JP2008081672A - Ink composition for inkjet and preparation method of planographic printing plate using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink composition for inkjet recording containing resin particles which is excellent in the dispersion stability and re-dispersion property of the resin particles and exhibits excellent storage stability and to provide a preparation method of a planographic printing plate which forms a printed matter drawn with clear and high-quality images, by using this ink composition for inkjet recording. <P>SOLUTION: The ink composition for inkjets contains (A) a non-aqueous dispersion medium and at least one selected from the group consisting of (B-1) a dispersed resin particle formed by the reaction of a resin particle having a neuleophilic group and a dispersant having an electrophilic group and (B-2) a dispersed resin particle formed by the reaction of a dispersant having a neucleophilic group and a resin particle having an electrophilic group. The preparation method of the planographic printing plate using the ink composition for inkjets is also provided. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

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

  As an image recording method for forming an image on a recording medium such as paper based on an image data signal, an electrophotographic method, a sublimation type and a melt type thermal transfer method, an ink jet method and the like have been known so far. 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, there is a so-called electrostatic method in which ink is ejected using electrostatic attraction, or a so-called drop-on-demand method (piezo-electric) in which ink is ejected using the vibration pressure of a piezo element. Various methods such as the so-called bubble (thermal) jet method, which ejects ink using the pressure generated by the formation and growth of bubbles by high heat, have been proposed. Can be obtained.

On the other hand, a conventional lithographic printing plate is obtained as follows.
That is, 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 then the image recording layer of the image portion. The plate is made by a method of exposing the hydrophilic support surface by dissolving and removing the image recording layer in the non-image area with an alkaline developer or an organic solvent to obtain a lithographic printing plate.
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.

Therefore, in recent years, an image is directly formed on a support such as an aluminum plate or a plastic film using the above-described ink jet recording method based on an image data signal created by a computer or the like, and an ink jet recording type CTP is produced. Is known to be capable of printing by attaching to a cylinder of a printing press without performing wet processing (see, for example, Patent Documents 1 to 6).
As such ink for ink jet recording type CTP, water-based ink (Patent Document 1), solid ink (Patent Document 2), UV ink (Patent Document 3), and oil-based ink (Patent Documents 4 to 6) are generally used. Yes.
However, water-based ink has high air bubble properties, and in addition to concerns about the ejection stability of the ink head, when an image is drawn on a hydrophilic support, the image on the plate material is blurred or dried. Is slow, and there is a problem that the image drawing speed decreases.
In the case of solid ink, since a heating device is required for the head, the system is complicated and the device is expensive. Further, since the ink viscosity at the time of ejection is high, there is a problem that it is difficult to eject fine ink droplets that enable high-resolution plate-making images.

  Furthermore, in recent years, a method using UV ink as described in Patent Document 3 has also been disclosed. However, like solid ink, since the viscosity of ink at the time of ejection is high, fine ink droplets that enable high-resolution plate-making images are provided. In addition to being difficult to eject, there are problems such as the head portion being exposed to visible light, the ink in the head portion being cured, and head clogging occurring.

On the other hand, the oil-based inks described in Patent Documents 4 to 6 can obtain an image with less blur when combined with a hydrophilic support. Further, since the head portion is not cured and clogged as seen in UV ink, and a low-viscosity ink is obtained, it is excellent in ink circulation suitability and running suitability inside the head. In addition, since fine ink droplets that enable high-resolution images can be ejected, the image reproducibility is excellent.
However, the oil-based ink described in Patent Document 4 has a problem in that when the dispersed resin particles are synthesized, the dispersant is often taken into the inside of the particles, and high dispersibility of the resin particles cannot be obtained. Yes.
Further, in the oil-based inks described in Patent Documents 5 and 6, since the dispersant is adsorbed non-covalently to the particles, the desorption of the dispersant is likely to occur on the particle surface, and the particles are aggregated and settled over time. There was a problem such as a problem.
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

This invention makes it a subject to achieve the following objectives.
That is, an object of the present invention is to provide an ink composition for ink jet recording containing resin particles, wherein the resin particles have good dispersion stability and redispersibility, and excellent storage stability. That is.
Another object of the present invention is to provide a method for preparing a lithographic printing plate that can obtain a printed material on which a clear and high-quality image is drawn using the ink composition for ink jet recording of the present invention.

As a result of intensive studies, the present inventor has found that the above problems can be solved by using dispersed resin particles obtained by chemically reacting resin particles with a dispersant, and has completed the present invention.
That is, the inkjet ink composition of the present invention comprises (A) a non-aqueous dispersion medium and (B-1) a resin particle having a nucleophilic group and a dispersant having an electrophilic group. It contains at least one selected from the group consisting of dispersed resin particles and (B-2) dispersed resin particles obtained by reacting a dispersant having a nucleophilic group and a resin particle having an electrophilic group. Ink jet ink composition characterized by the above.

In the inkjet ink composition of the present invention, it is preferable that the (B-1) dispersed resin particles and the (B-2) dispersed resin particles both have a volume average particle size of 0.8 μm or more.
Moreover, the ink composition for inkjet of this invention is suitable for the ink composition for lithographic printing plates used when drawing an image with the inkjet recording method on the support body for lithographic printing plates.

  Furthermore, the lithographic printing plate production method of the present invention is characterized in that an image portion is formed on a lithographic printing plate recording medium by the inkjet recording method using the inkjet ink composition of the present invention.

ADVANTAGE OF THE INVENTION According to this invention, the dispersion stability and redispersibility of a resin particle are favorable, and the ink composition for inkjet recordings which is excellent in storage stability can be provided. This ink composition for inkjet recording is suitable for forming an image portion of a lithographic printing plate.
Further, according to the method for preparing a lithographic printing plate of the present invention, it is possible to obtain a printed material on which a clear and high-quality image is drawn using the ink composition for inkjet recording of the present invention.

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) a non-aqueous dispersion medium, and (B-1) dispersed resin particles obtained by reacting a nucleophilic group-containing resin particle and an electrophilic group-containing dispersant ( Hereinafter, (B-1) referred to as specific dispersed resin particles), and (B-2) a dispersed resin obtained by reacting a dispersant having a nucleophilic group and a resin particle having an electrophilic group. An ink-jet ink composition comprising at least one selected from the group consisting of particles (hereinafter appropriately referred to as (B-2) specific dispersed resin particles).
In this specification, (B-1) specific dispersed resin particles and (B-2) specific dispersed resin particles may be collectively referred to as (B) specific dispersed resin particles.
Hereinafter, components constituting the ink composition of the present invention will be described in detail.

[(A) Non-aqueous dispersion medium]
Examples of the non-aqueous dispersion medium (A) constituting the ink composition of the present invention include linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and halogens of these hydrocarbons. Substituted products (halogenated 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.) and the like.

Note that the ratio of the non-hydrocarbon compound used by mixing with the above hydrocarbon compounds and their halogen-substituted compounds is the viscosity, non-aqueous type when drawing an image using an inkjet recording method such as a piezo method. It is determined in consideration of the boiling point of the dispersion medium, redispersibility and the like.
On the other hand, when drawing an image by using an electrostatic ink jet recording method, it is used by mixing with the above hydrocarbon compounds and their halogen substitutes from the viewpoint of lowering the dielectric constant of the non-aqueous dispersion medium. A lower ratio of the non-hydrocarbon compound is preferable.

