between the specific particles and the recording medium is improved. Further, for example, by using n-dodecyl mercaptan, when a long-chain alkyl group is introduced at the end of the polymer chain forming the particle, the redispersibility is improved.

  Specific examples of the chain transfer agent that can be used in the present invention include halogen compounds such as carbon tetrachloride and carbon tetrabromide, alcohols such as isopropyl alcohol and isobutyl alcohol, 2-methyl-1-butene, 2, 4 and the like. -Olefins such as diphenyl-4-methyl-1-pentene, ethanethiol, butanethiol, octanethiol, dodecanethiol, stearyl mercaptan, n-dodecyl mercaptan, nonyl mercaptan, mercaptoethanol, mercaptopropanol, methyl mercaptopropionate, mercapto Ethyl propionate, mercaptoacetic acid, mercaptopropionic acid, ethyl disulfide, sec-butyl disulfide, 2-hydroxyethyl disulfide, thiosalicylic acid, thiophenol, thiocresol, benzylme Captan, cyclopentyl mercaptan, cyclohexyl mercaptan, o- toluene thiol, m- toluene thiol, p- toluene thiol, but sulfur-containing compounds such as phenethyl mercaptan and the like, but is not limited thereto.

  More preferably, ethanethiol, butanethiol, octanethiol, dodecanethiol, stearyl mercaptan, n-dodecyl mercaptan, nonyl mercaptan, mercaptoethanol, mercaptopropanol, methyl mercaptopropionate, ethyl mercaptopropionate, mercaptoacetic acid, mercaptopropionic acid, Ethyl disulfide, sec-butyl disulfide, 2-hydroxyethyl disulfide, thiosalicylic acid, thiophenol, thiocresol, benzyl mercaptan, cyclopentyl mercaptan, cyclohexyl mercaptan, o-toluenethiol, m-toluenethiol, p-toluenethiol, especially Preferred chain transfer agents include ethanethiol, butanethiol, octanethiol, dodeca Thiol, stearyl mercaptan, n-dodecyl mercaptan, nonyl mercaptan, mercaptoethanol, mercaptopropanol, methyl mercaptopropionate, ethyl mercaptopropionate, mercaptoacetic acid, mercaptopropionic acid, ethyl disulfide, sec-butyl disulfide, 2-hydroxyethyl disulfide, etc. Is mentioned.

Such a chain transfer agent may use only 1 type and may use 2 or more types together.
The addition amount at the time of synthesis is preferably in the range of 10 ⁻³ to 30% by mass, more preferably in the range of 10 ⁻² to 15% by mass with respect to the monomer, and 5 × 10 ^−5. More preferably, it is in the range of ^{2 to} 12% by mass.

(Polymerization granulation method)
In order to produce organic fine particles by the polymerization granulation method, generally, a dispersant as described above and a monofunctional monomer are mixed with benzoyl peroxide, azobisisobutyronitrile, butyl in a non-aqueous solvent. Heat polymerization may be performed in the presence of a polymerization initiator such as lithium.
Specifically, (i) a method in which a polymerization initiator is added to a mixed solution of a dispersant and a monomer, and (ii) a monomer is dropped together with the polymerization initiator into a solution in which the dispersant is dissolved. Or (iii) a method of adding the remaining monomer together with the polymerization initiator into a mixed solution containing the whole amount of the dispersing agent and a part of the monomer, and (iv) in a non-aqueous solvent. There is a method of adding a mixed solution of a dispersant and a monomer together with a polymerization initiator, and any method can be used for production.
Moreover, when manufacturing specific particle | grains using a chain transfer agent, the method of adding a polymerization initiator in the mixed solution of a dispersing agent, a monomer, and a chain transfer agent can be used, for example.

The amount of the polymerization initiator is preferably from 0.1 to 20% by mass, more preferably from 0.5 to 10% by mass, based on the total amount of monomers.
Moreover, superposition | polymerization temperature is about 40-180 degreeC, Preferably it is 50-120 degreeC. The reaction time is preferably 3 to 15 hours.

  When a polar solvent such as the alcohols, ketones, ethers, esters described above is used in combination with the non-aqueous solvent used for the reaction, or unreacted monomers remaining to be polymerized and granulated remain. In this case, it is preferable to remove the solvent or monomer by heating to a boiling point or higher or removing it by distillation under reduced pressure.

  In such a polymerization granulation method, the particle size, Tg, and molecular weight of the organic fine particles are controlled by factors such as the type and concentration of the monofunctional monomer used, the type and concentration of the dispersant, non-water Addition of compounds involved in the polymerization reaction such as the type and concentration of the solvent, the polymerization initiator and the like, and adjustment of the addition amount, and further the reaction temperature, etc. Organic fine particles satisfying Tg and molecular weight can be obtained. Among these, a chain transfer agent is preferably used in order to easily adjust the molecular weight and to add a further function to the obtained organic fine particles.

-Preparation of colored organic fine particles by wet dispersion method-
The wet dispersion method in the present invention is a method in which a polymer constituting organic fine particles is finely divided (dispersed) using a dispersant in a non-aqueous solvent. The colored organic fine particles in the present invention can be obtained by using a colorant in combination with the fine particles (dispersing).
Hereinafter, components used in the wet dispersion method will be described.

(Polymer constituting organic fine particles)
Specific examples of polymers constituting the organic fine particles include rosins, rosin-modified phenolic resins, alkyd resins, (meth) acrylic polymers, polyurethanes, polyesters, polyamides, polyethylenes, polybutadienes, polystyrenes, polyvinyl acetates, polyvinyls. Examples include acetal-modified products of alcohol and polycarbonate.
Of these, from the viewpoint of ease of particle formation, the weight average molecular weight is in the range of 2,000 to 1,000,000, and the polydispersity (weight average molecular weight / number average molecular weight) is 1.0 to Polymers that are within the range of 5.0 are preferred. Furthermore, from the viewpoint of ease of fixing, a polymer having a softening point or glass transition point in the range of 25 ° C. to 150 ° C. is preferable.

  In the present invention, the polymer suitably used is a polymer containing at least one of the structural units represented by the following general formulas (1) to (4).

In the general formula (1), X ¹¹ represents an oxygen atom or —N (R ¹³ ) —. R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents a hydrocarbon group having 1 to 30 carbon atoms, and R ¹³ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
In the general formula (2), R ²¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
In the general formulas (3) and (4), R ³¹ , R ³² and R ⁴¹ each represent a divalent hydrocarbon group having 1 to 20 carbon atoms.
The hydrocarbon group of R ¹² , R ²¹ , R ³¹ , R ³² , and R ⁴¹ may contain an ether bond, an amino group, a hydroxy group, or a halogen substituent.

The polymer containing the structural unit represented by the general formula (1) can be obtained by radical polymerization of a corresponding radical polymerizable monomer by a known method.
Examples of the radical polymerizable monomer used include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, and (meth) acrylic. Octyl acid, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, (meth) (Meth) acrylic acid esters such as 2-hydroxyethyl acrylate, N-methyl (meth) acrylamide, N-propyl (meth) acrylamide, N-phenyl (meth) acrylamide, N, N-dimethyl (meth) Examples include (meth) acrylamides such as acrylamide.

The polymer containing the structural unit represented by the general formula (2) can be obtained by radical polymerization of a corresponding radical polymerizable monomer by a known method.
Examples of the radical polymerizable monomer used include ethylene, propylene, butadiene, styrene, and 4-methylstyrene.

The polymer containing the structural unit represented by the general formula (3) can be obtained by dehydrating condensation of a corresponding dicarboxylic acid or acid anhydride and a diol by a known method.
Examples of the dicarboxylic acid used include succinic anhydride, adipic acid, sebacic acid, isophthalic acid, terephthalic acid, 1,4-phenylenediacetic acid, diglycolic acid and the like.
Examples of the diol used include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, and 2-butene- Examples include 1,4-diol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-benzenedimethanol, and diethylene glycol.

The polymer containing the structural unit represented by the general formula (4) is known to dehydrate and condense a carboxylic acid having a corresponding hydroxy group, or a cyclic ester of a carboxylic acid having a corresponding hydroxy group. It can be obtained by ring-opening polymerization according to the method.
Examples of the carboxylic acid having a hydroxy group or a cyclic ester thereof include 6-hydroxyhexanoic acid, 11-hydroxyundecanoic acid, hydroxybenzoic acid, and ε-caprolactone.

The polymer containing at least one of the structural units represented by the general formulas (1) to (4) may be a homopolymer of the structural units represented by the general formulas (1) to (4). It may be a copolymer (copolymer) with these constituent components.
Moreover, these polymers may be used independently and may be used in combination of 2 or more type.

  Particularly preferred polymers include polyester, acrylic, styrene-acrylic, polyethylene, polyurethane and the like, and optimally include polyester, acrylic, styrene-acrylic, polyethylene and the like.

  In addition, the polymer which comprises these organic fine particles has a function which coat | covers the coloring material, when using the coloring material mentioned later together. Thus, by covering the colorant with the polymer, the charge of the colorant can be blocked and desired charge characteristics can be imparted to the resulting organic fine particles. In addition, plate inspection can be imparted.

(Dispersant)
In the wet dispersion method in the present invention, it is preferable to use a dispersant in order to control the diameter of the organic fine particles and suppress the sedimentation of the particles.
Suitable dispersants include surfactants represented by sorbitan fatty acid esters such as sorbitan monooleate and polyethylene glycol fatty acid esters such as polyoxyethylene distearate. Further, for example, a copolymer of styrene and maleic acid, and an amine-modified product thereof, a copolymer of styrene and a (meth) acrylic compound, a (meth) acrylic polymer, a copolymer of polyethylene and a (meth) acrylic compound, rosin, BYK-160, 162, 164, 182 (polyurethane polymer manufactured by Big Chemie), EFKA-401, 402 (acrylic polymer manufactured by EFKA), Solsperse 17000, 24000 (polyester polymer manufactured by Geneca), and the like.

The dispersant in the present invention has a weight average molecular weight in the range of 1,000 to 1,000,000 and a polydispersity (weight average molecular weight / weight) from the viewpoint of long-term storage stability of the ink composition. A polymer having a number average molecular weight) in the range of 1.0 to 7.0 is preferred.
Furthermore, it is most preferable to use a graft polymer or a block polymer.

  The polymer that is particularly preferably used as a dispersant in the present invention is represented by a polymer component composed of at least one of the structural units represented by the following general formulas (5) and (6), and the following general formula (7). And a polymer component containing at least a structural unit as a graft chain.

In the general formula (5), X ⁵¹ represents an oxygen atom or —N (R ⁵³ ) —. R ⁵¹ represents a hydrogen atom or a methyl group, R ⁵² represents a hydrocarbon group having 1 to 10 carbon atoms, and R ⁵³ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
In the general formula (6), R ⁶¹ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a hydroxyl group, or an alkoxy group having 1 to 20 carbon atoms.
In the general formula (7), X ⁷¹ represents an oxygen atom or —N (R ⁷³ ) —. R ⁷¹ represents a hydrogen atom or a methyl group, R ⁷² represents a hydrocarbon group having 4 to 30 carbon atoms, and R ⁷³ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
The hydrocarbon group of R ⁵² and R ⁷² may contain an ether bond, an amino group, a hydroxy group, or a halogen substituent.

  The graft polymer is obtained by polymerizing a radical polymerizable monomer corresponding to the general formula (7), preferably in the presence of a chain transfer agent, introducing a polymerizable functional group into the terminal of the obtained polymer, It can be obtained by copolymerizing with a radically polymerizable monomer corresponding to formula (5) and / or general formula (6).

  Examples of the radical polymerizable monomer corresponding to the general formula (5) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic acid. Hexyl (meth) acrylate cyclohexyl, phenyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic acid esters of 2-hydroxyethyl (meth) acrylate, and N-methyl (meth) acrylamide And (meth) acrylamides such as N-propyl (meth) acrylamide, N-phenyl (meth) acrylamide, and N, N-dimethyl (meth) acrylamide.

  Examples of the radical polymerizable monomer corresponding to the general formula (6) include styrene, 4-methylstyrene, chlorostyrene, methoxystyrene, and the like.

  Examples of the radical polymerizable monomer corresponding to the general formula (7) include hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, ( Examples thereof include stearyl methacrylate.

  Specific examples of these graft polymers include polymers represented by the following structural formulas.

A polymer component containing at least one of the structural units represented by the general formulas (5) and (6), a polymer component containing at least the structural unit represented by the general formula (7) as a graft chain, and The graft polymer containing may contain only the structural unit represented by general formula (5) and / or general formula (6) and general formula (7), or may contain other constituent components. May be.
Moreover, the preferable composition ratio of the polymer component containing a graft chain and the other polymer components is 10:90 to 90:10. Within this range, good particle formability is obtained, and a desired particle diameter is easily obtained, which is preferable. These polymers may be used alone as a dispersant, or may be used in combination of two or more.

  The content of these dispersants is preferably in the range of 0.01 to 30% by mass with respect to the total mass of the dispersion used when the polymer is atomized. Within this range, good particle formability can be obtained, and a desired particle diameter can be obtained.

(Non-aqueous solvent)
As the non-aqueous solvent used in the wet dispersion method in the present invention, the same non-aqueous solvent as used in the above-described polymerization granulation method can be used.
The non-aqueous solvent used in the wet dispersion method is usually a dispersion medium that constitutes the ink composition in the dispersion stage of the organic fine particles in order to omit steps such as substitution with the dispersion medium that constitutes the ink composition. It is preferable to use the same non-aqueous solvent.

  The amount of the dispersion medium used is preferably in the range of 0.01 to 30% by mass, and in the range of 0.05 to 27% by mass, with respect to the total mass of the dispersion used in the micronization of the polymer. It is more preferable that it is in the range of 0.1 to 25% by mass.

(Wet dispersion method)
The organic fine particles in the present invention can be produced by dispersing (making fine particles) the polymer constituting the organic fine particles using the above components.
Hereinafter, a method for producing organic fine particles using a wet dispersion method will be specifically described. Note that the organic fine particles produced here are charged particles containing a colorant.
1) A colorant and a polymer constituting organic fine particles are mixed in advance, and then dispersed (finely divided) using a dispersant and a nonaqueous solvent, and a charge adjusting agent is added.
2) A colorant, a polymer constituting organic fine particles, a dispersing agent, and a non-aqueous solvent are simultaneously dispersed (micronized), and a charge adjusting agent is added.
3) A colorant, a polymer constituting the organic fine particles, a dispersing agent, a charge adjusting agent, and a non-aqueous solvent are simultaneously used (dispersed).
In the method 1), when the colorant and the polymer constituting the organic fine particles are mixed, it is preferable to knead while heating at a temperature of 50 to 150 ° C.

  Here, examples of the apparatus used for mixing and dispersing include a kneader, a dissolver, a mixer, a high-speed disperser, a sand mill, a roll mill, a ball mill, an attritor, and a bead mill.

(Onium salt compound)
The organic fine particles obtained by the wet dispersion method can contain an onium salt compound from the viewpoint of improvement in charge generation efficiency and charge stability over time.
Such onium salt compounds are, for example, ammoniums, oxoniums, sulfoniums, seleniums, phosphoniums, and the like, preferably ammoniums, sulfoniums, phosphoniums, and the like.
More specifically, examples of ammoniums, sulfoniums, and phosphoniums include compounds represented by the following general formula (I).

In the general formula (I), Y represents an N, S or P atom. R ^{1 to} R ⁴ may be the same or different and each represents a hydrogen atom or a hydrocarbon group. The hydrocarbon group for R ^{1 to} R ⁴ represents an alkyl group having 1 to 22 carbon atoms, an alkenyl group, an aralkyl group, an alicyclic group, an aryl group, or a bridged cyclic hydrocarbon group, and these are substituted. Also good.

As preferred hydrocarbon groups for R ^{1 to} R ^4, an optionally substituted alkyl group having 1 to 22 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, heptyl group, octyl group) , Nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group, docosyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, etc.), an optionally substituted alkenyl group having 4 to 18 carbon atoms (for example, 2-methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group Group, decenyl group, dodecenyl group, tridecenyl group, hexadecenyl group, octadecenyl group, linolenyl group, etc.), C 7-12 optionally substituted aralkyl group (for example, benzyl group, phenethyl group, 3-phenylpropyl group) , Nabutylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), substituted with 5 to 8 carbon atoms Or an alicyclic group (for example, cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.) or an aromatic group having 6 to 12 carbon atoms which may be substituted (for example, phenyl group, naphthyl group) , Tolyl group, xylyl group, propylphenyl group, butylphenyl group, octyl Phenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl Group, butoxycarbonylphenyl group, acetamidophenyl group, propionamidophenyl group, dodeciloylamidophenyl group, etc.).

R ¹ and R ² and R ³ and R ⁴ may be bonded to each other to represent an organic residue that forms a ring with a nitrogen atom. This organic residue may further contain a hetero atom (for example, an oxygen atom, a nitrogen atom, a sulfur atom, etc.). Examples of the cyclic ammonium group to be formed include those obtained by quaternizing a morpholino group, piperidino group, pyridyl group, imidazolyl group, quinolyl group, oxazoline group and the like.
Examples of the cyclic sulfonium group include those obtained by quaternizing a thiophene group, a tetrahydrothiophene group, a benzothiophene group, a thiazole group, or the like.

X ⁻ represents an anion. Examples of the anion component include alkyl such as halogen, monomethyl sulfuric acid, p-toluenesulfonic acid, and phenylsulfonic acid, and arylbenzenesulfonic acid ions. In addition, various anions described in JP-A-59-137960 can also be mentioned.

The onium salt compound in the present invention may be a polymer containing an onium base (hereinafter sometimes referred to as an onium base-containing polymer) in addition to the low molecular weight compound. Examples of components constituting the polymer main chain include acrylic esters, methacrylic esters, acrylamides, methacrylamides, vinyl esters, styrenes, acrylic acid, methacrylic acid, acrylonitrile, maleic anhydride, maleic acid Well-known monomers, such as an imide, are mentioned.
Specific examples of acrylic esters include methyl acrylate, ethyl acrylate, (n- or i-) propyl acrylate, (n-, i-, sec- or t-) butyl acrylate, amyl acrylate, 2-ethylhexyl acrylate, Dodecyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypentyl acrylate, cyclohexyl acrylate, allyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, chloro Benzyl acrylate, hydroxybenzyl acrylate, hydroxyphenethyl acrylate, dihydroxyphenethyl Acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, hydroxyphenyl acrylate, chlorophenyl acrylate, sulfamoylphenyl acrylate, 2- (hydroxyphenyl carbonyloxy) ethyl acrylate.

  Specific examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, (n- or i-) propyl methacrylate, (n-, i-, sec- or t-) butyl methacrylate, amyl methacrylate, 2-ethylhexyl methacrylate, Dodecyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxypentyl methacrylate, cyclohexyl methacrylate, allyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, benzyl methacrylate, methoxybenzyl methacrylate, chloro Benzyl methacrylate, hydroxybenzyl methacrylate, hydroxyphene Chill methacrylate, dihydroxyphenethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, hydroxyphenyl methacrylate, chlorophenyl methacrylate, sulfamoylphenyl methacrylate, 2- (hydroxyphenyl carbonyloxy) ethyl methacrylate.

  Specific examples of acrylamides include acrylamide, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, N-benzylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, and N-tolylacrylamide. N- (hydroxyphenyl) acrylamide, N- (sulfamoylphenyl) acrylamide, N- (phenylsulfonyl) acrylamide, N- (tolylsulfonyl) acrylamide, N, N-dimethylacrylamide, N-methyl-N-phenylacrylamide , N-hydroxyethyl-N-methylacrylamide and the like.

  Specific examples of methacrylamides include methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-propylmethacrylamide, N-butylmethacrylamide, N-benzylmethacrylamide, N-hydroxyethylmethacrylamide, N -Phenylmethacrylamide, N-tolylmethacrylamide, N- (hydroxyphenyl) methacrylamide, N- (sulfamoylphenyl) methacrylamide, N- (phenylsulfonyl) methacrylamide, N- (tolylsulfonyl) methacrylamide, N , N-dimethylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-hydroxyethyl-N-methylmethacrylamide and the like.

Specific examples of vinyl esters include vinyl acetate, vinyl butyrate, vinyl benzoate and the like. Specific examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, propyl styrene, cyclohexyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, methoxy styrene, dimethoxy styrene. Chlorostyrene, dichlorostyrene, bromostyrene, iodostyrene, fluorostyrene, carboxystyrene, and the like.
In addition, a commercially available onium base-containing polymer and a commercially available polymer obtained by onium chloride can be used without particular limitation.

  The weight average molecular weight (Mw) of the onium base-containing polymer is, for example, in the range of 3,000 to 2,000,00, preferably 4,000 to 150,000, more preferably 5,000 to 120,000. is there.

The content of such an onium salt compound is, for example, 40 to 1% by mass, preferably 35 to 2% by mass, and more preferably 30 to 30% by mass of the total amount of organic fine particles as a functional group or monomer unit constituting the onium salt compound. 3% by mass.
In addition, the above-mentioned onium base-containing polymer may constitute part or all of the polymer constituting the above-described organic fine particles. Therefore, when an onium base-containing polymer is used as a polymer constituting organic fine particles, it can be used regardless of the content range.

(Compound having a proton-accepting neutral functional group having a pKb of 16 or less in water)
The organic fine particles obtained by the wet dispersion method contain a compound having a proton-accepting neutral functional group having a pKb of 16 or less in water from the viewpoint of improvement in charge generation efficiency and charge stability with time. Can do. The pKb is preferably 16 to -5, more preferably 12 to -2.
A compound having a proton-accepting neutral functional group having a pKb of 16 or less in water (hereinafter, water means water having a temperature of 25 ° C.) (hereinafter sometimes referred to as a proton-accepting group-containing compound). Examples thereof include compounds in which the neutral functional group is a functional group containing at least one atom of a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Secondary aliphatic amines (methylamine, ethylamine, propylamine, n-butylamine, n-hexylamine, 2-ethylhexylamine, dimethylamine, diethylamine, di-n-butylamine, di-n-hexylamine, methylethylamine, ethyl n- Butylamine, triethylamine, tri-n-butylamine, tri-n-hexylamine, dimethylethylamine, diethyl n- Tilamine, etc.), 1, 2 or tertiary aromatic amines (phenylamine, naphthylamine, p-bromophenylamine, p-methoxyphenylamine, m-bromophenylamine, methylphenylamine, ethylphenylamine, methylnaphthylamine, n -Butylphenylamine, 2-ethylhexylphenylamine, diphenylamine, dimethylphenylamine, diethylphenylamine, triphenylamine, methyldiphenylamine, n-butyldiphenylamine, etc.), hydrazines (hydrazine, dimethylhydrazine, diethylhydrazine, etc.), N atom Containing heterocycles (pyridine, imidazole, oxazoline, triazole, etc.), sulfides (dimethyl sulfide, diethyl sulfide, di-n-butyl sulfide, di-n-hexyl) Sulfide, diphenyl sulfide, methyl phenyl sulfide, etc.) and the like.
Among them, preferred are 1, 2 or tertiary aliphatic amines, 1, 2 or tertiary aromatic amines, and N atom-containing heterocycles, and more preferred are 1, 2 or tertiary aliphatic amines. , N atom-containing heterocycles.

  The proton-accepting group-containing compound in the present invention is a polymer containing a component corresponding to the proton-accepting group-containing compound in addition to the low molecular weight compound (hereinafter sometimes referred to as a proton-accepting group-containing polymer). There may be. Examples of components constituting the polymer main chain include acrylic esters, methacrylic esters, acrylamides, methacrylamides, vinyl esters, styrenes, acrylic acid, methacrylic acid, acrylonitrile, maleic anhydride, maleic acid. Known monomers such as imide, alkylene, phenylene chain and the like can be mentioned.

  Specific examples of acrylic esters include methyl acrylate, ethyl acrylate, (n- or i-) propyl acrylate, (n-, i-, sec- or t-) butyl acrylate, amyl acrylate, 2-ethylhexyl acrylate, Dodecyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypentyl acrylate, cyclohexyl acrylate, allyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, chloro Benzyl acrylate, hydroxybenzyl acrylate, hydroxyphenethyl acrylate, dihydroxyphenethyl Acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, hydroxyphenyl acrylate, chlorophenyl acrylate, sulfamoylphenyl acrylate, 2- (hydroxyphenyl carbonyloxy) ethyl acrylate.

  Specific examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, (n- or i-) propyl methacrylate, (n-, i-, sec- or t-) butyl methacrylate, amyl methacrylate, 2-ethylhexyl methacrylate, Dodecyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxypentyl methacrylate, cyclohexyl methacrylate, allyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, benzyl methacrylate, methoxybenzyl methacrylate, chloro Benzyl methacrylate, hydroxybenzyl methacrylate, hydroxyphene Chill methacrylate, dihydroxyphenethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, hydroxyphenyl methacrylate, chlorophenyl methacrylate, sulfamoylphenyl methacrylate, 2- (hydroxyphenyl carbonyloxy) ethyl methacrylate.

  Specific examples of acrylamides include acrylamide, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, N-benzylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, and N-tolylacrylamide. N- (hydroxyphenyl) acrylamide, N- (sulfamoylphenyl) acrylamide, N- (phenylsulfonyl) acrylamide, N- (tolylsulfonyl) acrylamide, N, N-dimethylacrylamide, N-methyl-N-phenylacrylamide , N-hydroxyethyl-N-methylacrylamide and the like.

  Specific examples of methacrylamides include methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-propylmethacrylamide, N-butylmethacrylamide, N-benzylmethacrylamide, N-hydroxyethylmethacrylamide, N -Phenylmethacrylamide, N-tolylmethacrylamide, N- (hydroxyphenyl) methacrylamide, N- (sulfamoylphenyl) methacrylamide, N- (phenylsulfonyl) methacrylamide, N- (tolylsulfonyl) methacrylamide, N , N-dimethylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-hydroxyethyl-N-methylmethacrylamide and the like.

  Specific examples of vinyl esters include vinyl acetate, vinyl butyrate, vinyl benzoate and the like.

  Specific examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, propyl styrene, cyclohexyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, methoxy styrene, dimethoxy styrene. Chlorostyrene, dichlorostyrene, bromostyrene, iodostyrene, fluorostyrene, carboxystyrene and the like.

  In addition, a commercially available proton-accepting group-containing polymer or a polymer obtained by introducing a proton-accepting neutral functional group having a pKb of 16 or less in water into a commercially available polymer can be used without particular limitation.

  The weight average molecular weight (Mw) of the proton-accepting group-containing polymer is, for example, in the range of 3,000 to 200,000, preferably 4,000 to 150,000, more preferably 5,000 to 120,000. It is.

The content of the proton-accepting group-containing compound is, for example, preferably 40 to 0.01% by mass of the total amount of organic fine particles, more preferably 35 to 0 as the functional group or monomer unit constituting the proton-accepting group-containing compound. 0.02% by mass, more preferably 30-0.03% by mass.
The content of the proton-accepting neutral functional group having a pKb of 16 or less in water is preferably 50 to 0.1% by mass, more preferably 40% of the total amount of organic fine particles as the proton-accepting group-containing compound. -0.5 mass%, More preferably, it is 30-1 mass%.

  The proton-accepting group-containing polymer described above may constitute part or all of the polymer constituting the organic fine particles. Therefore, when the proton-accepting group-containing polymer is used as a polymer constituting the organic fine particles, it can be used regardless of the content range.

(Polyester having hydrogen bonding group other than hydroxyl group and ester group)
The organic fine particles obtained by the wet dispersion method have a hydrogen bonding group other than a hydroxyl group and an ester group as a polymer constituting the organic fine particles from the viewpoint of achieving high-speed and low-temperature fixing, and from the following a) It is preferable to use a polyester that satisfies the physical property value of c) (hereinafter sometimes referred to as a specific polyester).
a) the dynamic modulus at 50 ℃ G ': ¹⁰ 4 Pa or more, preferably, 1 × ¹⁰ 5 Pa or more, more preferably, 5 × ¹⁰ 5 Pa or more, more preferably 5 × ¹⁰ 5 Pa~1 × 10 ⁸ Pa.
Dynamic modulus at 100 ℃ G ': ¹⁰ 3 Pa or more, preferably, 5 × ¹⁰ 3 Pa or more, more preferably, 1 × ¹⁰ 4 Pa or more, more preferably 1 × ¹⁰ 4 Pa~1 × ^{10 5} Pa.
b) Molecular weight (GPC mass average): 50,000 or less, preferably 40,000 or less, more preferably 35,000 or less, still more preferably 5,000 to 35,000. In addition, GPC mass average as used in the field of this invention means the weight average molecular weight measured by the gel permeation chromatography.
c) Glass transition point (Tg): 30 to 100 ° C, preferably 35 to 80 ° C, more preferably 35 to 70 ° C.

When the dynamic elastic modulus G ′ at 50 ° C. of the specific polyester is less than 10 ⁴ Pa, the polyester flows, and when a recording medium such as paper is superimposed on the image, the blocking phenomenon that adheres to the paper occurs. appear. On the other hand, when the dynamic elastic modulus G ′ at 100 ° C. is less than 10 ³ Pa, the rubber elasticity of the polyester is lost, causing cohesive failure in the image layer and causing an offset to the heat roller.
Further, when the molecular weight of the specific polyester exceeds 50,000, the cohesive strength of the polyester becomes high, and it becomes difficult to sufficiently reduce the size by a normal pulverization / dispersion method.
Furthermore, when the glass transition temperature (Tg) of the specific polyester is less than 30 ° C., the movement of the polymer chain of the polyester at 50 ° C. becomes active, the polyester flows, and a recording medium such as paper is formed on the image. When stacked, a blocking phenomenon occurs that adheres to paper. On the other hand, when the glass transition temperature (Tg) exceeds 100 ° C., the low-temperature fixability deteriorates.

In the present invention, the specific polyester is not particularly limited as long as it has a hydrogen-bonding group other than a hydroxyl group and an ester group and satisfies the above specific property value conditions, but preferably a hydrogen other than a hydroxyl group and an ester group. The binding group is preferably at least one selected from an amide group, a urethane group, a urea group, an amino group, a thiol group, a thiourethane group, and a thiourea group.
These hydrogen bonding groups may have a substituent. Further, the substituents that can be introduced may be the same or different and each represents a hydrocarbon group. The hydrocarbon group represents an alkyl group, alkenyl group, aralkyl group, alicyclic group, aryl group or bridged cyclic hydrocarbon group having 1 to 22 carbon atoms, which may be further substituted.

  Preferred hydrocarbon groups include alkyl groups having 1 to 22 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, Dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl, 2-methoxycarbonylethyl, 2-methoxyethyl, 3 -Bromopropyl group, etc.), an alkenyl group having 4 to 18 carbon atoms which may be substituted (for example, 2-methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group) 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, decenyl group, dode Nyl group, tridecenyl group, hexadecenyl group, octadecenyl group, linolenyl group, etc.), an aralkyl group having 7 to 12 carbon atoms which may be substituted (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2 A naphthylethyl group, a chlorobenzyl group, a bromobenzyl group, a methylbenzyl group, an ethylbenzyl group, a methoxybenzyl group, a dimethylbenzyl group, a dimethoxybenzyl group), an optionally substituted alicyclic group having 5 to 8 carbon atoms. (For example, cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.), aryl group having 6 to 12 carbon atoms which may be substituted (for example, phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl) Group, butylphenyl group, octylphenyl group, dodecylphenyl group, Xiphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamide Phenyl group, propionamidophenyl group, dodecylylamidophenyl group, etc.), bridged cyclic hydrocarbon group (for example, norbornyl group, adamantyl group, etc.) and the like.

  In addition, these substituents may be bonded to each other to represent an organic residue for forming a ring together with the hydrogen bonding groups containing nitrogen atoms listed above. This organic residue may further contain a hetero atom (for example, an oxygen atom, a nitrogen atom, a sulfur atom, etc.). Examples of the cyclic ammonium group to be formed include those obtained by quaternizing a morpholino group, piperidino group, pyridyl group, imidazolyl group, quinolyl group, oxazoline group and the like. In addition, examples of the cyclic sulfonium group include those obtained by quaternizing a thiophene group, a tetrahydrothiophene group, a benzothiophene group, a thiazole group, or the like.

The specific polyester is more preferably a polyester having structural units represented by the following general formula (a) and general formula (b).
-[CO-X-COO-YO]-General formula (a)
-[CONH-Z-NHCOO-W-O]-General formula (b)

(In general formula (a) and general formula (b), X, Y, Z, and W are each independently an alkylene group, a cycloalkylene group, an alkenylene group, an alkynylene group, an arylene group, which may be substituted. Represents an aralkylene group or a bridged cyclic hydrocarbon group.)

The linking groups X, Y, Z, and W are preferably a linking group of an alkylene group, alkenylene group, alkynylene group, cycloalkylene group, arylene group, aralkylene group, or bridged cyclic hydrocarbon group having 1 to 22 carbon atoms. Which may be substituted.
Specific embodiments of X, Y, Z, and W include alkylene groups having 1 to 22 carbon atoms (for example, methylene, ethylene, propylene, butylene, hexylene, heptylene, octylene, nonylene, decylene, and dodecylene). , Tridecylene, tetradecylene, hexadecylene, octadecylene, eicosylene, docosylene, 2-chloroethylene, 2-bromoethylene, 2-cyanoethylene, 2-methoxycarbonylethylene, 2-methoxyethylene, 3-bromopropylene, etc.), 4 to 4 carbon atoms 18 optionally substituted alkenylene groups (for example, 2-methyl-1-propenylene, 2-butenylene, 2-pentenylene, 3-methyl-2-pentenylene, 1-pentenylene, 1-hexenylene, 2-hexenylene, 4- Methyl-2-hexenylene, de Nylene, dodecenylene, tridecenylene, hexadecenylene, octadecenylene, linolenylene, etc.), alkynylene groups (eg, acetylene, methylacetylene, phenylacetylene, etc.), C 7-12 optionally substituted aralkylene groups (eg, benzylene, phenylene, 3 -Phenylpropylene, naphthylmethylene, 2-naphthylethylene, chlorobenzylene, bromobenzylene, methylbenzylene, ethylbenzylene, methoxybenzylene, dimethylbenzylene group, dimethoxybenzylene, etc.), C5-C8 substitution A cycloalkylene group (for example, cyclohexylene, 2-cyclohexylethylene, 2-cyclopentylethylene, etc.) which may be substituted, an arylene group having 6 to 12 carbon atoms which may be substituted (for example, phenylene, naphthyl) , Tolylene, xylylene, propylphenylene, butylphenylene, octylphenylene, dodecylphenylene, methoxyphenylene, ethoxyphenylene, butoxyphenylene, decyloxyphenylene, chlorophenylene, dichlorophenylene, bromophenylene, cyanophenylene, acetylphenylene, methoxycarbonylphenylene, Ethoxycarbonylphenylene, butoxycarbonylphenylene, acetamidophenylene, propionamidophenylene, dodeciloylamidophenylene, etc.) or a bridged cyclic hydrocarbon group (for example, norbornyl, adamantyl, etc.).