In the ink composition of the present invention, the content of the (A) non-aqueous dispersion medium is preferably in the range of 90 to 10% by mass, and in the range of 98 to 20% by mass with respect to the total mass of the ink composition. Is more preferable, and it is still more preferable that it is the range of 97-30 mass%.
(A) When the content of the non-aqueous dispersion medium is less than 10% by mass, the viscosity is increased and the discharge property is lowered, and (B) aggregation of the specific dispersed resin particles occurs, and the storage stability and dispersibility are improved. May decrease. On the other hand, when it exceeds 99 mass%, the density | concentration of (B) specific dispersion resin particle falls, and image forming property may fall. Moreover, when (B) specific dispersion resin particle is colored, color density may fall and visibility may fall.

[(B) specific dispersed resin particles]
The (B) specific dispersed resin particles, which are the most important components in the present invention, are obtained by chemical reaction of the dispersant and the resin particles as described below, and the (A) non-aqueous dispersion medium Any dispersible resin particles may be used, but particles obtained by a polymerization granulation method are preferable.
That is, (B-1) specific dispersed resin particles are dispersed resin particles obtained by reacting a resin particle having a nucleophilic group and a dispersant having an electrophilic group, and (B-2) a specific dispersed resin. The particles are dispersed resin particles formed by a reaction between a dispersant having a nucleophilic group and a resin particle having an electrophilic group.
Hereinafter, (B-1) specific dispersed resin particles and (B-2) specific dispersed resin particles will be described.

-(B-1) specific dispersed resin particles-
More specifically, (B-1) specific dispersed resin particles in the present invention are (a-1) a monomer having a nucleophilic group, and (b-1) a dispersant having an electrophilic group. (C) It is preferable to be prepared by adding a radical polymerization initiator in a non-aqueous solvent and then heating to cause a radical polymerization reaction.
By this method, resin particles having a nucleophilic group are formed, and the nucleophilic group of the resin particle reacts with the electrophilic group in the dispersant, whereby (B-1) specific dispersion in the present invention. Tree particles are obtained.
Hereinafter, the (B-1) polymerization granulation method of the specific dispersed resin particles in the present invention will be specifically described.

[(A-1) Monomer having a nucleophilic group]
(A-1) By polymerizing a monomer having a nucleophilic group, resin particles having a nucleophilic group for producing (B-1) specific dispersed resin particles can be obtained.
Here, as nucleophilic groups, “Graduate Lecture Organic Chemistry I (Molecular Structure and Reaction / Organic Metal Chemistry)” edited by Ryoji Noyori et al. The functional group is not particularly limited as long as it is a functional group described in a specialized book on organic chemistry such as “Organic Chemistry” McMurry (Tokyo Kagaku Dojin).
Specific examples of the nucleophilic group include a carboxyl group, primary amino group, secondary amino group, phenoxy group, alkoxy group, hydroxyl group, thioalkoxy group, thiophenoxy group, —COCHCO— group, —COCHSO ₂ —. _group, -SO ₂ NHSO 2 - group, and the like. Among these, a carboxyl group, a primary amino group, a secondary amino group, an alkoxy group, and a hydroxyl group are preferable because of high nucleophilicity.

(A-1) As the monomer having a nucleophilic group, any monomer having at least one nucleophilic group can be used without limitation.
Hereinafter, although the specific example (exemplary compound) of the monomer which has (a-1) nucleophilic group used for this invention is shown, this invention is not limited to these.

  In addition, from the viewpoint of improving the granulating property of the resin particles, in addition to the monomer having (a-1) a nucleophilic group, a monomer represented by the following general formula (I) may be used in combination. .

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 examples of the monomer represented by the general formula (I) include, for example, vinyls of aliphatic carboxylic acids having 1 to 20 carbon atoms (acetic acid, propionic acid, butyric acid, monochloroacetic acid, trifluoropropionic acid, etc.). Esters or allyl esters; C 1-10 optionally substituted alkyl esters or amides of unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid (as alkyl groups) 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-dimethyl) Ruamino) ethyl group, 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 , Bi Nylbenzenecarboxamide, vinylbenzenesulfoamide, etc.); unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid; cyclic acid anhydrides of maleic acid, itaconic acid; acrylonitrile; methacrylonitrile; Polymerizable double bond group-containing heterocyclic compounds (specifically, for example, compounds described in “Polymer Data Handbook -Basic Edition” edited by Polymer Society of Japan, p. N-vinyl pyridine, N-vinyl imidazole, N-vinyl pyrrolidone, vinyl thiophene, vinyl tetrahydrofuran, vinyl oxazoline, vinyl thiazole, N-vinyl morpholine, etc.).
These monomers may be used alone or in combination of two or more.

In this invention, the usage-amount of the monomer at the time of synthesize | combining (B-1) specific dispersion resin particle shall be 10 mass% or more with respect to the total solid in the liquid mixture used in the case of a synthesis | combination. Is more preferable, it is more preferable that it is 15 mass% or more, and it is still more preferable that it is 20 mass% or more. Further, the upper limit of the amount of the monomer used is preferably 99% by mass or less from the viewpoint of monodispersity and dispersion stability of the obtained (B-1) specific dispersed resin particles, and is 95% by mass or less. More preferably.
When the monomer content is less than 10% by mass, the (B) specific dispersed resin particles are difficult to precipitate from the (c) non-aqueous solvent, so that the synthesis becomes difficult. Moreover, monodispersity also falls.

In addition, the amount of the monomer (a-1) having a nucleophilic group is preferably 10% by mass or more, more preferably 15% by mass or more, based on the total monomers used in the synthesis. More preferably, it is more preferably 20% by mass or more.
(A-1) When the amount of the monomer having a nucleophilic group used is 10% by mass, the reaction amount with the dispersant having (b-1) an electrophilic group is insufficient, and the dispersibility, time Stability is reduced.

[(B-1) Dispersant having an electrophilic group]
The (b-1) dispersant having an electrophilic group used when granulating the (B-1) specific dispersed resin particles in the present invention will be described.
This (b-1) dispersant having an electrophilic group reacts with resin particles having a nucleophilic group obtained by polymerizing the monomer having the above-mentioned (a-1) nucleophilic group. It is used to make a stable resin particle dispersion.
In the present invention, (b-1) the dispersant having an electrophilic group is 1 to 50% by mass with respect to all monomers used when granulating the specific dispersed resin particles (B-1). It is preferable to use, More preferably, it is 5-40 mass%.

Here, the electrophilic group is a functional group that can react with a nucleophilic group to form a covalent bond. “Graduate Lecture Organic Chemistry I (Molecular Structure and Reaction / Organometallic Chemistry)” edited by Ryoji Noyori et al. ( Tokyo Chemical Doujin), “Organic Chemistry” by Morrison Boyd (Tokyo Chemical Doujin), “Organic Chemistry” McMurry (Tokyo Chemical Doujin), etc., are not particularly limited as long as they are functional groups described in specialized organic chemistry books.
Specific examples of electrophilic groups include epoxy groups, isocyanate groups, thioisocyanate groups, oxetane groups, chloroalkyl groups, bromoalkyl groups, iodoalkyl groups, alkyl sulfonate groups, alkyl trifluoromethanesulfonates, and pentafluoroethane. Examples thereof include perfluoroalkane sulfonic acid alkyl groups, tosylate alkyl groups, perfluoroalkane carboxylic acid alkyl groups, and the like, such as alkyl sulfonates. Among them, epoxy group, isocyanate group, oxetane group, chloroalkyl group, bromoalkyl group, iodoalkyl group, alkyl sulfonate group, alkyl trifluoromethanesulfonate, alkyl pentafluoroethanesulfonate, etc. from the point of high electrophilicity Of these, perfluoroalkanesulfonic acid alkyl groups are preferred.

(B-1) The dispersant having an electrophilic group is preferably synthesized using a monomer having at least one electrophilic group.
Hereinafter, specific examples (exemplary compounds) of monomers having an electrophilic group used when synthesizing a dispersant having (b-1) an electrophilic group are shown, but the present invention is limited to these. It is not something.

In the present invention, (b-1) the dispersant having an electrophilic group is a random copolymer, comb-type copolymer or partially cross-linked copolymer soluble in the above-mentioned (A) non-aqueous dispersion medium. Conventional dispersion stabilizers such as the above can be used.
Hereinafter, the dispersant suitable for the present invention will be described.

(Random copolymer)
Examples of the random copolymer in the present invention include a copolymer obtained by copolymerizing a monomer having an electrophilic group and a monomer shown below.
Specific examples of monomers used when synthesizing a random copolymer include alkyl chains and alkenyl chains having 6 to 32 carbon atoms (these aliphatic groups contain substituents such as halogen atoms and alkoxy groups). Acrylic acid, methacrylic acid, or crotonic acid having a main-chain carbon-carbon bond via a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. Higher fatty acid vinyls; alkyl vinyl ethers; olefins such as butadiene, isoprene and diisoprene; and the like. These may be used in combination of two or more.
Further, in addition to the above-mentioned monomers, the following various monomers can be used at a ratio within a range in which the obtained copolymer is soluble in the non-aqueous solvent (c).

  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 (Eg, styrene, vinyl toluene, α-methyl styrene, etc.); tertiary amino such as diethylaminoethyl methacrylate, N-vinylpyrrolidone, acrylamide, acrylonitrile, 2-chloroethyl methacrylate, 2,2,2-trifluoroethyl methacrylate, etc. And monomers containing various polar groups such as a group, an amide group, a cyano group, a halogen atom, and a heterocyclic ring.

  The weight average molecular weight of the random copolymer in the present invention is preferably in the range of 3000 to 200,000, and preferably in the range of 5000 to 150,000 in order to improve redispersibility and dispersibility in storage stability. More preferred.

(Comb-type copolymer)
As the comb-type copolymer in the present invention, a monomer having a specific reactive group and a macromonomer (MM) having the structure shown below and having a weight average molecular weight of 1 × 10 ^{3 to} 5 × 10 ⁴ are used. And a copolymer obtained by copolymerizing at least one of the above.
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 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 _{is, -COO -, - OCO -,} - CH 2 OCO-, CH 2 COC -, - O -, - SO 2 -, - CO -, - CONR 11 -, —SO ₂ NR ¹¹ — or —Ph (phenylene group) — is represented. 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 composed of a combination of 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 parts by weight, preferably 0.5 to 100 parts by weight, based on 100 parts by weight of all monomers used in radical polymerization. 5 parts 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 (B-1) specific dispersed resin particles obtained by polymerization granulation is uniform, and the obtained (B-1) specific dispersed resin particles The redispersibility is significantly 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 .

(Partially crosslinked copolymer)
The partially crosslinked copolymer in the present invention is a monomer having the above-mentioned electrophilic group and at least one monomer capable of forming a repeating unit represented by the following general formula (VI). (C) a resin that is soluble in a non-aqueous solvent, in which a part of the polymer main chain is crosslinked.

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 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 cross-linked copolymer in the present invention includes the above-mentioned monomer having an electrophilic group and at least one monomer capable of forming a repeating unit represented by the general formula (VI). In which the polymer main chain is partially cross-linked.
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.
The method of 1) preferably comprises forming a monomer having two or more polymerizable functional groups, a monomer having an electrophilic group, and a repeating unit represented by the general formula (VI). This is a method of cross-linking between polymer chains by polymerizing with a monomer capable of being polymerized.

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, as monomers having the same polymerizable functional group, styrene derivatives such as divinylbenzene and trivinylbenzene; polyhydric alcohols (for example, Ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol # 200, # 400, # 600, 1,3-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol, etc. ), 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;

  Polymerization is performed using the above-described monomer having two or more polymerizable functional groups in an amount of 10% by mass or less, preferably 8% by mass or less of the total monomer, and (c) a partial cross-linkable soluble in a non-aqueous solvent. A mold copolymer is formed.

  The partially crosslinked dispersant used in the present invention is specifically a monomer having an electrophilic group, which is a known method, and a single amount capable of forming the repeating unit represented by the general formula (VI). And a method of polymerizing with a polymerization initiator (for example, an azobis compound, a peroxide, etc.) in the coexistence of at least the above-mentioned polyfunctional monomer and the above-described polyfunctional monomer is simple and preferable. The polymerization initiator used here is 0.1 to 15% by mass, preferably 0.5 to 10% by mass, with respect to 100 parts by mass of all monomers.

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

[(C) Non-aqueous solvent]
Next, (c) non-aqueous solvent used when synthesizing (B-1) specific dispersed resin particles and (B-2) specific dispersed resin particles will be described.
Here, (c) the non-aqueous solvent is a linear or branched aliphatic hydrocarbon, alicyclic hydrocarbon, or aromatic hydrocarbon, and a halogen substitution product (halogenated hydrocarbon) of these hydrocarbons. Type). 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 non-aqueous dispersion medium (A) constituting the ink composition, (B-1) in the granulation stage of specific dispersed resin particles, (A) It is preferable to use the same (c) non-aqueous solvent as the non-aqueous dispersion medium.
Therefore, in the piezo ink jet recording method, the ratio of non-hydrocarbon compounds to be used by mixing with hydrocarbon compounds and their halogen substitutes is determined in consideration of viscosity, non-aqueous dispersion medium boiling point, redispersibility, etc. It is done.
On the other hand, in the case of drawing an image using the electrostatic ink jet recording method, from the viewpoint of lowering the dielectric constant of the non-aqueous dispersion medium, the non-carbonization used by mixing with the above hydrocarbon compounds and their halogen substitution products. A lower ratio of the hydrogen compound is preferable. Therefore, when (B-1) specific dispersed resin particles are prepared using the same (A) non-aqueous solvent as (A) non-aqueous dispersion medium, the non-hydrocarbon compound is added to the hydrocarbon compounds and their halogen substitution products. When the dielectric constant becomes 5.0 or more by mixing the non-hydrocarbon compound mixed when synthesizing the specific dispersed resin particles (B-1) so that the dielectric constant becomes 5.0 or less. It is preferable to increase the ratio of the hydrocarbon compound and lower the dielectric constant by using a method of removing under heating or reduced pressure, or a method of replacing the supernatant using a centrifugal separator.

(C) The amount of the non-aqueous solvent 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 It is preferable that it is the range of 20 to 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%.
(C) When the content of the non-aqueous solvent is less than 0.01% by mass, the particle size of the specific dispersed resin particles (B-1) does not become a desired size, and the monodispersibility decreases. . On the other hand, when it is more than 80% by mass, aggregation of the (B-1) specific dispersed resin particles occurs and monodispersibility and dispersibility are deteriorated.