  X, Y, Z, and W may each represent an organic residue that is bonded to form a ring with a nitrogen atom. This organic residue may further contain a hetero atom (for example, an oxygen atom, a nitrogen atom, a sulfur atom, etc.). Examples of the cyclic ammonium group to be formed include those obtained by quaternizing a morpholino group, piperidino group, pyridyl group, imidazolyl group, quinolyl group, oxazoline group and the like. In addition, examples of the cyclic sulfonium group include those obtained by quaternizing a thiophene group, a tetrahydrothiophene group, a benzothiophene group, a thiazole group, or the like.

The specific polyester described above may constitute part or all of the polymer constituting the organic fine particles.
Moreover, when using together specific polymer and the polymer which comprises the above-mentioned organic fine particle, the compounding ratio of the polymer which comprises the organic fine particle shall not exceed 40 mass% with respect to the polymer whole quantity. Preferably it is 30 mass% or less.
Here, specific polyester resin may be used independently and may be used in combination of 2 or more type.

[Colorant]
In the present invention, a colorant is used to obtain colored organic fine particles.
In the present invention, at least one of (A) colored organic fine particles having a volume average particle diameter of 0.8 μm or more and (B) colored organic fine particles having a volume average particle diameter of 0.7 μm or less is in the visible region. From the viewpoint of having absorption, the colorant used in the present invention preferably has absorption in the visible region. When the ink composition of the present invention is used for drawing an image on a lithographic printing plate, it is not necessary to form a colored image. However, in order to improve the visibility of the formed image portion, or the ink composition is used. When a colored image is to be formed, a colorant can be contained.

  As the colorant used in the ink composition of the present invention, known dyes and pigments can be used, and can be selected according to applications and purposes. For example, it is preferable to use a pigment from the viewpoint of the color tone of the recorded image recorded matter (printed matter) (for example, “Distribution Stabilization and Surface Treatment Technology / Evaluation” published on December 25, 2001, published by the Technical Information Association). (Refer to the 1st print, which may be referred to as “Reference 1” hereinafter.)

In addition, by changing the colorant, it is possible to create an ink composition of four colors of yellow, magenta, cyan, and black. In particular, the use of offset printing inks or pigments used for proofing is preferable because the same color tone as that of offset printed matter can be obtained.
On the other hand, when used as an ink composition for a lithographic printing plate, the colorant is not particularly limited as long as the plate can be inspected, and a dye or the like often used in a lithographic printing plate so far is used as a coloring material. Can do.

  Examples of pigments for yellow ink include C.I. I. Pigment yellow 1, C.I. I. Monoazo pigments such as CI Pigment Yellow 74; I. Pigment yellow 12, C.I. I. Disazo pigments such as C.I. Pigment Yellow 17; I. Non-benzidine azo pigments such as CI Pigment Yellow 180; I. Azo lake pigments such as C.I. Pigment Yellow 100; I. Condensed azo pigments such as CI Pigment Yellow 95; I. Pigment Yellow 115 and other acid dye lake pigments, C.I. I. Pigment Yellow 18 and other basic dye lake pigments, Flavantron Yellow and other anthraquinone pigments, Isoindolinone Yellow 3RLT and other isoindolinone pigments, Quinophthalone Yellow and other quinophthalone pigments, Isoindoline Yellow and other isoindoline pigments, C.I. I. Nitroso pigments such as C.I. Pigment Yellow 153, C.I. I. Metal complex azomethine pigments such as CI Pigment Yellow 117; I. And isoindolinone pigments such as CI Pigment Yellow 139.

  Examples of pigments for magenta ink include C.I. I. Monoazo pigments such as CI Pigment Red 3; I. Disazo pigments such as CI Pigment Red 38; I. Pigment red 53: 1 etc. and C.I. I. Azo lake pigments such as CI Pigment Red 57: 1; I. Condensed azo pigments such as CI Pigment Red 144; I. Pigment Red 174, acidic dye lake pigments, C.I. I. Basic dye lake pigments such as CI Pigment Red 81; I. Anthraquinone pigments such as CI Pigment Red 177; I. Thioindigo pigments such as CI Pigment Red 88; I. Perinone pigments such as CI Pigment Red 194; I. Perylene pigments such as CI Pigment Red 149; I. Quinacridone pigments such as C.I. Pigment Red 122; I. Pigment Red 180 and other isoindolinone pigments, C.I. I. And alizarin lake pigments such as CI Pigment Red 83.

  Examples of the pigment for cyan ink include C.I. Disazo pigments such as CI Pigment Blue 25, C.I. I. Phthalocyanine pigments such as CI Pigment Blue 15; I. Pigment Blue 24 and other acidic dye lake pigments, C.I. I. Basic dye lake pigments such as CI Pigment Blue 1; I. Anthraquinone pigments such as CI Pigment Blue 60; I. And alkaline blue pigments such as CI Pigment Blue 18.

  Examples of the pigment for black ink include organic pigments such as aniline black pigments and iron oxide pigments, and carbon black pigments such as furnace black, lamp black, acetylene black, and channel black.

  Furthermore, processed pigments typified by microlith pigments such as Microlith-A, -K, and -T can also be suitably used. Specific examples thereof include Microlith Yellow 4G-A, Micro Resled BP-K, Microlith Blue 4G-T, and Microlith Black CT.

  Various pigments can be used as necessary, such as calcium carbonate and titanium oxide pigments for white ink, aluminum powder for silver ink, and copper alloy for gold ink.

  Basically, it is preferable to use one type of pigment for each color from the viewpoint of ease of ink production. However, as a hue adjustment, for example, for black ink, phthalocyanine is mixed with carbon black. Depending on the case, two or more types may be used in combination. Further, the pigment may be used after being surface-treated by a known method such as rosin treatment (see Document 1).

  As dyes, azo dyes, metal complex dyes, naphthol dyes, anthraquinone dyes, indigo dyes, carbonium dyes, quinoneimine dyes, xanthene dyes, cyanine dyes, quinoline dyes, nitro dyes, nitroso dyes, benzoquinone dyes, naphthoquinone dyes, phthalocyanine dyes, Oil-soluble dyes such as metal phthalocyanine dyes are preferred.

These pigments and dyes may be used alone or in appropriate combination.
In addition, the content of the pigment and the dye is appropriately determined depending on the type and use of the color material (pigment or dye).
For example, when an image is drawn directly as a printed matter, the content of the pigment and the dye is preferably in the range of 0.1 to 100% by mass with respect to the mass of the organic fine particles in the ink composition. More preferably, it is in the range of ˜50 mass%. When the amount is 0.1% by mass or more, the coloring amount is sufficient, and a sufficiently good color is obtained in the printed matter. When the amount is 100% by mass or less, the storage stability, dispersibility, redispersibility, etc. of the organic fine particles are kept good. be able to.

  On the other hand, if the purpose is to obtain visibility such as plate inspection of a lithographic printing plate, the content of the pigment and the dye is 0.1 to 50 mass relative to the mass of the organic fine particles in the ink composition. % Is preferably within the range of 1% to 30% by mass. When the amount is 0.1% by mass or more, the coloring amount is sufficient and sufficiently good visibility is obtained, and when the amount is 30% by mass or less, the storage stability, dispersibility, redispersibility, etc. of the organic fine particles are kept good. Can do. More preferably, it is 1-20 mass%.

  These colorants may be dispersed in the dispersion medium as the dispersed particles in addition to the organic fine particles, or may be contained in the organic fine particles. As one of the methods of inclusion, there is a method of dyeing organic fine particles with a preferable dye as described in JP-A-57-48738. As another method, there is a method of chemically bonding organic fine particles and a dye as disclosed in JP-A-53-54029 or the like, or described in JP-B-44-22955 or the like. As described above, there is a method of preparing a dye-containing copolymer by using a monomer containing a dye in advance in the production by the polymerization granulation method.

The organic fine particles in the present invention have an elastic modulus of 1.0 × 10 ⁷ or more at room temperature (10 to 30 ° C. in the present invention) as their thermal properties, and a fixing temperature (80 to 150 in the present invention). C.) is preferably in the range of 5.0 × 10 ⁶ or less, in particular, the elastic modulus at room temperature is 1.0 × 10 ⁸ or more, and 1.0 × 10 ⁶ at the fixing temperature. The following range is more preferable.
The Tg of the organic fine particles in the present invention is preferably in the range of 25 to 150, more preferably in the range of 30 to 130, and still more preferably in the range of 35 to 100.

  In the ink composition of the present invention, the content of the organic fine particles (total amount) is in the range of 90 to 1% by mass with respect to the total mass of the ink composition, whereby a good image portion is formed, and the organic fine particles are formed. The storage stability and dispersibility of are increased. Moreover, it is more preferable that it is the range of 80-20 mass%, and it is still more preferable that it is the range of 70-3 mass%.

[Dispersion medium]
The ink composition of the present invention contains a dispersion medium in addition to the organic fine particles described above.
Examples of the dispersion medium include linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and halogen-substituted products (halogenated hydrocarbons) of these hydrocarbons. Specifically, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, Isopar E, Isopar G, Isopar H, Isopar L (Isopar; Exxon product name), Shellsol 70, Shellzol 71 (Shellsol; Shell Oil product name), Amsco OMS, Amsco 460 solvent (Amsco; Spirits product name), methylene dichloride, chloroform, carbon tetrachloride , Dichloroethane, methyl chloroform and the like can be used alone or in combination.

  In addition to the above hydrocarbon compounds and their halogen-substituted products, the following non-hydrocarbon compounds can also be mixed and used. Examples of compounds that can be mixed include alcohols (for example, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, and fluorinated alcohol), ketones (for example, acetone, methyl ethyl ketone, cyclohexanone, and the like), and carboxylic acid esters (for example, acetic acid). Methyl, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, etc.), ethers (eg, diethyl ether, dipropyl ether, tetrahydrofuran, dioxane, etc.) and the like.

The ratio of the above-mentioned hydrocarbon compounds and non-hydrocarbon compounds used in combination with their halogen substitution products is the viscosity, dispersion medium, etc. when drawing an image using an inkjet recording method such as a piezo method. Determined in consideration of boiling point, redispersibility, etc.
On the other hand, in the case of drawing an image using an electrostatic ink jet recording method, from the viewpoint of lowering the dielectric constant of the dispersion medium, non-carbonization used by mixing with the above hydrocarbon compounds and their halogen substitution products. A lower ratio of the hydrogen-based compound is preferable. Therefore, when the dielectric constant of the ink composition becomes 5.0 or more, a method of removing the non-hydrocarbon compound under heating or reduced pressure so as to be 5.0 or less, or a centrifugal separator is used. Thus, it is preferable to increase the ratio of the hydrocarbon compound and decrease the dielectric constant by using a method of replacing the supernatant.

  In the ink composition of the present invention, when the content of the dispersion medium is in the range of 90 to 10% by mass with respect to the total mass of the ink composition, a good image area is formed, and the storage stability of organic fine particles And dispersibility increase. Moreover, it is more preferable that it is the range of 98-20 mass%, and it is still more preferable that it is the range of 97-30 mass%.

[Charge control agent]
When the ink composition of the present invention is used to draw an image by the electrostatic ink jet recording method, it is preferable to use a charge adjusting agent in combination in order to enhance the response (electricity detection) of the organic fine particles to the pulse voltage.
To impart electroanalytical properties to the organic fine particles can be achieved by appropriately using the technique of a developer for wet electrophotography. Specifically, “Recent development and practical use of electrophotographic development systems and toner materials”, pages 139-148, Electrophotographic Society, “Basics and Applications of Electrophotographic Technology”, pages 497-505 (Corona, 1988) Yuji Harasaki, “Electrophotography” 16 (No. 2), page 44 (1977), etc., for example, using a charge control material, for example, a charge control agent and other additives.

Also, for example, British Patent Nos. 893,429, 934,038, U.S. Pat. Nos. 1,122,397, 3,900,412, 4,606,989, and Japanese Patent Publication No. 6 -19596, JP-B-6-19595, JP-B-6-23865, JP-B-4-51023, JP-A-2-13965, JP-A-60-185963, and the like, naphthenic acid Zirconium salts, metal salts of organic carboxylic acids such as zirconium octenoate, ammonium salts of organic carboxylic acids such as tetramethylammonium stearate, sodium dodecylbenzenesulfonate, magnesium dioctylsulfosuccinate, etc. Metal salt, ammonium salt of organic sulfonic acid such as toluenesulfonic acid tetrabutylammonium salt, styrene and A copolymer of carboxylic acid groups in a side chain such as a polymer containing a carboxylic acid group obtained by modifying a copolymer of hydromaleic acid with an amine, and a side chain such as a copolymer of stearyl methacrylate and a tetramethylammonium methacrylate salt. Polymer having acid anion group, polymer having nitrogen atom in side chain such as copolymer of styrene and vinylpyridine, butyl methacrylate and N- (2-methacryloyloxyethyl) -N, N, N-trimethylammonium tosylate Examples thereof include a polymer having an ammonium group in the side chain such as a copolymer with a salt.
The charge applied to the organic fine particles may be positively charged or negatively charged.

  It is preferable that the content of the current detection material with respect to the entire ink composition is in the range of 0.0001 to 20% by mass. Within this range, the electrical conductivity of the ink composition can be easily adjusted within the range of 10 nS / m to 1500 nS / m. Furthermore, the electric conductivity of charged particles (organic fine particles) can be easily adjusted to 50% or more of the electric conductivity of the ink composition.

[Charge control agent having a proton donating group having a pKa of 16 or less in water]
When the organic fine particles obtained by the wet dispersion method contain the aforementioned proton-accepting group-containing compound, as the charge adjusting agent, a charge adjusting agent having a proton donating group having a pKa in water of 16 or less (hereinafter referred to as proton donating) It may be referred to as a functional group-containing charge control agent). In addition, this pKa is preferably 16 to -5, and more preferably pKa is 12 to -2.
Examples of the proton-donating group-containing charge control agent include compounds having a proton-donating group such as a carboxyl group, a hydroxyl group, a phosphono group, a sulfo group, a thiol group, an imide group, and a sulfonamide group and soluble in a solvent. . Specifically, known monomers such as the above acrylic esters, methacrylic esters, acrylamides, methacrylamides, vinyl esters, styrenes, acrylic acid, methacrylic acid, acrylonitrile, maleic anhydride, maleic imide, etc. A polymer that is soluble in a solvent, in which a proton-donating group such as a carboxyl group, a hydroxyl group, a phosphono group, a sulfo group, a thiol group, an imide group, or a sulfonamide group is introduced into the polymer is preferable.
More preferable proton donating groups are a carboxyl group, a hydroxyl group, a phosphono group, a sulfo group, a thiol group, an imide group, and a sulfonamide group, and among them, a carboxyl group, a phosphono group, a sulfo group, and a sulfonamide group are particularly preferable. preferable.
The proton-donating group-containing charge control agent may be a polymer having a proton-donating group as described above and a monomer having a pKa in water of 16 or less as a constituent component.

In addition to such a proton-donating group-containing charge control agent, a known charge control agent as described above can be used in combination, but in this case, the amount of the known charge control agent used is the charge control agent. 5-50 mass% is preferable with respect to the whole quantity.
As described above, the proton-donating group-containing charge control agent has the property of being “soluble in a solvent”, and the solvent here indicates a dispersion medium constituting the ink composition.

[Other ingredients]
In the present invention, a preservative for preventing corruption, a surfactant for controlling surface tension, and the like can be further contained depending on the purpose.

As described above, the ink composition of the present invention is an oil-based ink containing, as essential components, a dispersion medium and two or more kinds of organic fine particles having different meltability with respect to heat.
Therefore, the ink composition of the present invention, as described above, has improved dispersion stability and redispersion in addition to the effect of improving the fixability to the recording medium and improving the printing durability when producing a lithographic printing plate. In addition, the effect derived from the oil-based ink is excellent in that it is excellent in stability and storage stability (aging stability) and can be applied to an ink jet recording method to form a high-definition image with good reproducibility.
In addition, the ink composition of the present invention is inkjet-recorded on a recording medium and then fixed by a heating means such as a heat roller or an oven. At this time, the organic fine particles are melted by heat and can be fixed efficiently. .