[(B-1) Granulation method of specific dispersed resin particles]
In order to produce the (B-1) specific dispersed resin particles used in the present invention, in general, (a-1) a monomer having a nucleophilic group as described above, and (b-1) an electrophile What is necessary is just to heat-polymerize the dispersing agent which has an ionic group in (c) nonaqueous solvent in presence of polymerization initiators, such as a benzoyl peroxide, an azobisisobutyronitrile, and a butyl lithium.
In this method, the amount of the polymerization initiator used is preferably (a-1) 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, based on the total amount of monomers having a nucleophilic group. It is.
Moreover, superposition | polymerization temperature is about 40-180 degreeC, Preferably it is 50-120 degreeC. The reaction time is preferably 3 to 15 hours.

  (C) When a polar solvent such as alcohols, ketones, ethers, esters or the like is used in combination with the non-aqueous solvent used in the reaction, unreacted monomers that are polymerized and granulated Is still removed by heating to a temperature equal to or higher than the boiling point of the solvent or monomer, or by performing post-treatment such as distillation under reduced pressure to remove the polar solvent and unreacted substances.

-(B-2) specific dispersed resin particles-
Next, a method for producing (B-2) specific dispersed resin particles in the present invention will be described.
(B-2) The specific dispersed resin particles include (a-2) a monomer having an electrophilic group and (b-2) a dispersant having a nucleophilic group (c) a non-aqueous solvent. It is preferable to be prepared by adding a radical polymerization initiator therein and then heating to cause a radical polymerization reaction.
By this method, resin particles having an electrophilic group are formed, and the electrophilic group of the resin particle reacts with the nucleophilic group in the dispersant, whereby (B-2) specific dispersion in the present invention. Tree particles are obtained.
Hereinafter, the (B-2) polymerization granulation method of the specific dispersed resin particles in the present invention will be specifically described.

[(A-2) Monomer having electrophilic group]
(A-2) By polymerizing a monomer having an electrophilic group, (B-2) resin particles having an electrophilic group for producing specific dispersed resin particles can be obtained.
Here, the electrophilic group is synonymous with the electrophilic group contained in the dispersant having the electrophilic group (b-1) described above, and preferred ones are also the same.

(A-2) As the monomer having an electrophilic group, any monomer having at least one kind of electrophilic group can be used without limitation.
Specific examples of the monomer (a-2) having an electrophilic group used in the present invention include (a-1) used when synthesizing the above-described dispersant having an electrophilic group (a-1). -2) Specific examples (exemplary compounds) of monomers having an electrophilic group are exemplified, but the present invention is not limited thereto.
In addition, from the viewpoint of enhancing the granulating property of the resin particles, in addition to the monomer (a-2) having an electrophilic group, the monomer represented by the general formula (I) may be used in combination. .

In this invention, the usage-amount of the monomer at the time of synthesize | combining (B-2) specific dispersion resin particle shall be 10 mass% or more with respect to the total solid in the liquid mixture used in the case of a synthesis | combination. Is more preferable, it is more preferable that it is 15 mass% or more, and it is still more preferable that it is 20 mass% or more. Further, the upper limit of the amount of the monomer used is preferably 99% by mass or less from the viewpoint of monodispersity and dispersion stability of the obtained (B-2) specific dispersed resin particles, and is 95% by mass or less. More preferably.
When the monomer content is less than 10% by mass, the (B) specific dispersed resin particles are difficult to precipitate from the (c) non-aqueous solvent, which makes synthesis difficult. Moreover, monodispersity also falls.

The amount of the monomer having an electrophilic group (a-2) is preferably 10% by mass or more, and 15% by mass or more, based on the total monomers used in the synthesis. More preferably, it is more preferably 20% by mass or more.
(A-2) When the amount of the monomer having an electrophilic group used is 10% by mass, the amount of reaction with the dispersant having (b-2) the nucleophilic group is insufficient, and the dispersibility, time Stability is reduced.

[(B-2) Dispersant having a nucleophilic group]
The (b-2) dispersant having a nucleophilic group used when granulating the (B-2) specific dispersed resin particles in the present invention will be described.
This (b-2) dispersant having a nucleophilic group reacts with the resin particles having an electrophilic group obtained by polymerizing the above-mentioned monomer having an electrophilic group (a-2). It is used to make a stable resin particle dispersion.
In the present invention, (b-2) the dispersant having a nucleophilic group is 1 to 50% by mass with respect to all monomers used when granulating the specific dispersed resin particles (B-2). It is preferable to use, More preferably, it is 5-40 mass%.

Here, (b-2) the nucleophilic group of the dispersant having a nucleophilic group is synonymous with the nucleophilic group of the monomer having the (a-1) nucleophilic group described above, The preferable ones are also the same.
(B-2) The dispersant having a nucleophilic group is preferably synthesized using a monomer having at least one nucleophilic group.
(B-2) Specific examples of the monomer having a nucleophilic group used when synthesizing a dispersant having a nucleophilic group include (a-1) a monomer having a nucleophilic group. Although the specific example (exemplary compound) is mentioned, this invention is not limited to these.

In the present invention, (b-2) the dispersant having a nucleophilic group includes a random copolymer, comb copolymer, and partially crosslinked copolymer that is soluble in the above-mentioned (A) non-aqueous dispersion medium. Conventional dispersion stabilizers such as the above can be used.
Specifically, in the random copolymer, comb copolymer, and partially cross-linked copolymer described as the above-mentioned (b-1) dispersant having an electrophilic group, the electrophilic group What was synthesize | combined using the monomer which has a nucleophilic group instead of the monomer which has can be used as a preferable thing.

[(C) Non-aqueous solvent]
(B-2) (c) The non-aqueous solvent used when synthesizing the specific dispersed resin particles is omitted in order to omit steps such as substitution with a non-aqueous dispersion medium (A) constituting the ink composition. It is preferable to use the same non-aqueous dispersion medium.
Therefore, as in the case of synthesizing the above-mentioned (B-1) specific dispersed resin particles, it is preferable that the selection of the compound to be used and the ratio thereof are determined according to the applied inkjet recording method.
In addition, the usage-amount of (c) non-aqueous solvent at the time of synthesize | combining (B-2) specific dispersion resin particle is the same as that at the time of synthesize | combining the above-mentioned (B-1) specific dispersion resin particle.

[(B-2) Granulation method of specific dispersed resin particles]
In order to produce the (B-2) specific dispersed resin particles used in the present invention, in general, (a-2) a monomer having an electrophilic group as described above, and (b-2) nucleophilicity The dispersant having a functional group may be heated and polymerized in the presence of a polymerization initiator such as benzoyl peroxide, azobisisobutyronitrile, or butyl lithium in a non-aqueous solvent (c).
In this method, the amount of the polymerization initiator used, the polymerization temperature, the reaction time, and the post-treatment are the same as in the production of (B-1) specific dispersed resin particles.

[(B) Preferred physical properties of specific dispersed resin particles]
The specific dispersed resin particles (B) produced as described above preferably have a volume average particle size of 0.8 μm or more, and the upper limit of the volume average particle size is dispersion stability and storage stability. From the viewpoints of properties and redispersibility, it is preferably 5.0 μm. The volume average particle size is more preferably in the range of 1.0 to 4.0 μm, and still more preferably in the range of 1.2 to 3.0 μm.
This volume average particle diameter is determined by CAPA-500 (trade name, manufactured by Horiba, Ltd.).

  (B) By setting the volume average particle size of the specific dispersed resin particles in the above range, even when the ink composition of the present invention is applied to the electrostatic ink jet recording method, the ejection stability is good. Thus, it is possible to discharge at a low voltage. Further, there is an advantage that the droplets are difficult to spread when attached on the recording medium. Thereby, even if it is a case where it applies to the inkjet recording method of various systems, the blur of an image can be prevented.

  In the present invention, (B) the factors controlling the particle diameter of the specific dispersed resin particles include the types and concentrations of monomers used for synthesizing the resin particles, the types and concentrations of the dispersant, and the types of solvents. And the density | concentration, the presence or absence of an additive, reaction temperature, etc. are mentioned, By adjusting these suitably, the (B) specific dispersion resin particle of a desired particle size can be obtained.

The weight average molecular weight of the (B) specific dispersed resin particles in the present invention is preferably 1 × 10 ³ to 1 × 10 ⁶ , more preferably 3 × 10 ^{3 to} 5 × 10 ⁵ , most preferably 5 × 10 ³ to 1 × 10 ⁵ .
Further, the (B) specific dispersed resin 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, In the invention, the elastic modulus at 80 to 150 ° 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 at the fixing temperature. More preferably, it is in the range of 1.0 × 10 ⁶ or less.

In the ink composition of the present invention, the content of the (B) specific dispersed resin particles is preferably in the range of 90 to 1% by mass, and in the range of 80 to 20% by mass with respect to the total mass of the ink composition. It is more preferable that it is in the range of 70 to 3% by mass.
When the content of the (B) specific dispersed resin particles is less than 1% by mass, the concentration of the (B) specific dispersed resin particles may be lowered, and the image formability may be lowered. Moreover, when (B) specific dispersion resin particle is colored, color density may fall and visibility may fall. In addition, when the content of the (B) specific dispersed resin particles is more than 90% by mass, the viscosity is increased and the discharge property is lowered, and the aggregation of the (B) specific dispersed resin particles occurs, and the storage stability and dispersibility are increased. May decrease.
In the present invention, one or more selected from the group consisting of (B-1) specific dispersed resin particles and (B-2) specific dispersed resin particles may be used, and two or more types may be used in combination.

  The ink composition of the present invention is an oil-based ink containing (A) a non-aqueous dispersion medium and (B) specific dispersed resin particles. As described above, the (B) specific dispersed resin particle is formed by a reaction between a nucleophilic group and an electrophilic group, and a covalent bond is formed between the resin particle and the dispersant. Presumed to be. Therefore, (B) the dispersibility of the specific dispersed resin particles continues for a long time, and (B) even if the specific dispersed resin particles are precipitated, the redispersibility is excellent. As a result, the ink composition is excellent in storage stability (time stability).

[Color material]
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, When a colored image is to be formed, a coloring material (coloring agent) can be contained.

  As the coloring material 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.)

Further, by changing the color material, it is possible to create an ink composition of four colors of yellow, magenta, cyan, and black (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 color material 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 the color 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 C.I. 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, 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 kind of pigment for each color from the viewpoint of simplicity of ink production, but as a hue adjustment, for example, for black ink, phthalocyanine is mixed with carbon black depending on circumstances. Are preferably used in combination of two or more. 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 in the range of 0.1 to 100% by mass with respect to the mass of the (B) specific dispersed resin particles in the ink composition. It is preferable that it is in the range of 1 to 50% by 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, (B) storage stability, dispersibility, and redispersibility of the specific dispersed resin particles are obtained. Etc. can be kept good.

  On the other hand, for the purpose of obtaining visibility such as plate inspection of a lithographic printing plate, the content of the pigment and dye is 0 with respect to the mass of the (B) specific dispersed resin particles in the ink composition. 0.1 to 50% by mass is preferable, and 1 to 30% by mass is more preferable. When the amount is 0.1% by mass or more, the coloring amount is sufficient, and sufficiently good visibility is obtained. When the amount is 30% by mass or less, (B) storage stability, dispersibility, redispersibility, etc. of the specific dispersed resin particles are obtained. Can be kept good. More preferably, it is 1-20 mass%.

  These color materials may be dispersed in (A) the dispersion medium as (D) the specific dispersion resin particles, and (B) the specific dispersion resin particles. Also good. As one of the methods for inclusion, as described in JP-A-57-48738, there is a method of dyeing (B) specific dispersed resin particles with a preferable dye. As another method, as disclosed in JP-A-53-54029, there is a method of chemically binding (B) the specific dispersed resin particles and the dye, or, Japanese Patent Publication No. 44-22955. As described in No. 1, etc., there is a method of using a monomer containing a dye in advance to produce a dye-containing copolymer when it is produced by a polymerization granulation method.

[Charge control agent]
When the ink composition of the present invention is used to draw an image by an electrostatic ink jet recording method, it is preferable to use a charge adjusting agent in combination in order to enhance the responsiveness (electricity detection) of particles to the pulse voltage.
To impart electroanalytical properties to the particles, it 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 and zirconium naphthenate Metal, organic carboxylic acid metal salt such as zirconium octenoate salt, organic carboxylic acid ammonium salt such as tetramethylammonium stearate salt, organic sulfonic acid metal such as sodium dodecylbenzenesulfonate, magnesium dioctylsulfosuccinate Salt, organic sulfonic acid ammonium salt such as toluene sulfonic acid tetrabutylammonium salt, styrene and A copolymer of maleic acid modified with an amine, a polymer having a carboxylic acid group in the side chain, such as a polymer having a carboxylic acid group, a carboxylate anion in the side chain, such as a copolymer of stearyl methacrylate and a tetramethylammonium salt of methacrylic acid A polymer having a group, a polymer having a nitrogen atom in a side chain such as a copolymer of styrene and vinylpyridine, butyl methacrylate and N- (2-methacryloyloxyethyl) -N, N, N-trimethylammonium tosylate salt And polymers having an ammonium group in the side chain, such as a copolymer of
The charge applied to the 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 (specific particles) can be easily adjusted to 50% or more of the electric conductivity of 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.

[Inkjet recording device]
The ink composition of the present invention discharges ink using the vibration pressure of a piezo element, so-called drop-on-demand method (piezo method), 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 particles in the ink composition are positively charged has been described. However, the 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 lithographic printing plate production method of the present invention uses the inkjet ink composition of the present invention on a recording medium (lithographic printing plate recording medium) that functions as a lithographic printing plate support by an inkjet recording method. And drawing an image.
That is, the method for producing a lithographic printing plate of the present invention uses the inkjet recording apparatus as described above on the lithographic printing plate support, which is one of the recording media, of the inkjet ink composition of the present invention. The image portion is formed by discharging.
In the method for producing 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.

[Support for lithographic printing plate]
In the method for producing a lithographic printing plate of the present invention, a lithographic printing plate support (hereinafter sometimes simply referred to as a support) is used as a recording medium. The lithographic printing plate support in the present invention is not particularly limited as long as it is a dimensionally stable plate having the required strength and durability. For example, paper, plastic (for example, polyethylene, polypropylene, Paper laminated with polystyrene, etc.), metal plate (eg, aluminum, zinc, copper, etc.), plastic film (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene) Terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), metal laminated 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, it is preferable to use a support in which a sol-gel hydrophilic layer is provided on a surface-treated aluminum plate and polyester film as a support for a lithographic printing plate.
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 the sol-gel structure in the present invention (hereinafter sometimes simply referred to as hydrophilic layer crossing) 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 having at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom (for example, the hetero group). Examples of the ring include a pyran ring, a furan ring, a thiophene ring, a morpholine ring, a pyrrole ring, a thiazole ring, an oxazole ring, a pyridine ring, a piperidine ring, a pyrrolidone ring, a benzothiazole ring, a benzoxazole ring, a quinoline ring, and a tetrahydrofuran ring. It 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 (1).