[Inkjet recording device]
The ink composition of the present invention is a so-called drop-on-demand method (piezo method) in which ink is ejected using the vibration pressure of a piezo element, and pressure generated by forming and growing bubbles by high heat. Any of various ink jet recording methods such as a so-called bubble (thermal) jet method in which ink is ejected using the above can be used without limitation, and a commercially available ink jet recording apparatus can be used.
The ink composition of the present invention is also suitably used for an ink jet recording apparatus using an electrostatic field. Ink jet recording methods that use an electrostatic field concentrate the charged particles of the ink composition at the discharge position by electrostatic force by applying a voltage between the control electrode and the back electrode on the back of the recording medium, and record from the discharge position. This is a method of flying to a medium. For example, when the charged particles are positive, the voltage applied between the control electrode and the back electrode is such that the control electrode is a positive electrode and the back electrode is a negative electrode. The same effect can be obtained by charging the recording medium instead of applying a voltage to the back electrode.

  In addition, as a method of flying the ink composition, for example, there is a method of flying ink from a needle-like tip such as an injection needle, and the ink composition of the present invention can be applied to this method. However, it is difficult to replenish charged particles after the charged particles are concentrated and discharged, and it is difficult to perform stable long-term recording. When the ink is circulated in order to forcibly supply charged particles, the ink overflows from the tip of the injection needle, so the meniscus shape at the tip of the injection needle, which is the discharge position, is not stable, and stable recording is performed. It is difficult to do and is suitable for short-term recording.

  On the other hand, a method of circulating the ink composition without overflowing the ink composition from the ejection opening is preferably used. For example, ink is circulated in an ink chamber having an ejection opening, and a voltage is applied to a control electrode formed at the periphery of the ejection opening, so that it exists in the ejection opening and the leading end faces the recording medium side. In the method in which the concentrated ink droplets fly from the tip of the ink guide, the replenishment of charged particles by the circulation of the ink and the meniscus stability at the ejection position can be compatible, so that stable recording can be performed for a long time. it can. Furthermore, in this method, since the ink composition has very few portions in contact with the outside air, only the discharge opening, evaporation of the solvent is suppressed and the ink physical properties are stabilized, so that the ink composition can be suitably used in the present invention.

A configuration example of an ink jet recording apparatus suitable for applying the ink composition of the present invention is shown below.
First, an outline of an apparatus that performs single-sided four-color printing on a recording medium shown in FIG. 1 will be described.
An ink jet recording apparatus 1 shown in FIG. 1 supplies ink to an ejection head 2 composed of ejection heads 2C, 2M, 2Y and 2K for four colors for forming a full-color image. A head driver 4 for driving the ejection head 2 by an output from an external device such as a computer, RIP (not shown), and a position control means 5. Further, the ink jet recording apparatus 1 includes a transport belt 7 stretched around three rollers 6A, 6B, and 6C, a transport belt position detection unit 8 including an optical sensor that can detect the position of the transport belt 7 in the width direction, An electrostatic attraction unit 9 for holding the recording medium P on the conveyance belt, a static elimination unit 10 and a mechanical unit 11 for peeling the recording medium P from the conveyance belt 7 after completion of image formation are provided. Upstream and downstream of the conveying belt 7, the feed roller 12 and the guide 13 that supply the recording medium P from the stocker (not shown) to the conveying belt 7, the ink is fixed to the recording medium P after peeling, and the discharge stocker (not shown). A fixing unit 14 and a guide 15 for conveying the toner are disposed. In addition, the inkjet printing apparatus 1 has a recording medium position detecting means 16 at a position facing the ejection head 2 with the conveyance belt 7 interposed therebetween, and further collects the solvent vapor generated from the ink composition. A solvent recovery unit comprising the exhaust fan 17 and the solvent vapor adsorbent 18 is disposed, and the vapor inside the apparatus is discharged outside the apparatus through the recovery unit.

  A known roller can be used as the feed roller 12, and the feed roller 12 is arranged so as to increase the feeding ability to the recording medium. Further, since dirt, paper powder, or the like may adhere on the recording medium P, it is desirable to remove them. The recording medium P supplied by the feed roller is transported to the transport belt 7 through the guide 13. The back surface (preferably metal back surface) of the conveyor belt 7 is installed via a roller 6A. The recording medium transported is electrostatically attracted onto the transport belt by the electrostatic attracting means 9. In FIG. 1, electrostatic adsorption is performed by a scorotron charger connected to a negative high voltage power source. The recording medium 9 is electrostatically adsorbed without floating on the conveying belt 7 by the electrostatic adsorption means 9 and the surface of the recording medium is uniformly charged. Here, the electrostatic attraction means is also used as a charging means for the recording medium, but may be provided separately. The charged recording medium P is transported to the ejection head portion by the transport belt 7, and electrostatic ink jet image formation is performed by superimposing the recording signal voltage with the charging potential as a bias. The recording medium P on which the image is formed is neutralized by the neutralizing unit 10, peeled off by the conveying unit 7 by the mechanical unit 11, and conveyed to the fixing unit. The peeled recording medium P is sent to the image fixing means 14 and fixed. The fixed recording medium P is discharged through a guide 15 to a discharge stocker (not shown). The apparatus also has a means for recovering the solvent vapor generated from the ink composition. The recovery means is composed of the solvent vapor absorbing material 18, and a gas containing solvent vapor in the apparatus is introduced into the adsorbent by the exhaust fan 17, and after the vapor is adsorbed and recovered, it is exhausted outside the apparatus. The apparatus is not limited to the above example, and the number, shape, relative arrangement, charging polarity, and the like of constituent devices such as rollers and chargers can be arbitrarily selected. In the above system, four-color drawing is described. However, a multicolor system may be combined with light color ink or special color ink.

  The ink jet recording apparatus used in the above ink jet printing method includes an ejection head 2 and an ink circulation system 3. The ink circulation system 3 further includes an ink tank, an ink circulation device, an ink concentration control device, an ink temperature management device, and the like. In addition, the ink tank may include a stirring device.

As the ejection head 2, a single channel head, a multi-channel head, or a full line head can be used, and main scanning is performed by the rotation of the transport belt 7.
An ink jet head suitably used in the present invention is an ink jet method in which charged particles in an ink flow path are electrophoresed to increase the ink density near the opening and discharge, and is mainly a recording medium or a recording target. Ink droplets are ejected by electrostatic attraction caused by the counter electrode disposed on the back surface of the medium. Therefore, if the recording medium or the counter electrode does not face the head, or if no voltage is applied to the recording medium or the counter electrode even at the position facing the head, the voltage is accidentally applied to the ejection electrode. Ink droplets are not ejected even when a pressure is applied or vibration is applied, and the inside of the apparatus is not soiled.

  An ejection head suitably used for the ink jet apparatus is shown in FIGS. As shown in FIGS. 2 and 3, the inkjet head 70 includes an electrically insulating substrate 74 that forms the upper wall of the ink flow path 72 where the ink flow Q in one direction is formed, and the ink to the recording medium P. And a plurality of discharge portions 76 that discharge toward the surface. Each of the ejection portions 76 is provided with an ink guide portion 78 that guides the ink droplet G flying from the ink flow path 72 toward the recording medium P, and the substrate 74 has an opening through which the ink guide portion 78 is inserted. 75 is formed, and the ink meniscus 42 is formed between the ink guide portion 78 and the inner wall surface of the opening 75. The gap d between the ink guide portion 78 and the recording medium P is preferably about 200 μm to 1000 μm. Further, the ink guide part 78 is fixed to the support bar part 40 on the lower end side.

  The substrate 74 includes an insulating layer 44 that electrically isolates two discharge electrodes at a predetermined interval, a first discharge electrode 46 formed above the insulating layer 44, and an insulation that covers the first discharge electrode 46. It has a layer 48, a guard electrode 50 formed on the insulating layer 48, and an insulating layer 52 that covers the guard electrode 50. The substrate 74 includes a second ejection electrode 56 formed below the insulating layer 44 and an insulating layer 58 that covers the second ejection electrode 56. The guard electrode 50 is provided in order to prevent an electric field from being affected by the voltage applied to the first ejection electrode 46 and the second ejection electrode 56 in the adjacent ejection section.

Further, the ink jet head 70 constitutes the bottom surface of the ink flow path 72, and the ink flow is generated by the induced voltage that is constantly generated by the pulsed discharge voltage applied to the first discharge electrode 46 and the second discharge electrode 56. A floating conductive plate 62 that moves positively charged ink particles (charged particles) R in the path 72 upward (that is, toward the recording medium side) is provided in an electrically floating state. In addition, a coating film 64 that is electrically insulating is formed on the surface of the floating conductive plate 62 to prevent the physical properties and components of the ink from becoming unstable due to charge injection into the ink. The electrical resistance of the insulating coating film is preferably 10 ¹² Ω · cm or more, and more preferably 10 ¹³ Ω · cm or more. In addition, the insulating coating film is desirably resistant to corrosion with respect to ink, and this prevents the floating conductive plate 62 from being corroded by ink. Further, the floating conductive plate 62 is covered with the insulating member 66 from below, and the floating conductive plate 62 is completely electrically insulated by such a configuration.

  There are one or more floating conductive plates 62 per head unit (for example, when there are four heads C, M, Y, and K, the number of floating conductive plates is at least one each, and C and M The floating conductive plate is not shared between the head units.

  As shown in FIG. 3, in order to cause ink to fly from the inkjet head 70 and record on the recording medium P, the ink in the ink flow path 72 is circulated to generate an ink flow Q, and the guard electrode A predetermined voltage (for example, +100 V) is applied to 50. Further, a flying electric field that attracts the positive charged particles R in the ink droplet G that has been guided by the ink guide portion 78 and flew from the opening 75 to the recording medium P is generated by the first ejection electrode 46 and the second ejection electrode. A positive voltage is applied to the first ejection electrode 46, the second ejection electrode 56, and the recording medium P so as to be formed between the recording medium P and the recording medium P (1 kV when the gap d is 500 μm). A potential difference of about ~ 3.0 kV is taken as a guide).

In this state, when a pulse voltage is applied to the first ejection electrode 46 and the second ejection electrode 56 in accordance with the image signal, the ink droplet G having an increased charged particle concentration is ejected from the opening 75 (for example, initial charged particles). When the concentration is 3 to 15%, the charged particle concentration of the ink droplet G is 30% or more).
At that time, the ink droplet G is applied to the first ejection electrode 46 and the second ejection electrode 56 so that the ink droplet G is ejected only when the pulse voltage is applied to both the first ejection electrode 46 and the second ejection electrode 56. Adjust the voltage value.

  In this way, when a pulsed positive voltage is applied, the ink droplet G is guided by the ink guide portion 78 from the opening 75 and flies to adhere to the recording medium P, and the first ejection is applied to the floating conductive plate 62. A positive induced voltage is generated by the positive voltage applied to the electrode 46 and the second ejection electrode 56. Even if the voltage applied to the first ejection electrode 46 and the second ejection electrode 56 is pulsed, the induced voltage is a substantially steady voltage. Therefore, the charged particles R that are positively charged in the ink flow path 72 are subjected to the upward movement force by the electric field formed between the floating conductive plate 62 and the guard electrode 50 and the recording medium P, and The concentration of charged particles R increases near the substrate 74. As shown in FIG. 3, when the number of ejection units (that is, channels for ejecting ink droplets) to be used is large, the number of charged particles necessary for ejection increases, but the first ejection electrode 46 and the second ejection electrode to be used are used. Since the number of 56 increases, the induced voltage induced in the floating conductive plate 62 increases, and the number of charged particles R moving to the recording medium side also increases.

  In the above, an example in which the colored particles are positively charged has been described. However, the colored particles may be negatively charged. In that case, all the above-mentioned charging polarities are reversed.

  In the present invention, it is preferable to fix the ink by an appropriate heating means after discharging the ink onto the recording medium. As the heating means used, a contact-type heating device such as a heat roller, a heat block, or a belt heating, and a non-contact type heating device such as a dryer, an infrared lamp, a visible light lamp, an ultraviolet lamp, or a hot air oven may be used. it can. These heating devices are preferably continuous with and integrated with the ink jet recording apparatus. The temperature of the recording medium at the time of fixing is preferably in the range of 40 ° C. to 200 ° C. for ease of fixing. The fixing time is preferably in the range of 1 microsecond to 20 seconds.

[Replenishment of ink composition when using an inkjet recording system utilizing an electrostatic field]
In the ink jet recording method using an electrostatic field, charged particles in the ink composition are concentrated and discharged. Accordingly, when the ink composition is discharged for a long time, the charged particles in the ink composition are reduced, and the electrical conductivity of the ink composition is lowered. Further, the ratio between the electric conductivity of the charged particles and the electric conductivity of the ink composition changes. Furthermore, since charged particles having a larger particle diameter tend to be discharged preferentially than charged particles having a smaller particle size, the average diameter of the charged particles is reduced. Further, since the solid content in the ink composition changes, the viscosity also changes.

  Due to these changes in physical property values, as a result, ejection failure occurs, the optical density of recorded images decreases, and ink bleeding occurs. For this reason, by reducing the amount of charged particles by replenishing the ink composition having a higher concentration (higher solid content concentration) than the ink composition initially charged in the ink tank, the electrical conductivity of the ink composition The ratio between the electric conductivity of the charged particles and the electric conductivity of the ink composition can be kept within a certain range. Moreover, a particle size and a viscosity can be maintained. Further, by maintaining the physical property value of the ink composition within a certain range, the ink discharge is stably and uniformly performed for a long time. The replenishment at this time is preferably performed mechanically or manually, for example, by detecting a physical property value such as the electrical conductivity or optical density of the ink liquid being used and calculating the deficiency. Further, the amount of the ink composition to be used may be calculated based on the image data, and may be made mechanically or manually.

[Recording medium]
In the present invention, various recording media can be used depending on the application. For example, if paper, plastic film, metal, and paper on which plastic or metal is laminated or vapor-deposited, plastic film on which metal is laminated or vapor-deposited, etc., printed matter can be obtained directly by ink jet recording. Further, if a support having a roughened metal such as aluminum is used, a lithographic printing plate or an offset printing plate can be obtained. Furthermore, if a plastic support is used, a flexographic printing plate or a color filter for a liquid crystal screen can be obtained. The shape of the recording medium may be planar such as a sheet shape or three-dimensional such as a cylindrical shape. Further, if a silicon wafer or a wiring board is used as a recording medium, it can be applied to manufacture of a semiconductor or a printed wiring board.

<Preparation method of lithographic printing plate>
The method for producing a lithographic printing plate of the present invention is characterized in that an image is drawn on an ink receptor by the ink jet recording method using the ink composition for ink jet recording of the present invention.
That is, the lithographic printing plate production method of the present invention forms an image portion by ejecting the ink composition for ink jet recording of the present invention onto an ink receptor using the ink jet recording apparatus as described above. It is.
In the method for preparing a lithographic printing plate precursor according to the invention, it is preferable to use an electrostatic ink jet recording method from the viewpoint of obtaining high resolution and high ink landing position accuracy. The ink receiver is prepared by the following steps including a support, a silicate treatment, a hydrophilic layer having a sol-gel structure, and the like.

[Support]
A support is used in the method for producing the ink receiver of the present invention. The support in the present invention is not particularly limited as long as it is a dimensionally stable plate-like material having a low solvent absorbability of the support and having the required strength and durability. For example, paper, plastic (for example, , Polyethylene, polypropylene, polystyrene, etc., laminated paper, metal plates (eg, aluminum, zinc, copper, etc.), plastic films (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate) Cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), paper laminated with metal, or vapor-deposited paper, or plastic film.

Among them, in the present invention, a polyester film or an aluminum plate is preferable, and among them, an aluminum plate that has good dimensional stability and is relatively inexpensive is particularly preferable. A suitable aluminum plate is a pure aluminum plate or an alloy plate containing aluminum as a main component and containing a trace amount of different elements, and may be a plastic film on which aluminum is laminated or vapor-deposited. Examples of foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, and titanium. The content of foreign elements in the alloy is at most 10% by mass. In the present invention, a support in which a sol-gel hydrophilic layer is provided on a surface-treated aluminum plate and polyester film is preferable.
These are described below.

[Aluminum support]
Particularly suitable aluminum in the present invention is pure aluminum, but completely pure aluminum is difficult to produce in the refining technique, and may contain slightly different elements.
Thus, the composition of the aluminum plate applied to the present invention is not specified, and an aluminum plate made of a publicly known material can be appropriately used. The thickness of the aluminum plate used in the present invention is about 0.1 mm to 0.6 mm, preferably 0.15 mm to 0.4 mm, and particularly preferably 0.15 mm to 0.3 mm.

Such an aluminum plate may be subjected to a surface treatment such as a roughening treatment or an anodizing treatment, if necessary. Hereinafter, such a surface treatment will be briefly described.
Prior to roughening the aluminum plate, a degreasing treatment with, for example, a surfactant, an organic solvent or an alkaline aqueous solution for removing rolling oil on the surface is performed as desired. The surface roughening treatment of the aluminum plate is performed by various methods. For example, a method of mechanically roughening, a method of electrochemically dissolving and roughening a surface, and a method of selectively dissolving a surface chemically. This is done by the method of As the mechanical method, a known method such as a ball polishing method, a brush polishing method, a blast polishing method, or a buff polishing method can be used. Further, as an electrochemical surface roughening method, there is a method of performing alternating current or direct current in hydrochloric acid or nitric acid electrolyte. Further, as disclosed in JP-A-54-63902, a method in which both are combined can also be used.