In the general formula (1), 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 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, 0 to 10 carbon atoms. A nitrogen atom, 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 of the general formula (1) 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 radical polymerizable monomer represented by the following general formula (2), and a silane coupling agent having chain transfer ability in the radical polymerization represented by the following general formula (3): And can be synthesized by radical polymerization. Since the silane coupling agent, general formula (3), has chain transfer ability, it is possible to synthesize a polymer in which a silane coupling group is introduced at the polymer main chain terminal in radical polymerization.
In general formula (2) and general formula (3), R ¹ , R ² , R ³ , R ⁴ , m, n, Y, and L have the same meaning as in general formula (1).

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 an intermediate layer (adhesion layer) containing polyacrylamide or the like is provided between the polyester film and the adhesion layer in order to improve adhesion. May be provided.

By the method as described above, a high-definition 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 a high-definition image portion, it is possible to print a printed matter on which a clear and high-quality image is drawn.

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

<(B-1) Synthesis Example of Dispersant Having Electrophilic Group>
[Synthesis of Random Copolymer (CI)]
Toluene (200 g) was heated to 80 ° C. with stirring under a nitrogen stream. Thereto, a monomer having an electrophilic group: glycidyl methacrylate (0.3 mol), stearyl methacrylate (0.7 mol), and 2,2′-azobis (isobutyronitrile) (abbreviation A. Toluene (200 g) in which IB (N) was dissolved was added dropwise over 3 hours. After completion of the dropping, the reaction was carried out at 80 ° C. for 2 hours. I. B. 2 g of N was added and reacted for 2 hours. After cooling, the mixed solution was reprecipitated in 5 liters of methanol, and the powder was collected by filtration and dried to obtain a white solid (CI) in a yield of 92%.
The obtained random copolymer (CI) had a weight average molecular weight (abbreviated as Mw) of 4.3 × 10 ⁴ . The structure was identified by NMR and IR.

[Synthesis of Random Copolymer (C-II)]
Toluene (200 g) was heated to 80 ° C. with stirring under a nitrogen stream. Thereto, a monomer having an electrophilic group: Karenz MOI (2-methacryloyloxyethyl isocyanate, Showa Denko KK, 0.3 mol), hexadecyl methacrylate (0.7 mol), and 2,2′- Toluene (200 g) in which azobis (isobutyronitrile) (abbreviation AIBN) was dissolved was added dropwise over 3 hours. After completion of the dropping, the reaction was carried out at 80 ° C. for 2 hours. I. B. 2 g of N was added and reacted for 2 hours. After cooling, the mixed solution was reprecipitated in 5 liters of methanol, and the powder was collected by filtration and dried to obtain a white solid (C-II) with a yield of 94%.
The obtained random copolymer (C-II) had a weight average molecular weight (abbreviated as Mw) of 3.8 × 10 ⁴ . The structure was identified by NMR and IR.

[Synthesis of comb-type copolymer (C-III)]
(Production Example of Macromonomer (MM) 1: Macromonomer MM-1)
A mixed solution of 100 g of octadecyl methacrylate, 3 g of mercaptopropionic acid, and 300 g of toluene was heated to a temperature of 75 ° C. while stirring under a nitrogen stream. 1.0 g of 2,2′-azobisisobutyronitrile (abbreviation AIBN) was added and reacted for 4 hours. I. B. N. 0.5 g was added for 3 hours. I. B. N. Was reacted for 3 hours. Next, 8 g of glycidyl methacrylate, 1.0 g of N, N-dimethyldodecylamine and 0.5 g of t-butylhydroquinone were added to this reaction solution, and the mixture was stirred at a temperature of 100 ° C. for 12 hours. After cooling, the reaction solution was reprecipitated in 2 liters of methanol to obtain a white powder with a yield of 86%. The weight average molecular weight of the polymer was 1.8 × 10 ⁴ . The structure was identified by NMR and IR.

Monomer having electrophilic group: glycidyl methacrylate (0.5 mol), macromonomer MM-1 obtained by the above method (0.5 mol), and a mixed solution of 250 g of toluene under a nitrogen stream The temperature was raised to 80 ° C. with stirring. 3.0 g of 2,2′-azobis (isobutyronitrile) (abbreviation AIBN) was added and reacted for 4 hours. A. I. B. N. Was added for 1.0 hour and reacted for 2 hours. I. B. N. Was added and reacted for 2 hours. After cooling, the mixed solution was reprecipitated in 3.5 liters of methanol, and the powder was collected by filtration and dried to obtain a white powder with a yield of 92%.
The resulting comb-type copolymer (C-III) had a weight average molecular weight (abbreviated as Mw) of 1.8 × 10 ⁴ . The structure was identified by NMR and IR.

[Synthesis of comb-type copolymer (C-IV)]
(Production Example 2 of Macromonomer (MM): Macromonomer MM-2)
A mixed solution of 70 g of dodecyl methacrylate, 30 g of octadecyl acrylate, 5 g of thioethanol, and 250 g of toluene was heated to a temperature of 75 ° C. while stirring under a nitrogen stream. A. I. B. N. Was reacted for 4 hours. Furthermore, A.I. I. B. N. 0.5 g was added for 3 hours, and then A. was further added. I. B. N. Was reacted for 3 hours. The reaction solution was cooled to room temperature, and 18.2 g of 2-carboxyethyl acrylate was added thereto, and a mixed solution of 24 g of dicyclohexylcarbodiimide (abbreviation DCC) and 150 g of methylene chloride was added dropwise over 1 hour. . 1.0 g of t-butylhydroquinone was added and stirred as it was for 4 hours.
The filtrate obtained by filtering the precipitated crystals was reprecipitated in 2 liters of methanol. The precipitated oil was collected by decantation, dissolved in 150 cc of methylene chloride, and reprecipitated again in 1 liter of methanol. The oil was collected and dried under reduced pressure to obtain a polymer having a yield of 72% and a weight average molecular weight of 1.3 × 10 ⁴ . The structure was identified by NMR and IR.

Monomer having an electrophilic group: Karenz MOI (2-methacryloyloxyethyl isocyanate, Showa Denko, 0.5 mol), macromonomer MM-2 obtained by the above method (0.5 mol) And a mixed solution of 250 g of toluene was heated to a temperature of 80 ° C. while stirring under a nitrogen stream. 3.0 g of 2,2′-azobis (isobutyronitrile) (abbreviation AIBN) was added and reacted for 4 hours. A. I. B. N. Was added for 1.0 hour and reacted for 2 hours. I. B. N. Was added and reacted for 2 hours. After cooling, this mixed solution was reprecipitated in 3.5 liters of methanol, and the powder was collected by filtration and dried to obtain a white powder with a yield of 95%.
The resulting comb-type copolymer (C-IV) had a weight average molecular weight (abbreviated as Mw) of 4.9 × 10 ⁴ . The structure was identified by NMR and IR.