[surface treatment]
The support in the present invention is preferably formed by subjecting the aforementioned aluminum plate to a surface treatment. For example, it is preferable that a structure in which two or more kinds of irregularities with different periods are superimposed is formed on the support surface by this surface treatment.
In order to obtain a support having such a surface shape, specifically, it is preferably obtained by subjecting an aluminum plate to a roughening treatment and an anodizing treatment.
The manufacturing process of such a support is not particularly limited, and may include various processes other than the roughening process and the anodizing process. For example, a mechanical surface roughening treatment, an aluminum plate, a mechanical surface roughening treatment, an alkali etching treatment, a desmutting treatment with an acid, and an electrochemical surface roughening treatment using an electrolytic solution in sequence. Alkali etching treatment, acid desmutting treatment and electrochemical surface roughening treatment using different electrolyte solutions multiple times, aluminum plate alkali etching treatment, acid desmutting treatment and electrochemical roughening using electrolyte solution Examples include a method of sequentially performing surface treatment, a method of performing alkaline etching treatment, desmutting treatment with acid, and electrochemical surface roughening treatment using a different electrolyte solution a plurality of times on an aluminum plate. It is not limited. In these methods, after the electrochemical surface roughening treatment, an alkali etching treatment and an acid desmutting treatment may be further performed.
The support obtained by these methods has a structure in which two or more kinds of irregularities with different periods are superimposed on the surface, and is excellent in both stain resistance and printing durability when used as a lithographic printing plate. It has the following advantages.
Hereafter, each process of the surface treatment applicable in this invention is demonstrated in detail.

(Mechanical roughening treatment)
The mechanical roughening treatment is effective as a roughening treatment means because it can form an uneven surface with an average wavelength of 5 to 100 μm at a lower cost than the electrochemical roughening treatment. is there. Examples of the mechanical surface roughening treatment include, for example, a wire brush grain method in which the aluminum surface is scratched with a metal wire, a ball grain method in which the aluminum surface is grained with a polishing ball and an abrasive, JP-A-6-135175, and Japanese Patent Publication A brush grain method in which the surface is grained with a nylon brush and an abrasive described in Japanese Patent No. 50-40047 can be used. A transfer method in which the uneven surface is pressed against the aluminum plate can also be used. That is, in addition to the methods described in JP-A-55-74898, JP-A-60-36195, and JP-A-60-20396, transfer is performed several times. The method described in Japanese Patent Application No. -55871 and Japanese Patent Application No. 4-204235 (Japanese Patent Laid-Open No. 6-024168) characterized in that the surface is elastic is also applicable.

  In addition, by using electric discharge machining, shot blasting, laser, plasma etching, etc., a method of repeatedly transferring using a transfer roll etched with fine irregularities, and an uneven surface coated with fine particles on an aluminum plate It is also possible to use a method in which an uneven pattern corresponding to the average diameter of the fine particles is repeatedly transferred to the aluminum plate a plurality of times by contacting the surface and applying a pressure a plurality of times from above. As a method for imparting fine irregularities to the transfer roll, known methods described in JP-A-3-8635, JP-A-3-66404, JP-A-63-65017, etc. may be used. it can. Further, a fine groove may be cut in two directions using a die, a cutting tool, a laser, or the like on the roll surface, and a square unevenness may be formed on the surface. The roll surface may be subjected to a known etching process or the like so that the formed square irregularities are rounded. Further, in order to increase the surface hardness, quenching, hard chrome plating, or the like may be performed. In addition, as the mechanical surface roughening treatment, methods described in JP-A Nos. 61-162351 and 63-104889 can be used. In the present invention, the above-described methods can be used in combination in consideration of productivity and the like. These mechanical surface roughening treatments are preferably performed before the electrochemical surface roughening treatment.

Hereinafter, the brush grain method used suitably as a mechanical roughening process is demonstrated. The brush grain method generally uses a roller-shaped brush in which a large number of brush hairs such as synthetic resin hair made of synthetic resin such as nylon (trade name), propylene, and vinyl chloride resin are implanted on the surface of a cylindrical body. This is performed by rubbing one or both of the surfaces of the aluminum plate while spraying a slurry liquid containing an abrasive on a rotating roller brush. Instead of the roller brush and the slurry liquid, a polishing roller which is a roller having a polishing layer on the surface can be used. When a roller brush is used, the flexural modulus is preferably 10,000 to 40,000 kg / cm ² , more preferably 15,000 to 35,000 kg / cm ² , and the bristle strength is preferably Brush hair that is 500 g or less, more preferably 400 g or less is used. The diameter of the brush bristles is generally 0.2 to 0.9 mm. The length of the bristle can be appropriately determined according to the outer diameter of the roller brush and the diameter of the trunk, but is generally 10 to 100 mm.

A well-known thing can be used for an abrasive | polishing agent. For example, abrasives such as pumicestone, silica sand, aluminum hydroxide, alumina powder, silicon carbide, silicon nitride, volcanic ash, carborundum, and gold sand; a mixture thereof can be used. Of these, pumiston and silica sand are preferable.
In particular, silica sand is preferable in terms of excellent surface roughening efficiency because it is harder and less likely to break than Pamiston. The average particle diameter of the abrasive is preferably 3 to 50 μm, and more preferably 6 to 45 μm from the viewpoints of excellent surface roughening efficiency and narrowing the graining pitch. For example, the abrasive is suspended in water and used as a slurry. In addition to the abrasive, the slurry liquid may contain a thickener, a dispersant (for example, a surfactant), a preservative, and the like. The specific gravity of the slurry liquid is preferably 0.5-2.

  As an apparatus suitable for the mechanical surface roughening treatment as described above, for example, an apparatus described in Japanese Patent Publication No. 50-40047 can be given.

(Electrochemical roughening treatment)
In the electrochemical surface roughening treatment, an electrolytic solution used for the electrochemical surface roughening treatment using a normal alternating current can be used. Among these, a characteristic uneven structure can be formed on the surface by using an electrolytic solution mainly composed of hydrochloric acid or nitric acid. As the electrolytic surface roughening treatment in the present invention, it is preferable to perform the first and second electrolytic treatments with an alternating waveform current in an acidic solution before and after the cathodic electrolytic treatment. By cathodic electrolysis, hydrogen gas is generated on the surface of the aluminum plate and smut is generated, so that the surface state is made uniform, and uniform electrolytic surface roughening is possible during subsequent electrolysis with alternating waveform current. . This electrolytic surface roughening treatment can be performed, for example, according to the electrochemical grain method (electrolytic grain method) described in Japanese Patent Publication No. 48-28123 and British Patent No. 896,563. This electrolytic grain method uses a sinusoidal alternating current, but it may be performed using a special waveform as described in JP-A-52-58602. Further, the waveform described in JP-A-3-79799 can also be used. JP-A-55-158298, JP-A-56-28898, JP-A-52-58602, JP-A-52-152302, JP-A-54-85802, JP-A-60-190392, JP-A-58-120531, JP-A-63-176187, JP-A-1-5889, JP-A-1-280590, JP-A-1-118489, JP-A-1-148592, and JP-A-1-17896. JP-A-1-188315, JP-A-1-1549797, JP-A-2-235794, JP-A-3-260100, JP-A-3-253600, JP-A-4-72079, JP-A-4-72098, The methods described in JP-A-3-267400 and JP-A-1-141094 can also be applied. In addition to the above, it is also possible to perform electrolysis using an alternating current having a special frequency that has been proposed as a method of manufacturing an electrolytic capacitor. For example, it is described in US Pat. Nos. 4,276,129 and 4,676,879.

  Various electrolyzers and power sources have been proposed. U.S. Pat. No. 4,203,637, JP-A-56-123400, JP-A-57-59770, JP-A-53-12738, JP-A-53. -32821, JP-A 53-32822, JP-A 53-32823, JP-A 55-122896, JP-A 55-13284, JP-A 62-127500, JP-A-1-52100 JP-A-1-52098, JP-A-60-67700, JP-A-1-230800, JP-A-3-257199 and the like can be used. Also, JP-A-52-58602, JP-A-52-152302, JP-A-53-12738, JP-A-53-12739, JP-A-53-32821, JP-A-53-32822, JP 53-32833, JP 53-32824, JP 53-32825, JP 54-85802, JP 55-122896, JP 55-13284, JP 48-28123, JP-B-51-7081, JP-A-52-13338, JP-A-52-133840, JP-A-52-133844, JP-A-52-133845, JP-A-53- Nos. 149135 and 54-146234 can be used.

  As an acidic solution which is an electrolytic solution, in addition to nitric acid and hydrochloric acid, U.S. Pat. Nos. 4,671,859, 4,661,219, 4,618,405, 4,600, 482, 4,566,960, 4,566,958, 4,566,959, 4,416,972, 4,374,710, The electrolyte solution described in each specification of 4,336,113 and 4,184,932 can also be used.

  The concentration of the acidic solution is preferably 0.5 to 2.5% by mass, but it is particularly preferably 0.7 to 2.0% by mass in consideration of use in the smut removal treatment. Moreover, it is preferable that liquid temperature is 20-80 degreeC, and it is more preferable that it is 30-60 degreeC.

  An aqueous solution mainly composed of hydrochloric acid or nitric acid is an aqueous solution of hydrochloric acid or nitric acid having a concentration of 1 to 100 g / L, nitric acid compounds having nitrate ions such as aluminum nitrate, sodium nitrate, and ammonium nitrate, or aluminum chloride, sodium chloride, ammonium chloride, etc. At least one of the hydrochloric acid compounds having hydrochloric acid ions can be used by adding in a range from 1 g / L to saturation. Moreover, the metal contained in aluminum alloys, such as iron, copper, manganese, nickel, titanium, magnesium, a silica, may melt | dissolve in the aqueous solution which has hydrochloric acid or nitric acid as a main component. Preferably, a solution obtained by adding aluminum chloride, aluminum nitrate or the like to an aqueous solution of hydrochloric acid or nitric acid having a concentration of 0.5 to 2% by mass so that aluminum ions are 3 to 50 g / L is preferably used.

  Further, by adding and using a compound capable of forming a complex with Cu, uniform graining is possible even for an aluminum plate containing a large amount of Cu. Examples of the compound capable of forming a complex with Cu include ammonia; hydrogen atom of ammonia such as methylamine, ethylamine, dimethylamine, diethylamine, trimethylamine, cyclohexylamine, triethanolamine, triisopropanolamine, EDTA (ethylenediaminetetraacetic acid). And amines obtained by substituting with a hydrocarbon group (aliphatic, aromatic, etc.); metal carbonates such as sodium carbonate, potassium carbonate, potassium hydrogen carbonate and the like. In addition, ammonium salts such as ammonium nitrate, ammonium chloride, ammonium sulfate, ammonium phosphate, and ammonium carbonate are also included. The temperature is preferably 10-60 ° C, more preferably 20-50 ° C.

  The AC power supply wave used for the electrochemical surface roughening treatment is not particularly limited, and a sine wave, a rectangular wave, a trapezoidal wave, a triangular wave or the like is used, but a rectangular wave or a trapezoidal wave is preferable, and a trapezoidal wave is particularly preferable. A trapezoidal wave means what was shown in FIG. In this trapezoidal wave, the time (TP) until the current reaches a peak from zero is preferably 1 to 3 msec. If it is less than 1 msec, processing irregularities such as chatter marks that occur perpendicular to the traveling direction of the aluminum plate are likely to occur. When TP exceeds 3 msec, especially when a nitric acid electrolyte is used, it is easily affected by trace components in the electrolyte typified by ammonium ions and the like that spontaneously increase by electrolytic treatment, and uniform graining is performed. It becomes hard to be broken. As a result, the stain resistance tends to decrease when a lithographic printing plate is obtained.

  A duty ratio of trapezoidal wave alternating current of 1: 2 to 2: 1 can be used. However, as described in Japanese Patent Laid-Open No. 5-195300, in an indirect power feeding method in which no conductor roll is used for aluminum, a duty is used. A ratio of 1: 1 is preferred. A trapezoidal AC frequency of 0.1 to 120 Hz can be used, but 50 to 70 Hz is preferable in terms of equipment. When the frequency is lower than 50 Hz, the carbon electrode of the main electrode is easily dissolved, and when the frequency is higher than 70 Hz, it is easily affected by an inductance component on the power supply circuit, and the power supply cost is increased.

  One or more AC power supplies can be connected to the electrolytic cell. As shown in FIG. 6, the current ratio between the AC anode and cathode applied to the aluminum plate facing the main electrode is controlled to achieve uniform graining and to dissolve the carbon of the main electrode. In addition, it is preferable to install an auxiliary anode and divert part of the alternating current. In FIG. 6, 111 is an aluminum plate, 112 is a radial drum roller, 113a and 113b are main poles, 114 is an electrolytic treatment solution, 115 is an electrolyte supply port, and 116 is a slit. 117 is an electrolyte passage, 118 is an auxiliary anode, 119a and 119b are thyristors, 120 is an AC power source, 121 is a main electrolytic cell, and 122 is an auxiliary anode cell. An anodic reaction that acts on the aluminum plate facing the main electrode by diverting a part of the current value as a direct current to an auxiliary anode provided in a separate tank from the two main electrodes via a rectifier or switching element It is possible to control the ratio between the current value for the current and the current value for the cathode reaction. On the aluminum plate facing the main electrode, the ratio of the amount of electricity involved in the anodic reaction and the cathodic reaction (the amount of electricity at the time of cathode / the amount of electricity at the time of anode) is preferably 0.3 to 0.95.

  As the electrolytic cell, electrolytic cells used for known surface treatments such as a vertical type, a flat type, and a radial type can be used, but a radial type electrolytic cell as described in JP-A-5-195300 is particularly preferable. . The electrolytic solution passing through the electrolytic cell may be parallel to the traveling direction of the aluminum web or may be a counter.

-Nitric acid electrolysis-
Pits having an average opening diameter of 0.5 to 5 μm can be formed by electrochemical surface roughening using an electrolytic solution mainly composed of nitric acid. However, when the amount of electricity is relatively large, the electrolytic reaction is concentrated, and honeycomb pits exceeding 5 μm are also generated. To obtain such a grain, the total amount of electricity furnished to anode reaction on the aluminum plate up until the electrolysis reaction is completed is preferably from ^{1~1000C / dm 2, 50~300C / dm} 2 It is more preferable that The current density at this time is preferably ²⁰ to 100 A / dm ² . Further, when a high concentration or high temperature nitric acid electrolytic solution is used, a small wave structure having an average opening diameter of 0.2 μm or less can be formed.

-Hydrochloric acid electrolysis-
Since hydrochloric acid itself has a strong ability to dissolve aluminum, it is possible to form fine irregularities on the surface with only slight electrolysis. These fine irregularities have an average opening diameter of 0.01 to 0.2 μm and are uniformly generated on the entire surface of the aluminum plate. Such grained total amount of electricity furnished to anode reaction on the aluminum plate up until the electrolysis reaction is completed in order to obtain the, is preferably from 1~100C / dm ^2, in 20~70C / dm ² More preferably. The current density at this time is preferably ²⁰ to 50 A / dm ² .

In such an electrochemical surface roughening treatment with an electrolyte mainly composed of hydrochloric acid, a large crater-like swell is simultaneously formed by increasing the total amount of electricity involved in the anode reaction to 400 to 1000 C / dm ^2. In this case, fine irregularities having an average opening diameter of 0.01 to 0.4 μm are formed on the entire surface by being superimposed on a crater-like wave having an average opening diameter of 10 to 30 μm.

The aluminum plate is preferably subjected to cathodic electrolysis treatment during the first and second electrolytic surface-roughening treatments performed in the electrolytic solution such as nitric acid and hydrochloric acid. By this cathodic electrolysis treatment, smut is generated on the surface of the aluminum plate, and hydrogen gas is generated to enable more uniform electrolytic surface roughening treatment. This cathodic electrolysis treatment is carried out in an acidic solution at a cathode electric quantity of preferably 3 to 80 C / dm ² , more preferably 5 to 30 C / dm ² . If the amount of cathodic electricity is less than 3 C / dm ² , the amount of smut adhesion may be insufficient, and if it exceeds 80 C / dm ² , the amount of smut adhesion may be excessive. Further, the electrolytic solution may be the same as or different from the solution used in the first and second electrolytic surface roughening treatments.

(Alkaline etching treatment)
The alkali etching treatment is a treatment for dissolving the surface layer by bringing the aluminum plate into contact with an alkaline solution.
The alkali etching treatment performed before the electrolytic surface roughening treatment removes rolling oil, dirt, natural oxide film, etc. on the surface of the aluminum plate (rolled aluminum) when the mechanical surface roughening treatment is not performed. For this purpose, and when the mechanical surface roughening treatment has already been performed, the edge portion of the unevenness generated by the mechanical surface roughening treatment is dissolved, and the steep unevenness is converted into a surface having smooth undulations. It is done for the purpose of changing.

If you do not mechanical surface-roughening treatment before the alkali etching treatment, the etching amount is preferably from 0.1 to 10 g / ^{m 2,} and more preferably 1 to 5 g / ^{m 2.} If the etching amount is less than 0.1 g / m ² , rolling oil, dirt, natural oxide film, etc. may remain on the surface, so that uniform pits cannot be generated in the subsequent electrolytic surface roughening treatment, resulting in unevenness. May occur. On the other hand, when the etching amount is 1 to 10 g / m ² , the surface rolling oil, dirt, natural oxide film, and the like are sufficiently removed. An etching amount exceeding the above range is economically disadvantageous.