[Partially crosslinked copolymer (C-V)]
A mixed solution of octadecyl methacrylate (0.5 mol), divinylbenzene (0.1 mol), monomer having an electrophilic group: glycidyl methacrylate (0.4 mol), and 300 g of toluene was stirred under a nitrogen stream. The temperature was raised to 85 ° C. 4.0 g of 2,2′-azobis (isobutyronitrile) (abbreviation AIBN) was added and reacted for 4 hours. A. I. B. N. Was added and reacted for 2 hours. After cooling, this mixed solution was reprecipitated in 1.5 liters of methanol, and the powder was collected by filtration and dried to obtain a white powder with a yield of 96%.
The obtained partially crosslinked copolymer (C-V) had a weight average molecular weight of 2.4 × 10 ⁴ . The structure was identified by NMR and IR.

<(B-2) Synthesis Example of Dispersant Having Nucleophilic Group>
[Synthesis of Random Copolymer (C-VI)]
Toluene (200 g) was heated to 80 ° C. with stirring under a nitrogen stream. A monomer having a nucleophilic group: methacrylic acid (0.3 mol), stearyl methacrylate (0.7 mol), and 2,2′-azobis (isobutyronitrile) (abbreviated as AI). .B.N) dissolved in toluene (200 g) was added dropwise over 3 hours. After completion of the dropping, the reaction was carried out at 80 ° C. for 2 hours. I. B. 2 g of N was added and reacted for 2 hours. After cooling, the mixed solution was reprecipitated in 5 liters of methanol, and the powder was collected by filtration and dried to obtain a white solid (C-VI) in a yield of 92%.
The obtained random copolymer (C-VI) had a weight average molecular weight (abbreviated as Mw) of 5.4 × 10 ⁴ . The structure was identified by NMR and IR.

[Synthesis of Random Copolymer (C-VII)]
Toluene (200 g) was heated to 80 ° C. with stirring under a nitrogen stream. A monomer having a nucleophilic group: 2-hydroxyethyl methacrylate (0.3 mol), hexadecyl methacrylate (0.7 mol), 2,2′-azobis (isobutyronitrile) (abbreviation) A.I.B.N) dissolved in toluene (200 g) was added dropwise over 3 hours. After completion of the dropping, the reaction was carried out at 80 ° C. for 2 hours. I. B. 2 g of N was added and reacted for 2 hours. After cooling, the mixed solution was reprecipitated in 5 liters of methanol, and the powder was collected by filtration and dried to obtain a white solid (C-VII) with a yield of 94%.
The obtained random copolymer (C-VII) had a weight average molecular weight (abbreviated as Mw) of 5.8 × 10 ⁴ . The structure was identified by NMR and IR.

[Synthesis of comb-type copolymer (C-VIII)]
Monomer having a nucleophilic group: acrylic acid (0.5 mol), a mixed solution of macromonomer MM-1 obtained by the above-mentioned method (0.5 mol), and 250 g of toluene are stirred under a nitrogen stream. The temperature was raised to 80 ° C. 3.0 g of 2,2′-azobis (isobutyronitrile) (abbreviation AIBN) was added and reacted for 4 hours. A. I. B. N. Was added for 1.0 hour and reacted for 2 hours. I. B. N. Was added and reacted for 2 hours. After cooling, the mixed solution was reprecipitated in 3.5 liters of methanol, and the powder was collected by filtration and dried to obtain a white powder with a yield of 92%.
The resulting comb-type copolymer (C-VIII) had a weight average molecular weight (abbreviated as Mw) of 7.2 × 10 ⁴ . The structure was identified by NMR and IR.

[Synthesis of comb-type copolymer (C-IX)]
Monomer having a nucleophilic group: HO-MS (the following structure, 0.5 mol), a macromonomer MM-2 obtained by the above method (0.5 mol), and a mixed solution of 250 g of toluene. The mixture was heated to 80 ° C. with stirring under a nitrogen stream. 3.0 g of 2,2′-azobis (isobutyronitrile) (abbreviation AIBN) was added and reacted for 4 hours. A. I. B. N. Was added for 1.0 hour and reacted for 2 hours. I. B. N. Was added and reacted for 2 hours. After cooling, this mixed solution was reprecipitated in 3.5 liters of methanol, and the powder was collected by filtration and dried to obtain a white powder with a yield of 95%.
The resulting comb-type copolymer (C-IX) had a weight average molecular weight (abbreviated as Mw) of 8.5 × 10 ⁴ . The structure was identified by NMR and IR.

[Partially crosslinked copolymer (C-X)]
A mixed solution of octadecyl methacrylate (0.5 mol), divinylbenzene (0.1 mol), monomer having a nucleophilic group: 2-hydroxyethyl methacrylate (0.4 mol), and 300 g of toluene is streamed with nitrogen. The mixture was heated to 85 ° C. with stirring. 4.0 g of 2,2′-azobis (isobutyronitrile) (abbreviation AIBN) was added and reacted for 4 hours. A. I. B. N. Was added and reacted for 2 hours. After cooling, this mixed solution was reprecipitated in 1.5 liters of methanol, and the powder was collected by filtration and dried to obtain a white powder with a yield of 96%.
The obtained partially crosslinked copolymer (C-X) had a weight average molecular weight of 4.6 × 10 ⁴ . The structure was identified by NMR and IR.

<Synthesis Example of Comparative Dispersant>
[Synthesis of Random Copolymer (PI)]
Toluene (200 g) was heated to 80 ° C. with stirring under a nitrogen stream. Thereto, styrene (0.3 mol), stearyl methacrylate (0.7 mol), 2,2′-azobis (isobutyronitrile) (abbreviation AIBN) dissolved in 200 g of toluene were added. It was dripped over 3 hours. After completion of the dropping, the reaction was carried out at 80 ° C. for 2 hours. I. B. 2 g of N was added and reacted for 2 hours. After cooling, the mixed solution was reprecipitated in 5 liters of methanol, and the powder was collected by filtration and dried to obtain a white solid (CI) in a yield of 92%.
The obtained random copolymer (PI) had a weight average molecular weight (abbreviated as Mw) of 2.9 × 10 ⁴ . The structure was identified by NMR and IR.

[Synthesis of Random Copolymer (P-II)]
Toluene (200 g) was heated to 80 ° C. with stirring under a nitrogen stream. Thereto, styrene (0.3 mol), hexadecyl methacrylate (0.7 mol), and 2,2′-azobis (isobutyronitrile) (abbreviation AIBN) dissolved in 200 g of toluene were added. It was dripped over 3 hours. After completion of the dropping, the reaction was carried out at 80 ° C. for 2 hours. I. B. 2 g of N was added and reacted for 2 hours. After cooling, the mixed solution was reprecipitated in 5 liters of methanol, and the powder was collected by filtration and dried to obtain a white solid (C-II) with a yield of 94%.
The obtained random copolymer (P-II) had a weight average molecular weight (abbreviated as Mw) of 4.1 × 10 ⁴ . The structure was identified by NMR and IR.

[Synthesis of comb-type copolymer (P-III)]
A mixed solution of methyl methacrylate (0.5 mol), macromonomer MM-1 obtained by the above method (0.5 mol) and 250 g of toluene was heated to 80 ° C. while stirring under a nitrogen stream. 3.0 g of 2,2′-azobis (isobutyronitrile) (abbreviation AIBN) was added and reacted for 4 hours. A. I. B. N. Was added for 1.0 hour and reacted for 2 hours. I. B. N. Was added and reacted for 2 hours. After cooling, the mixed solution was reprecipitated in 3.5 liters of methanol, and the powder was collected by filtration and dried to obtain a white powder with a yield of 92%.
The resulting comb-type copolymer (P-III) had a weight average molecular weight (abbreviated as Mw) of 2.4 × 10 ⁴ . The structure was identified by NMR and IR.