When performing mechanical surface-roughening treatment before the alkali etching treatment, the etching amount is preferably from 3 to 20 g / ^{m 2,} and more preferably 5 to 15 g / ^{m 2.} If the etching amount is less than 3 g / m ² , unevenness formed by mechanical surface roughening may not be smoothed, and uniform pit formation may not be possible in subsequent electrolytic treatment. In addition, the stain may deteriorate during printing. On the other hand, when the etching amount exceeds 20 g / m ² , the concavo-convex structure may disappear.

The alkali etching treatment performed immediately after the electrolytic surface roughening treatment is performed for the purpose of dissolving the smut generated in the acidic electrolytic solution and dissolving the edge portion of the pit formed by the electrolytic surface roughening treatment. . Since the pits formed by the electrolytic surface roughening treatment are different depending on the type of the electrolytic solution, the optimum etching amount is also different, but the etching amount of the alkali etching treatment performed after the electrolytic surface roughening treatment is 0.1 to 5 g / m. ² is preferred. When a nitric acid electrolyte is used, the etching amount needs to be set larger than when a hydrochloric acid electrolyte is used. When the electrolytic surface roughening treatment is performed a plurality of times, an alkali etching treatment can be performed as necessary after each treatment.

  Examples of the alkali used in the alkaline solution include caustic alkali and alkali metal salts. Specifically, examples of caustic alkali include caustic soda and caustic potash. Examples of alkali metal salts include alkali metal silicates such as sodium silicate, sodium silicate, potassium metasilicate, and potassium silicate; alkali metal carbonates such as sodium carbonate and potassium carbonate; sodium aluminate and alumina. Alkali metal aluminates such as potassium acid; alkali metal aldones such as sodium gluconate and potassium gluconate; dibasic sodium phosphate, dibasic potassium phosphate, tribasic sodium phosphate, tertiary potassium phosphate, etc. An alkali metal hydrogen phosphate is mentioned. Among these, a caustic alkali solution and a solution containing both a caustic alkali and an alkali metal aluminate are preferable from the viewpoint of high etching rate and low cost. In particular, an aqueous solution of caustic soda is preferable.

  Although the density | concentration of an alkaline solution can be determined according to the etching amount, it is preferable that it is 1-50 mass%, and it is more preferable that it is 10-35 mass%. When aluminum ions are dissolved in the alkaline solution, the concentration of aluminum ions is preferably 0.01 to 10% by mass, and more preferably 3 to 8% by mass. The temperature of the alkaline solution is preferably 20 to 90 ° C. The treatment time is preferably 1 to 120 seconds.

  Examples of the method of bringing the aluminum plate into contact with the alkaline solution include, for example, a method in which the aluminum plate is passed through a tank containing the alkaline solution, a method in which the aluminum plate is immersed in a tank containing the alkaline solution, The method of spraying on the surface of a board is mentioned.

(Desmut treatment)
After the electrolytic surface roughening treatment or alkali etching treatment, pickling (desmut treatment) is performed to remove dirt (smut) remaining on the surface. Examples of the acid used include nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, and borohydrofluoric acid. The desmutting treatment is performed, for example, by bringing the aluminum plate into contact with an acidic solution having a concentration of 0.5 to 30% by mass (containing 0.01 to 5% by mass of aluminum ions) such as hydrochloric acid, nitric acid, and sulfuric acid. . Examples of the method of bringing the aluminum plate into contact with the acidic solution include, for example, a method of passing the aluminum plate through a bath containing the acidic solution, a method of immersing the aluminum plate in a bath containing the acidic solution, and an acidic solution containing aluminum. The method of spraying on the surface of a board is mentioned. In the desmutting treatment, the acid solution is mainly composed of an aqueous solution mainly composed of nitric acid or an aqueous solution mainly composed of hydrochloric acid discharged in the above-described electrolytic surface-roughening treatment, or sulfuric acid discharged in an anodic oxidation process described later. It is possible to use a waste solution of an aqueous solution. It is preferable that the liquid temperature of a desmut process is 25-90 degreeC. Moreover, it is preferable that processing time is 1-180 second. Aluminum and aluminum alloy components may be dissolved in the acidic solution used for the desmut treatment.

  The aluminum plate roughened as described above is subjected to an anodizing treatment as necessary in order to enhance the water retention and wear resistance of the surface as desired. As the electrolyte used for the anodizing treatment of the aluminum plate, various electrolytes that form a porous oxide film can be used. In general, sulfuric acid, phosphoric acid, oxalic acid, chromic acid, or a mixed acid thereof is used. The concentration of these electrolytes is appropriately determined depending on the type of electrolyte.

The treatment conditions for anodization vary depending on the electrolyte used, and thus cannot be specified in general. In general, however, the electrolyte concentration is 1 to 80% by mass solution, the liquid temperature is 5 to 70 ° C., and the current density is 5 to 60 A / dm ^2. A voltage of 1 to 100 V and an electrolysis time of 10 seconds to 5 minutes are suitable. If the amount of the anodic oxide film is less than 2.0 g / m ² , the non-image portion of the planographic printing plate is likely to be scratched, and so-called “scratch stain” in which ink adheres to the scratch portion during printing tends to occur.
After the anodizing treatment, the aluminum surface is preferably further subjected to a hydrophilic treatment with silicate.

(Silicate processing)
Silicate treatment, that is, hydrophilization treatment with an aqueous solution of an alkali metal silicate such as sodium silicate or potassium silicate is disclosed in US Pat. No. 2,714,066 and US Pat. No. 3,181,461. Can be carried out according to the methods and procedures described in the document. Examples of the alkali metal silicate include sodium silicate, potassium silicate, and lithium silicate. The aqueous solution of alkali metal silicate may contain an appropriate amount of sodium hydroxide, potassium hydroxide, lithium hydroxide or the like. The aqueous solution of alkali metal silicate may contain an alkaline earth metal salt or a Group 4 (Group IVA) metal salt. Examples of the alkaline earth metal salt include nitrates such as calcium nitrate, strontium nitrate, magnesium nitrate, and barium nitrate; sulfates; hydrochlorides; phosphates; acetates; oxalates; Examples of Group 4 (Group IVA) metal salts include titanium tetrachloride, titanium trichloride, potassium titanium fluoride, titanium oxalate, titanium sulfate, titanium tetraiodide, zirconium chloride, zirconium dioxide, zirconium oxychloride. And zirconium tetrachloride. These alkaline earth metal salts and Group 4 (Group IVA) metal salts are used alone or in combination of two or more.

The amount of silicate adhering is 1.0 to 30.0 mg / m ² , more preferably 2.0 to 20.0, from the viewpoint of ink bleeding, stain resistance, and printing durability.

[Polyester film support]
In the present invention, a polyester film suitable as a lithographic printing plate support preferably has a hydrophilic layer containing the following sol-gel structure on its surface.
In addition, the hydrophilic layer containing this sol-gel structure is applicable also to the support body of materials other than a polyester film.

(Hydrophilic layer containing sol-gel structure)
The hydrophilic layer containing a sol-gel structure in the present invention (hereinafter sometimes simply referred to as a hydrophilic layer) contains a hydrophilic binder. The hydrophilic binder is preferably a sol-gel converting material composed of a metal hydroxide and metal oxide system, and among them, a sol-gel converting system having a property of forming a polysiloxane gel structure is most preferable.
In addition, this hydrophilic binder acts as a dispersion medium for the components of the hydrophilic layer, improving the physical strength of the layer, improving the dispersibility of the components constituting the layer, improving the coating properties, and improving the printability. The structure is suitable for various purposes such as the convenience of plate making workability.
The hydrophilic binder is preferably 30% by mass or more, and more preferably 35% by mass or more, based on the total solid content of the hydrophilic layer. If it is 30% by mass or less, the hydrophilic layer cannot obtain sufficient water resistance and abrasion resistance.

  As the hydrophilic binder suitably used for the hydrophilic layer in the present invention, an organic polymer compound for the purpose of imparting appropriate strength and hydrophilicity of the surface as the hydrophilic layer can be used. Specifically, polyvinyl alcohol (PVA), modified PVA such as carboxy-modified PVA, starch and derivatives thereof, cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose, casein, gelatin, polyvinylpyrrolidone, vinyl acetate-crotonic acid Polymers, styrene-maleic acid copolymers, polyacrylic acid and salts thereof, polyacrylamides, and water-soluble acrylic copolymers containing water-soluble acrylic monomers such as acrylic acid and acrylic amide as main components Water-soluble resin is mentioned.

  In addition, as a water-resistant agent for crosslinking and curing the organic polymer compound, initial condensates of aminoplasts such as glyoxal, melamine formaldehyde resin, urea formaldehyde resin, methylolated polyamide resin, polyamide / polyamine / epichlorohydrin adduct, Examples thereof include polyamide epichlorohydrin resin and modified polyamide polyimide resin. In addition, ammonium chloride, a crosslinking catalyst for a silane coupling agent, and the like can be used in combination.

The systems capable of sol-gel conversion that can be particularly preferably applied to the present invention are Sakuo Sakuo “Science of Sol-Gel Method”, Agne Jofusha (published) (1988), Satoshi Hirashima “Latest Sol-Gel Method” Is described in detail in books such as “Functional Thin Film Fabrication Technology” by the General Technology Center (published) (1992).
That is, the bonding group coming out of the polyvalent element forms a network structure through oxygen atoms, and at the same time, the polyvalent metal also has an unbonded hydroxyl group or an alkoxy group, resulting in a resinous structure in which these are mixed. The polymer is in a sol state at the stage where there are many alkoxy groups and hydroxyl groups before coating, and after coating, as the ester bond proceeds, the network-like resinous structure becomes stronger and gel state. become. Further, in addition to the property of changing the hydrophilicity of the resin structure, it also has a function of modifying the surface of the solid fine particles by bonding a part of the hydroxyl groups to the solid fine particles to change the hydrophilicity. The polyvalent binding element of the compound having a hydroxyl group or an alkoxy group that performs sol-gel conversion is aluminum, silicon, titanium, zirconium, and the like. Any of these can be used in the present invention, but the following can be most preferably used. A sol-gel conversion system using a siloxane bond will be described. Sol-gel conversion using aluminum, titanium, and zirconium can be performed by replacing silicon described below with each element.

  The hydrophilic matrix formed by sol-gel conversion is preferably a resin having a siloxane bond and a silanol group, and the hydrophilic layer in the present invention is a sol system containing a silane compound having at least one silanol group. The coating solution is formed by the progress of hydrolysis and condensation of silanol groups to form a siloxane skeleton structure and progress of gelation over time after coating. A siloxane resin forming a gel structure is represented by the following general formula (A), and a silane compound having at least one silanol group is represented by the following general formula (B). Moreover, the substance system contained in the hydrophilic layer that changes from hydrophilicity to hydrophobicity does not necessarily need to be the silane compound of the general formula (B) alone, and generally consists of an oligomer in which the silane compound is partially hydrolyzed. Alternatively, it may be a mixed composition of a silane compound and its oligomer.

The siloxane-based resin of the general formula (A) is formed by sol-gel conversion from a dispersion containing at least one silane compound represented by the following general formula (B), and R ⁰¹ in the general formula (A). At least one to R ⁰³ represents a hydroxyl group and the other represents an organic residue selected from R ⁰ and Y ¹ symbols in the following general formula (B).

Formula (B) (R ⁰ ) _n Si (Y ¹ ) _4-n

In the general formula (B), R ⁰ represents a hydroxyl group, a hydrocarbon group, or a heterocyclic group. Y ¹ represents a hydrogen atom, a halogen atom, —OR ¹¹ , —OCOR ¹² , or —N (R ¹³ ) (R ¹⁴ ) (R ¹¹ , R ¹² each represents a hydrocarbon group, and R ¹³ , R ¹⁴ May be the same or different and each represents a hydrogen atom or a hydrocarbon group). n represents 0, 1, 2 or 3.

As the hydrocarbon group or heterocyclic group of R ^{0 in} the general formula (B), a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, Propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, etc .; as a group substituted by these groups, a halogen atom (chlorine atom, fluorine atom, bromine atom) ), Hydroxy group, thiol group, carboxy group, sulfo group, cyano group, epoxy group, —OR ¹ group (R ¹ is methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group, Decyl group, propenyl group, butenyl group, hexenyl group, octenyl group, 2-hydroxyethyl group, 3-chloropropyl group, 2-cyanoethyl group, N, N-dimethylamino group Indicating group, bromoethyl group, 2- (2-methoxyethyl) oxyethyl group, 2-methoxycarbonylethyl group, 3-carboxypropyl group, a benzyl group, etc.), - OCOR ² group ^{(R 2,} said R ¹ represents the same content as ¹ ), -COOR ² group, -COR ² group, -N (R ³ ) (R ³ ) (R ³ represents the same content as a hydrogen atom or R ¹ , May be different), -NHCONHR ² group, -NHCOOR ² group, -Si (R ² ) ₃ group, -CONHR ³ group, -NHCOR ² group, etc. These substituents may be included in the alkyl group. Optionally substituted), an optionally substituted linear or branched alkenyl group having 2 to 12 carbon atoms (for example, vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, octenyl group) Examples of the group substituted with these groups such as a nyl group, a decenyl group, and a dodecenyl group include those having the same content as the group substituted with the alkyl group), and are substituted with 7 to 14 carbon atoms. Aralkyl groups (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, etc.); Those having the same contents may be mentioned, and a plurality of them may be substituted), an optionally substituted alicyclic group having 5 to 10 carbon atoms (for example, a cyclopentyl group, a cyclohexyl group, a 2-cyclohexylethyl group, Examples of the group substituted by these groups such as 2-cyclopentylethyl group, norbornyl group, adamantyl group, and the like include those having the same contents as the substituents of the alkyl group. A plurality of substituted groups), an aryl group having 6 to 12 carbon atoms which may be substituted (for example, a phenyl group or a naphthyl group, and the substituent is the same as the group substituted by the alkyl group) Or a heterocyclic group which may be condensed (for example, the above-mentioned group may be substituted), or containing at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom. Heterocycles include pyran ring, furan ring, thiophene ring, morpholine ring, pyrrole ring, thiazole ring, oxazole ring, pyridine ring, piperidine ring, pyrrolidone ring, benzothiazole ring, benzoxazole ring, quinoline ring, tetrahydrofuran ring, etc. , May contain a substituent. Examples of the substituent include those having the same content as the substituent in the alkyl group, and a plurality of substituents may be substituted.

As the —OR ¹¹ group, —OCOR ¹² group, or N (R ¹³ ) (R ¹⁴ ) group of Y ^{1 in} the general formula (B), for example, the following groups are represented.
In the -OR ¹¹ group, R ¹¹ is an aliphatic group having 1 to 10 carbon atoms which may be substituted (for example, methyl group, ethyl group, propyl group, butoxy group, heptyl group, hexyl group, pentyl group, octyl group). Group, nonyl group, decyl group, propenyl group, butenyl group, heptenyl group, hexenyl group, octenyl group, decenyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 2-methoxyethyl group, 2- (methoxyethyloxo) ) Ethyl group, 2- (N, N-diethylamino) ethyl group, 2-methoxypropyl group, 2-cyanoethyl group, 3-methyloxapropyl group, 2-chloroethyl group, cyclohexyl group, cyclopentyl group, cyclooctyl group, chloro Cyclohexyl group, methoxycyclohexyl group, benzyl group, phenethyl group, dimethoxybe Jill group, a methylbenzyl group, bromobenzyl group, and the like).

In the -OCOR ¹² group, R ¹² is an aliphatic group having the same content as R ¹¹ or an optionally substituted aromatic group having 6 to 12 carbon atoms (the aromatic group is an aryl group in the R). And the same as those exemplified in the above.
More preferably, the total number of carbon atoms of R ¹¹ and R ¹² is 16 or less.

In the —N (R ¹³ ) (R ¹⁴ ) group, R ¹³ and R ¹⁴ may be the same or different from each other, and each may be a hydrogen atom or an optionally substituted aliphatic group having 1 to 10 carbon atoms. Represents a group (for example, those having the same contents as R ¹¹ of the —OR ¹¹ group described above).

Specific examples of the silane compound represented by the general formula (B) include the following.
That is, tetrachlorosilane, tetrabromosilane, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, methyltrichlorosilane, methyltribromosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxy Silane, methyltri-t-butoxysilane, ethyltrichlorosilane, ethyltribromosilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltrit-butoxysilane, n-propyltrichlorosilane, n-propyltribromo Silane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltriisopropoxysilane, n-propyltrit-butoxysilane, -Hexyltrichlorosilane, n-hexyltribromosilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexyltriisopropoxysilane, n-hexyltri-t-butoxysilane, n-decyltrichloro Silane, n-decyltribromosilane, n-decyltrimethoxysilane, n-decyltriethoxysilane, n-decyltriisopropoxysilane, n-decyltrit-butoxysilane, n-octadecyltrichlorosilane, n-octadecyltribromo Silane, n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane, n-octadecyltriisopropoxysilane, n-octadecyltri-t-butoxysilane, phenyltrichlorosilane, phenyltribromosilane, phenyl Limethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, phenyltri-t-butoxysilane, dimethoxydiethoxysilane, dimethyldichlorosilane, dimethyldibromosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldichlorosilane , Diphenyldibromosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldichlorosilane, phenylmethyldibromosilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, triethoxyhydrosilane, tribromohydrosilane, trimethoxyhydrosilane, Isopropoxyhydrosilane, tri-t-butoxyhydrosilane, vinyltrichlorosilane, vinyltribromosilane, vinyltrime Toxisilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltri-t-butoxysilane, trifluoropropyltrichlorosilane, trifluoropropyltribromosilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, trifluoropropyltri Isopropoxysilane, trifluoropropyltri-t-butoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane,

γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriisopropoxysilane, γ-glycidoxypropyltri-t-butoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyl Diethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriisopropoxysilane, γ-methacryloxypropyltrit-butoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyl Diethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropyltrit-butoxysilane, γ-mercaptopropylmethyldi Toxisilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltriisopropoxysilane, γ-mercaptopropyltri-t-butoxysilane, β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and the like.

A metal compound capable of forming a film by bonding to a resin during sol-gel conversion of Ti, Zn, Sn, Zr, Al, etc. together with the silane compound represented by the general formula (B) used for forming the hydrophilic layer according to the present invention Can be used in combination. Examples of the metal compound to be used include Ti (OR ² ) ₄ (R ² is methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, etc.), TiCl ₄ , Zn (OR ² ) ₂ , Zn (CH ₃ COCHCOCH ₃ ) ₂ , Sn (OR ² ) ₄ , Sn (CH ₃ COCHCOCH ₃ ) ₄ , Sn (OCOR ² ) ₄ , SnCl ₄ , Zr (OR ² ) ₄ , Zr (CH ₃ COCHCOCH ₃ ) ₄ al ^(OR _{2) 3} and the like.

  In addition, this gel structure matrix has a silane coupling group at the end of the polymer main chain for the purpose of improving physical properties such as film strength and flexibility, improving coating properties, and adjusting hydrophilicity. It is possible to add a hydrophilic polymer or a crosslinking agent.

  Examples of the hydrophilic polymer having a silane coupling group at the end of the polymer main chain include a polymer represented by the following general formula (C).

In the general formula (C), R ¹ , R ² , R ³ , and R ⁴ each represent a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms, m represents 0, 1, or 2, n represents an integer of 1 to 8, and p represents an integer of 30 to 300. Y represents —NHCOCH ₃ , —CONH ₂ , —CON (CH ₃ ) ₂ , —COCH ₃ , —OCH ₃ , —OH, —CO ₂ M, or CONHC (CH ₃ ) ₂ SO ₃ M; It represents one selected from the group consisting of a hydrogen atom, an alkali metal, an alkaline earth metal and onium.

  L in the general formula (C) represents a single bond or an organic linking group. Here, the organic linking group represents a polyvalent linking group composed of a nonmetallic atom, specifically 1 to 60 carbon atoms. It is a group consisting of atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 20 sulfur atoms. More specific examples of the linking group include the following structural units or groups formed by combining these structural units.

  Specific examples of the hydrophilic polymer having a silane coupling group represented by the general formula (C) include the following polymers. In the specific examples below, p can be any value between 100 and 250.

The hydrophilic polymer according to the present invention includes a monomer capable of radical polymerization represented by the following general formula (C-1) and a silane having chain transfer ability in radical polymerization represented by the following general formula (C-2). And can be synthesized by radical polymerization using a coupling agent. Since the compound represented by the general formula (C-2) is a silane coupling agent and has a chain transfer ability, it is possible to synthesize a polymer in which a silane coupling group is introduced at the end of the polymer main chain in radical polymerization. .
In the following general formula (C-1) and general formula (C-2), R ¹ , R ² , R ³ , R ⁴ , m, n, L, and Y are the same as those in the formula (C). Synonymous with R ¹ , R ² , R ³ , R ⁴ , m, n, L, and Y.

Thickness of the hydrophilic layer in the invention is preferably from 0.1 to 10 g / ^{m 2,} and more preferably 0.5 to 5 g / ^{m 2.}

  The hydrophilic layer as described above may be provided directly on the polyester film, but in order to improve the adhesion between the polyester film and the hydrophilic layer, an intermediate layer (adhesion layer) containing polyacrylamide or the like is used. ) May be provided.

By the method as described above, an image portion is formed by the ink composition of the present invention, and a lithographic printing plate is obtained.
Since the obtained lithographic printing plate has an image portion having excellent fixability and high mechanical strength, a large number of printed matter can be printed.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.

<Synthesis of dispersant [BZ-2] used in wet dispersion method>
The dispersant [BZ-2] having the following structure is a polymer of stearyl methacrylate having a methacryloyl group at the terminal by radical polymerization of stearyl methacrylate in the presence of 2-mercaptoethanol and further reacting with methacrylic anhydride. The weight average molecular weight was 7,600), and was obtained by radical polymerization with styrene.
The weight average molecular weight of the obtained dispersant [BZ-2] was 110,000.

<Synthesis of Charge Control Agent [CT-1] Used in Wet Dispersion Method>
The charge control agent [CT-1] having the following structure was obtained by reacting 1-octadecene and maleic anhydride copolymer with 1-hexadecylamine.
The weight average molecular weight of the obtained charge control agent [CT-1] was 17,000.

<Synthesis of polymer [AP-1] constituting organic fine particles used in wet dispersion method>
A polymer [AP-1] having the following structure is obtained by polymerizing methyl methacrylate, butyl methacrylate, stearyl methacrylate, and 2- (N, N-diethylamino) ethyl methacrylate as a polymerization initiator (V-601: dimethyl 2,2). It was obtained by radical polymerization using '-azobis (2-methylpropionate)).
The obtained polymer [AP-1] had a weight average molecular weight of 25,000 and a polydispersity (weight average molecular weight / number average molecular weight) of 2.8. The glass transition point (midpoint) was 43 ° C.

<Synthesis of polymer [AP-2] constituting organic fine particles used in wet dispersion method>
A polymer [AP-2] having the following structure comprises styrene, 4-methylstyrene, butyl acrylate, lauryl methacrylate, and N, N, N-trimethylammonium ethyl methacrylate p-toluenesulfonate, as a polymerization initiator (V -601) was used for radical polymerization.
The obtained polymer [AP-2] had a weight average molecular weight of 32,000 and a polydispersity (weight average molecular weight / number average molecular weight) of 2.5. The glass transition point (mid point) was 47 ° C.

<Synthesis of polymer [AP-3] constituting organic fine particles used in wet dispersion method>
Polymer [AP-3] having the following structure comprises methyl methacrylate, butyl methacrylate, stearyl methacrylate, and N, N, N-trimethylammonium ethyl methacrylate p-toluenesulfonate, as a polymerization initiator (V-601). It was obtained by radical polymerization using
The obtained polymer [AP-3] had a weight average molecular weight of 50,000 and a polydispersity (weight average molecular weight / number average molecular weight) of 3.5. The glass transition point (mid point) was 50 ° C.

<Synthesis of polymer [AP-4] constituting organic fine particles used in wet dispersion method>
Polymer [AP-4] having the following structure is formed by using methyl initiator, benzyl methacrylate, butyl methacrylate, and 2- (N, N-dimethylamino) ethyl methacrylate with a polymerization initiator (V-601). Obtained by radical polymerization.
The obtained polymer [AP-4] had a weight average molecular weight of 45,000 and a polydispersity (weight average molecular weight / number average molecular weight) of 3.4. The glass transition point (midpoint) was 38 ° C.

<Preparation of dispersion [EC-1]>
1 g of cyan pigment and 20 g of polymer [AP-1] were placed in a desktop kneader PBV-0.1 manufactured by Irie Shokai Co., Ltd., and the heater temperature was set to 100 ° C. and melt kneaded for 2 hours. 21 g of the obtained mixture was coarsely pulverized with a trioblender manufactured by Trio Science Co., Ltd., and further finely pulverized with a SK-M10 type sample mill manufactured by Kyoritsu Riko Co., Ltd. 21 g of the finely pulverized product thus obtained was predispersed in a paint shaker manufactured by Toyo Seiki Seisakusho together with 7.3 g of the dispersant [BZ-2], Isopar G75 g, and glass beads having a diameter of about 3.0 mm. After removing the glass beads, together with the zirconia ceramic beads having a diameter of about 0.6 mm, the type KDL dynomill manufactured by Shinmaru Enterprises Co., Ltd. was used for 5 hours while maintaining the internal temperature at 25 ° C., followed by 45 ° C. for 5 hours. Dispersion (micronization) was performed at a rotational speed of 000 rpm.
Zirconia ceramic beads are removed from the obtained dispersion, and ISOPAR G316g and a charge control agent [CT-1] 0.6 g are added to contain organic fine particles (polymer [AP-1]) having a volume average particle diameter of 1.02 μm. A dispersion [EC-1] was obtained.

<Preparation of dispersion [EC-2]>
In the preparation of the dispersion [EC-1], the same applies except that the polymer [AP-1] is changed to the polymer [AP-2] and the amount of the dispersant [BZ-2] is changed to 6.0 g. By the method, a dispersion [EC-2] containing organic fine particles (polymer [AP-2]) having a volume average particle size of 1.35 μm was obtained.

<Preparation of dispersion [EC-3]>
In the preparation of the dispersion [EC-1], the polymer [AP-1] was changed to the polymer [AP-3], the amount of the dispersant [BZ-2] was changed to 5.0 g, and the heater temperature was changed to 130 ° C. Except for the above, a dispersion [EC-3] containing organic fine particles (polymer [AP-3]) having a volume average particle size of 1.48 μm was obtained in the same manner.

<Preparation of dispersion [EC-4]>
In the preparation of the dispersion [EC-1], the polymer [AP-1] was changed to the polymer [AP-4], the amount of the dispersant [BZ-2] was changed to 8.0 g, and the heater temperature was changed to 90 ° C. A dispersion [EC-4] containing organic fine particles (polymer [AP-4]) having a volume average particle size of 0.9 μm was obtained in the same manner except that the change was made.
<Preparation of dispersion [EC-5]>
Organic particles having a volume average particle diameter of 1.13 μm were obtained by the same method except that the cyan pigment was not added in the preparation of the dispersion [EC-4]. Thereafter, 1 g of a cyan pigment was added to obtain a dispersion [EC-5].

  Here, physical properties of the organic fine particles constituting the dispersions [EC-1] to [EC-5] obtained as described above are also shown in Table 1 below.

<Synthesis of dispersion stabilizing resin (dispersant) [P-1] used in polymerization granulation method>
A mixed solution of 96 g of octadecyl methacrylate, 4 g of 4- (2-methacryloyloxyethyloxycarbonyl) butyric acid and 200 g of toluene was heated to a temperature of 75 ° C. under a nitrogen stream. As a polymerization initiator, 1.5 g of 2,2′-azobisisobutyronitrile (abbreviation AIBN) was added and reacted for 4 hours. I. B. N. Was added and heated to a temperature of 80 ° C. and reacted for 4 hours.
After cooling the reaction mixture to 25 ° C., 6 g of allyl alcohol was added with stirring, followed by 10 g of dicyclohexylcarbodiimide (abbreviated DCC), 0.1 g of 4- (N, N-diethylamino) pyridine and A mixed solution of 30 g of methylene chloride was added dropwise over 1 hour. The reaction was further continued for 3 hours to complete the reaction. Next, 10 g of 80% formic acid was added to the reaction mixture and the mixture was stirred for 1 hour. Insoluble matters were filtered off, and the filtrate was reprecipitated in 2.5 liters of methanol. After the precipitate was collected by filtration, it was dissolved again in 200 g of toluene, the insoluble matter was filtered off, and the filtrate was reprecipitated in 1 liter of methanol. The precipitate was collected by filtration and dried.
The yield of the obtained polymer: dispersion stabilizing resin [P-1] (the following structure) was 70 g, and Mw was 5 × 10 ⁴ .

<Preparation of organic fine particles [D-1] by polymerization granulation method>
A mixed solution of 7.5 g of dispersion stabilizing resin [P-1], 24 g of methyl methacrylate, 24 g of methyl acrylate, 2 g of acrylic acid, and 106.3 g of Isopar G was heated to 70 ° C. while stirring under nitrogen. V-65: 0.75g was added to this, and it reacted as it was for 2 hours. Furthermore, 0.5 g of a polymerization initiator (V-65) was added and reacted for 2 hours, and then the temperature was raised to 85 ° C. and stirred for 30 minutes. After cooling, a dispersion containing a white dispersion was obtained through a 200-mesh nylon cloth.
The obtained white dispersion (organic fine particles [D-1]) had a volume average particle size of 0.73 μm and a glass transition point (Tg) of 47 ° C.

<Preparation of organic fine particles [D-2] by polymerization granulation method>
In the production of the organic fine particles [D-1], a volume average particle size of 1.10 μm and a glass transition point (Tg) of 45 are obtained in the same manner except that the dispersion stabilizing resin [P-1] is changed to 5.0 g. Organic fine particles [D-2] at 0 ° C. were obtained.

<Preparation of organic fine particles [D-3] by polymerization granulation method>
A mixed solution of 10 g of dispersion stabilizing resin [P-1], 20 g of methyl methacrylate, 30 g of methyl acrylate, and 200.0 g of Isopar G was heated to 70 ° C. while stirring under nitrogen. To this, 0.75 g of a polymerization initiator (V-65) was added and reacted for 2 hours. Further, V-65: 0.5 g was added and reacted for 2 hours, and then the temperature was raised to 85 ° C. and stirred for 30 minutes. After cooling, a dispersion containing a white dispersion was obtained through a 200-mesh nylon cloth.
The obtained white dispersion (organic fine particles [D-3]) had a volume average particle size of 0.56 μm and a glass transition point (Tg) of 40 ° C.

<Preparation of organic fine particles [D-4] by polymerization granulation method>
A mixed solution of 6.5 g of dispersion stabilizing resin [P-1], 18.2 g of methyl methacrylate, 27.2 g of methyl acrylate, 4.6 g of 2- (N, N-diethylamino) ethyl methacrylate, and 200 g of Isopar G The mixture was heated to 70 ° C. with stirring under nitrogen. To this, 0.75 g of a polymerization initiator (V-65) was added and reacted for 2 hours. Further, V-65: 0.5 g was added and reacted for 2 hours, and then the temperature was raised to 85 ° C. and stirred for 30 minutes. After cooling, a dispersion containing a white dispersion was obtained through a 200-mesh nylon cloth.
The obtained white dispersion (organic fine particles [D-4]) had a volume average particle size of 0.58 μm and a glass transition point (Tg) of 48 ° C.

<Preparation of Dispersion [IK-1]>
The dispersion containing the organic fine particles (D-1) obtained as described above is obtained by using Isopar G, the solid content of the organic fine particles is 50 g, and the dispersion contains 20% by mass of the organic fine particles. Then, 5 g of Victoria Pure Blue was added thereto and reacted at 60 ° C. for 4 hours. After completion of the reaction, filtration was performed with a filter of 4 μm, and the charge adjusting agent [CT-1] was added so as to be 0.1% by mass with respect to the ink solid content to obtain a dispersion [IK-1]. This is a blue colored ink composition.

<Preparation of Dispersions [IK-2], [IK-3], [IK-4]>
The same method except that the organic fine particles (D-1) were replaced with the organic fine particles (D-2), (D-3), or (D-4) in the preparation of the dispersion [IK-1]. Dispersions [IK-2], [IK-3], and [IK-4] were obtained.
<Preparation of dispersion [IK-5]>
Dispersion [IK-5] was obtained in the same manner as in the preparation of dispersion [IK-4] except that Victoria Pure Blue was added and no heating was applied.
Here, the physical properties of the organic fine particles constituting the dispersions [IK-1] to [IK-5] obtained as described above are also shown in Table 2 below.

[Examples 1 to 10, Comparative Examples 1 to 4, Reference Examples 1 to 2]
The dispersions obtained as described above were mixed and mixed so that the mass ratio of the organic fine particles became the mass ratio shown in Table 3 and Table 4 below. 4. Ink compositions of Reference Examples 1 and 2 were prepared.
Among the prepared ink compositions, the ink compositions of Examples 1 to 5, and the ink compositions of Comparative Examples 1 and 2 and Reference Example 1 were evaluated by an electrostatic inkjet recording method. On the other hand, the ink compositions of Examples 6 to 10, and the ink compositions of Comparative Examples 3 to 4 and Reference Example 2 were evaluated by a piezo ink jet recording method.

<Evaluation>
The fixability of the obtained ink composition to the ink receptor, the redispersibility of the ink composition, and the printing durability when a lithographic printing plate was produced using the ink composition were evaluated as follows. .
First, the electrostatic ink jet recording method used in this evaluation will be described.

[Electrostatic ink jet recording method]
The ink composition obtained in the ink jet recording apparatus shown in FIGS. Here, a 150 dpi (three-row staggered arrangement with a channel density of 50 dpi) and 833 channel head of the type shown in FIG. 2 was used as the ejection head, and a silicon rubber heat roller incorporating a 1 kW heater was used as the fixing means. As the ink temperature control means, a throw-in heater and a stirring blade were provided in the ink tank, the ink temperature was set to 30 ° C., and the temperature was controlled with a thermostat while rotating the stirring blade at 30 rpm. Here, the stirring blade was also used as a stirring means for preventing precipitation and aggregation. In addition, the ink flow path is partially transparent, the LED light emitting element and the light detecting element are arranged between them, and the ink dilution liquid (Isopar G) or concentrated ink (the solid content concentration of the ink composition is determined by the output signal). The concentration was controlled by charging. An aluminum support was used as the recording medium. After removing dust on the surface of the recording medium by air pump suction, the ejection head is brought close to the recording medium to the image forming position, image data to be recorded is transmitted to the image data calculation control unit, and the recording belt is rotated by rotation of the conveying belt. The ink composition was discharged while sequentially moving the discharge head while transporting the recording medium, and an image was formed with a drawing resolution of 2400 dpi. As the conveyor belt, a metal belt and polyimide film bonded together are used, and a line-shaped marker is placed in the vicinity of one end of the belt along the conveyor direction, and this is optically read by the conveyor belt position detection means. An image was formed by driving the control means. At this time, the distance between the ejection head and the recording medium was kept at 0.5 mm by the output from the optical gap detector. Further, the surface potential of the recording medium is set to −1.5 kV at the time of ejection, and a pulse voltage of +500 V is applied (pulse width 50 μsec) at the time of ejection, and the following aluminum support is performed at a driving frequency of 15 kHz. The body was imaged. Thereafter, the image was fixed by heating in an oven at 125 ° C. for 20 seconds.

[Piezo inkjet recording method]
As described above, the ink compositions of Examples 6 to 10, and the ink compositions of Comparative Examples 3 to 4 and Reference Example 2 were evaluated using the following piezo ink jet recording method.
That is, the ink composition was ink-jet recorded with a suitable amount of 1.5 pl on the ink receiver using PX-G920 manufactured by Seiko Epson Corporation. Thereafter, the image was fixed by heating in an oven at 125 ° C. for 20 seconds.

[Evaluation of fixability]
Using the obtained ink composition, images are formed on the following aluminum support and PET support having a sol-gel hydrophilic layer by the electrostatic inkjet recording method or the piezo inkjet recording method. did. The evaluation index is as follows. The results are shown in Tables 3 and 4.
A ・ ・ The organic fine particles are dissolved and the shape is changed B ・ ・ Part of the organic fine particles are dissolved and part of the shape is changed C ・ ・ The organic fine particles are dissolved almost And the shape has not changed

[Evaluation of printing durability]
Using the obtained ink composition, an image is formed on the aluminum support shown below by the above-described electrostatic ink jet recording method or piezo ink jet recording method, and then the image is fixed and lithographic printing is performed. Got a version.
The obtained lithographic printing plate was used with Komori Corporation's Lithrone printing machine using a 3% aqueous solution of Ecology-2 (manufactured by Fuji Photo Film Co., Ltd.) as fountain solution. Printing was performed using a DIC-GEOS (N) black ink manufactured, and the printing durability was evaluated based on the number of printed sheets when it was visually recognized that the density of the solid image started to decrease. The evaluation result was expressed as a printing durability index with Comparative Example 1 as a reference (100). The larger the printing durability index, the higher the printing durability. The results are shown in Tables 3 and 4.
[Evaluation of redispersibility]
The obtained ink composition was filled in a glass bottle and allowed to stand at 25 ° C. for 2 days. After that, the presence or absence of aggregated particles was observed with a stirrer for 10 minutes by SEM to evaluate redispersibility. . The case where there was no aggregation was marked with ◯, and the case where there was aggregation was marked with ×. The results are shown in Table 2.

<Preparation of ink receptor>
[Aluminum support]
Si: 0.06 mass%, Fe: 0.30 mass%, Cu: 0.005 mass%, Mn: 0.001 mass%, Mg: 0.001 mass%, Zn: 0.001 mass%, Ti: It contains 0.03% by mass, and the balance is prepared by using an aluminum alloy of Al and inevitable impurities. After the molten metal treatment and filtration, an ingot having a thickness of 500 mm and a width of 1200 mm is obtained by a DC casting method. Created. After the surface was shaved with a chamfering machine with an average thickness of 10 mm, it was kept soaked at 550 ° C. for about 5 hours, and when the temperature dropped to 400 ° C., rolling with a thickness of 2.7 mm using a hot rolling mill A board was used. Furthermore, after performing heat processing using a continuous annealing machine at 500 degreeC, it finished by cold rolling to 0.24 mm in thickness, and obtained the aluminum plate of JIS1050 material. After making this aluminum plate width 1030mm, it used for the surface treatment shown below.

[surface treatment]
In the surface treatment, the following various treatments (a) to (j) were continuously performed. In addition, after each process and water washing, the liquid was drained with the nip roller.

(A) Mechanical roughening treatment Using an apparatus as shown in FIG. 4, a suspension of a polishing agent (pumice) having a specific gravity of 1.12 and water is supplied as a polishing slurry to the surface of the aluminum plate. However, a mechanical surface roughening treatment was performed with a rotating roller-like nylon brush. In FIG. 4, 101 is an aluminum plate, 102 and 104 are roller brushes, 103 is a polishing slurry, and 105, 106, 107 and 108 are support rollers. The average particle size of the abrasive was 40 μm, and the maximum particle size was 100 μm. The material of the nylon brush was 6 · 10 nylon, the hair length was 50 mm, and the hair diameter was 0.3 mm. The nylon brush was planted so as to be dense by making a hole in a stainless steel tube having a diameter of 300 mm. Three rotating brushes were used. The distance between the two support rollers (φ200 mm) at the bottom of the brush was 300 mm. The brush roller was pressed until the load of the drive motor for rotating the brush became 7 kW plus with respect to the load before the brush roller was pressed against the aluminum plate. The rotating direction of the brush was the same as the moving direction of the aluminum plate. The rotation speed of the brush was 200 rpm.

(B) Alkali etching treatment The aluminum plate obtained above was subjected to an etching treatment by spraying using an aqueous solution having a caustic soda concentration of 2.6% by mass, an aluminum ion concentration of 6.5% by mass and a temperature of 70 ° C. / M ^{2 was} dissolved. Then, water washing by spraying was performed.

(C) Desmutting treatment The desmutting treatment was performed by spraying with a 1% by mass aqueous solution of nitric acid at a temperature of 30 ° C. (containing 0.5% by mass of aluminum ions), and then washed with water by spraying. The nitric acid aqueous solution used for the desmut treatment was a waste liquid from a process of performing an electrochemical surface roughening treatment using alternating current in a nitric acid aqueous solution.

(D) Electrochemical roughening treatment An electrochemical roughening treatment was carried out continuously using an alternating voltage of 60 Hz. The electrolytic solution at this time was a 10.5 g / L aqueous solution of nitric acid (containing 5 g / L of aluminum ions and 0.007% by mass of ammonium ions) at a liquid temperature of 50 ° C. The AC power supply waveform is the waveform shown in FIG. 5, the time TP until the current value reaches a peak from zero is 0.8 msec, the duty ratio is 1: 1, a trapezoidal rectangular wave AC is used, with the carbon electrode as the counter electrode An electrochemical roughening treatment was performed. Ferrite was used for the auxiliary anode. The electrolytic cell used was the one shown in FIG. The current density was 30 A / dm ² at the peak current value, and the amount of electricity was 220 C / dm ² in terms of the total amount of electricity when the aluminum plate was the anode. 5% of the current flowing from the power source was shunted to the auxiliary anode. Then, water washing by spraying was performed.

(E) Alkaline etching treatment An aluminum plate was subjected to etching treatment at 32 ° C. using an aqueous solution having a caustic soda concentration of 26 mass% and an aluminum ion concentration of 6.5 mass%, and the aluminum plate was dissolved at 0.25 g / m ² . Removes the smut component mainly composed of aluminum hydroxide that was generated when electrochemical roughening treatment was performed using the alternating current of the previous stage, and also melted the edge part of the generated pit to smooth the edge part. did. Then, water washing by spraying was performed.

(F) Desmut treatment Desmut treatment by spraying was performed with a 15% by weight aqueous solution of sulfuric acid at a temperature of 30 ° C. (containing 4.5% by weight of aluminum ions), and then washed with water by spraying. The nitric acid aqueous solution used for the desmut treatment was a waste liquid from a process of performing an electrochemical surface roughening treatment using alternating current in a nitric acid aqueous solution.

(G) Electrochemical surface roughening treatment An electrochemical surface roughening treatment was performed continuously using an alternating voltage of 60 Hz. The electrolytic solution at this time was a hydrochloric acid 7.5 g / L aqueous solution (containing 5 g / L of aluminum ions) at a temperature of 35 ° C. The AC power supply waveform is the waveform shown in FIG. 5, the time TP until the current value reaches a peak from zero is 0.8 msec, the duty ratio is 1: 1, a trapezoidal rectangular wave AC is used, with the carbon electrode as the counter electrode An electrochemical roughening treatment was performed. Ferrite was used for the auxiliary anode. The electrolytic cell used was the one shown in FIG. The current density was 25 A / dm ² at the peak current value, and the amount of electricity was 50 C / dm ² in terms of the total amount of electricity when the aluminum plate was the anode. Then, water washing by spraying was performed.

(H) Alkali etching treatment An aluminum plate was sprayed using an aqueous solution having a caustic soda concentration of 26% by mass and an aluminum ion concentration of 6.5% by mass at 32 ° C., and the aluminum plate was dissolved at 0.10 g / m ² . Removes the smut component mainly composed of aluminum hydroxide that was generated when electrochemical roughening treatment was performed using the alternating current of the previous stage, and also melted the edge part of the generated pit to smooth the edge part. did. Then, water washing by spraying was performed.

(I) Desmutting treatment A desmutting treatment by spraying was performed with a 25% by weight aqueous solution of sulfuric acid at a temperature of 60 ° C. (containing 0.5% by weight of aluminum ions), followed by washing with water by spraying.

(J) Anodizing treatment Anodizing treatment was carried out using an anodizing apparatus having a structure shown in FIG. 7 to obtain a lithographic printing plate support. Sulfuric acid was used as the electrolytic solution supplied to the first and second electrolysis units. All electrolytes had a sulfuric acid concentration of 170 g / L (containing 0.5 mass% of aluminum ions) and a temperature of 38 ° C. Then, water washing by spraying was performed. The final oxide film amount was 2.7 g / m ² .

  The centerline average roughness of the lithographic printing plate support obtained as described above is 0.55 μm, the average wavelength of large waves is 65 μm, the average opening diameter of medium waves is 1.4 μm, the average opening diameter of small waves is 0.14 μm, The ratio of the depth to the average opening diameter of the small wave was 0.46.

[Preparation of PET support]
A coating solution having the following composition was prepared, and an adhesion layer having a thickness of 1.0 g / m ² was prepared on a 188 μm polyester film (Toyobo A4100) subjected to easy adhesion treatment on the surface.

(Adhesion layer coating solution)
-Butyral resin BM-S (manufactured by Sekisui Chemical Co., Ltd.) 59g
(10 mass% MEK solution)
-Carbon black dispersion (solid content 21%) 13.5g
・ MEK (methyl ethyl ketone) 62.7g

A hydrophilic layer coating solution having the following composition is bar-coated on the above film, followed by oven drying at 80 ° C. for 10 minutes to form a hydrophilic layer having a dry coating amount of 3.0 g / m ^2. A PET support having a conductive layer was prepared.

(Hydrophilic layer coating solution)
・ Colloidal silica dispersion (20% by mass aqueous solution) 100 g
(Snowtex C)
・ 500g of the following sol / gel preparation
・ 30 g of 5% by weight aqueous solution of an anionic surfactant
(Nikko Chemicals, Nikkor OTP-75)
・ Purified water 450g

(Sol / gel preparation)
In 19.2 g of ethyl alcohol, 0.86 g of acetylacetone, 0.98 g of tetraethyl orthotitanate, and 8.82 g of purified water, 1.04 g of tetramethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and silane coupling at the following terminals It was prepared by mixing 0.34 g of a hydrophilic polymer having a group and aging for 2 hours at room temperature.

(Synthesis of hydrophilic polymer having a silane coupling group at the end)
Add 3Og of acrylamide, 3.5g of 3-mercaptopropyltrimethoxysilane and 51.3g of dimethylformamide to a three-flask and heat to 65 ° C under a nitrogen stream. 2,2'-azobis (2,4-dimethylvaleronitrile) 0.25 g was added to start the reaction. After stirring for 6 hours, the mixture was returned to room temperature and poured into 1.5 L of ethyl acetate, and a solid precipitated. Thereafter, filtration was performed, and the product was sufficiently washed with ethyl acetate and dried (yield 21 g). It was confirmed by GPC (polystyrene standard) that the polymer had a weight average molecular weight (Mw) of 5,000.

As is apparent from Tables 3 and 4, the ink compositions of Examples 1 to 10 (the ink composition of the present invention) have a fixing property to the ink receptor regardless of the ink jet recording method and the type of the ink receptor. It turns out that it is excellent.
Further, the ink compositions of Examples 1 to 10 (the ink composition of the present invention) are superior in printing durability and redispersibility when a lithographic printing plate is prepared as compared with the ink composition of Comparative Example. I understand.

1 is an overall configuration diagram schematically showing an example of an ink jet printing apparatus suitable for an ink composition of the present invention. It is a perspective view which shows the structure of the inkjet head of the inkjet recording device in this invention (In order to make it intelligible, the edge of the guard electrode in each discharge part is not drawn). FIG. 3 is a side sectional view showing a distribution state of charged particles when the number of ejection units of the inkjet head shown in FIG. 2 is large (corresponding to an arrow XX in FIG. 2). It is a side view which shows the concept of the process of the brush graining used for the mechanical roughening process in preparation of the support body for lithographic printing plates which concerns on this invention. It is a graph which shows an example of the alternating waveform current waveform figure used for the electrochemical roughening process in preparation of the support body for lithographic printing plates which concerns on this invention. It is a side view which shows an example of the radial type cell in the electrochemical roughening process using alternating current in preparation of the support body for lithographic printing plates which concerns on this invention. It is the schematic of the anodizing apparatus used for the anodizing process in preparation of the support body for lithographic printing plates which concerns on this invention.

Explanation of symbols

G Injected ink droplet P Recording medium Q Ink flow R Charged particle 1 Inkjet recording device 2, 2Y, 2M, 2C, 2K ejection head 3 Ink circulation system 4 Head driver 5 Position control means 6A, 6B, 6C Conveying belt stretch Roller 7 Conveying belt 8 Conveying belt position detecting means 9 Electrostatic adsorption means 10 Static elimination means 11 Mechanical means 12 Feed roller 13 Guide 14 Image fixing means 15 Guide 16 Recording medium position detecting means 17 Discharge fan 18 Solvent vapor adsorbing material 38 Ink guide DESCRIPTION OF SYMBOLS 40 Support rod part 42 Ink meniscus 44 Insulating layer 46 1st discharge electrode 48 Insulating layer 50 Guard electrode 52 Insulating layer 56 2nd discharge electrode 58 Insulating layer 62 Floating conductive plate 64 Coating film 66 Insulating member 70 Inkjet head 72 Ink flow path 74 Substrate 75, 75A, 75B Open 76, 76A, 76B Discharge part 78 Discharge part 101 Aluminum plate 102, 104 Roller brush 103 Polishing slurry liquid 105, 106, 107, 108 Support roller 111 Aluminum plate 112 Radial drum roller 113a, 113b Main electrode 114 Electrolytic treatment liquid 115 Electrolysis Liquid supply port 116 Slit 117 Electrolyte passage 118 Auxiliary anode 119a, 119b Thyristor 120 AC power supply 121 Main electrolysis tank 122 Auxiliary anode tank 410 Anodizing apparatus 412 Power supply tank 414 Electrolysis process tank 416 Aluminum plate 418, 426 Electrolyte solution 420 Power supply electrode 422, 428 Roller 424 Nip roller 430 Electrolysis electrode 432 Tank wall 434 DC power supply

Claims (6)

  It contains (A) colored organic fine particles having a volume average particle size of 0.8 μm or more, (B) colored organic fine particles having a volume average particle size of 0.7 μm or less, and (C) a dispersion medium. An ink composition for inkjet recording.   The mass ratio of (A) colored organic fine particles having a volume average particle size of 0.8 μm or more and (B) colored organic fine particles having a volume average particle size of 0.7 μm or less is 1: 9 to 9: 1. The ink composition for ink jet recording according to claim 1, wherein:   At least one of the (A) colored organic fine particles having a volume average particle diameter of 0.8 μm or more and the (B) colored organic fine particles having a volume average particle diameter of 0.7 μm or less has absorption in the visible region. The ink composition for ink jet recording according to claim 1 or 2, wherein the ink composition is used for ink jet recording.   The ink composition for ink jet recording according to any one of claims 1 to 3, wherein the ink composition is used for an electrostatic ink jet recording method. (A) a step of discharging the ink composition for ink jet recording according to any one of claims 1 to 4 onto an ink receptor; and (b) a step of fixing the discharged ink composition;
A method for producing a lithographic printing plate comprising:   A lithographic printing plate produced by the method for producing a lithographic printing plate according to claim 5.

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