[Synthesis of comb-type copolymer (P-IV)]
A mixed solution of methyl methacrylate (0.5 mol), macromonomer MM-2 obtained by the above method (0.5 mol) and 250 g of toluene was heated to a temperature of 80 ° C. while stirring under a nitrogen stream. 3.0 g of 2,2′-azobis (isobutyronitrile) (abbreviation AIBN) was added and reacted for 4 hours. A. I. B. N. Was added for 1.0 hour and reacted for 2 hours. I. B. N. Was added and reacted for 2 hours. After cooling, this mixed solution was reprecipitated in 3.5 liters of methanol, and the powder was collected by filtration and dried to obtain a white powder with a yield of 95%.
The resulting comb-type copolymer (P-IV) had a weight average molecular weight (abbreviated as Mw) of 4.1 × 10 ⁴ . The structure was identified by NMR and IR.

[Partially crosslinked copolymer (P-V)]
A mixed solution of octadecyl methacrylate (0.5 mol), divinylbenzene (0.1 mol), methyl methacrylate (0.4 mol), and toluene 300 g was heated to a temperature of 85 ° C. while stirring under a nitrogen stream. 4.0 g of 2,2′-azobis (isobutyronitrile) (abbreviation AIBN) was added and reacted for 4 hours. A. I. B. N. Was added and reacted for 2 hours. After cooling, this mixed solution was reprecipitated in 1.5 liters of methanol, and the powder was collected by filtration and dried to obtain a white powder with a yield of 96%.
The weight average molecular weight of the obtained partially crosslinked copolymer (P-V) was 2.6 × 10 ⁴ . The structure was identified by NMR and IR.

[Dispersant (P-VI)]
A mixed solution of 100 g of tetradecyl methacrylate, 2 g of thioethanol, and 200 g of toluene was heated to a temperature of 70 ° C. while stirring under a nitrogen stream. A. I. B. N. Was added and reacted for 4 hours. Furthermore, A.I. I. B. N. 0.5 g was added for 3 hours, and then A. was further added. I. B. N. Was reacted for 3 hours. The reaction solution was cooled to room temperature, 8 g of 2-carboxyethyl acrylate was added thereto, and a mixed solution of 12.7 g of dicyclohexylcarbodiimide (abbreviation DCC) and 60 g of methylene chloride was added dropwise thereto over 1 hour. Further, 1.0 g of t-butylhydroquinone was added and stirred as it was for 4 hours. The filtrate obtained by filtering the precipitated crystals was reprecipitated in 2 liters of methanol. The precipitated oil was collected by decantation, dissolved in 150 ml of methylene chloride, and reprecipitated again in 1 liter of methanol. The oil was collected and dried under reduced pressure to obtain a polymer (dispersant (P-VI) having the following structure) with a yield of 60 g and a weight average molecular weight of 8 × 10 ³ .

<Preparation of ink composition>
[(B-1) Synthesis of specific dispersed resin particles (X-1)]
(B-1) Dispersant (C-I) 20 g having an electrophilic group, methyl methacrylate 20 g, methyl acrylate 40 g, and (a-1) a monomer having a nucleophilic group: methacrylic acid A mixed solution of 40 g and (c) 200 g of Isopar G as a non-aqueous solvent was heated to a temperature of 70 ° C. while stirring under a nitrogen stream. As a polymerization initiator, A.I. I. V. N. Was added and reacted for 3 hours. In addition, initiator A.I. I. B. N. 1.0 g was added, and the mixture was heated to 80 ° C. and reacted for 4 hours. Subsequently, the temperature was raised to 100 ° C. and stirred for 1 hour to distill off unreacted monomers. After cooling, it was passed through a 200-mesh nylon cloth. The resulting white dispersion had a polymerization rate of 98.1%, a volume average particle size of 1.05 μm, and Mw containing particles of 8.4 × 10 ⁴ .
The particle size was measured with CAPA-500 (manufactured by Horiba, Ltd.).

[Synthesis of (B-1) Specific Dispersed Resin Particles (X-2) to (X-10)]
Monomers (including a monomer having (a-1) a nucleophilic group) for synthesizing resin particles having the structure described in Table 1 below are used, and ( b-1) Using the same method as the synthesis method of the specific dispersion resin particle (X-1) except that a dispersant having an electrophilic group is used, (B-1) the specific dispersion resin particle (X -2) to (X-10) were synthesized.

[Synthesis of (B-1) Specific Dispersed Resin Particles (X-11)]
(B-1) Dispersant (C-I) 20 g having an electrophilic group, methyl methacrylate 20 g, methyl acrylate 40 g, and (a-1) a monomer having a nucleophilic group: methacrylic acid A mixed solution of 40 g and (c) 800 g of Isopar G as a non-aqueous solvent was heated to a temperature of 70 ° C. while stirring under a nitrogen stream. As a polymerization initiator, A.I. I. V. N. Was added and reacted for 3 hours. In addition, initiator A.I. I. B. N. 1.0 g was added, and the mixture was heated to 80 ° C. and reacted for 4 hours. Subsequently, the temperature was raised to 100 ° C. and stirred for 1 hour to distill off unreacted monomers. After cooling, it was passed through a 200-mesh nylon cloth, and the resulting white dispersion had a polymerization rate of 90.1%, a volume average particle size of 0.41 μm, and Mw containing particles of 8.4 × 10 ⁴ .
The particle size was measured with CAPA-500 (manufactured by Horiba, Ltd.).

[Synthesis of (B-1) Specific Dispersed Resin Particles (X-12) to (X-15)]
Monomers (including a monomer having (a-1) a nucleophilic group) for synthesizing resin particles having the structure described in Table 1 below are used, and ( b-1) Using the same method as the synthesis method of the specific dispersion resin particle (X-11) except that a dispersant having an electrophilic group is used, (B-1) the specific dispersion resin particle (X -12) to (X-15) were synthesized.

[(B-2) Synthesis of specific dispersed resin particles (X-16)]
(B-2) 20 g of a dispersant (C-VI) having a nucleophilic group, 20 g of methyl methacrylate, 40 g of dimethylaminoethyl methacrylate, and (a-2) a monomer having an electrophilic group: A mixed solution of 40 g of glycidyl methacrylate and (c) 200 g of Isopar G as a non-aqueous solvent was heated to a temperature of 70 ° C. while stirring under a nitrogen stream. As a polymerization initiator, A.I. I. V. N. Was added and reacted for 3 hours. In addition, initiator A.I. I. B. N. 1.0 g was added, and the mixture was heated to 80 ° C. and reacted for 4 hours. Subsequently, the temperature was raised to 100 ° C. and stirred for 1 hour to distill off unreacted monomers. After cooling, it was passed through a 200-mesh nylon cloth. The resulting white dispersion had a polymerization rate of 99.1%, a volume average particle size of 1.79 μm, and Mw containing particles of 6.3 × 10 ⁴ .
The particle size was measured with CAPA-500 (manufactured by Horiba, Ltd.).

[Synthesis of (B-2) Specific Dispersed Resin Particles (X-17) to (X-25)]
Monomers (including a monomer having an electrophilic group (a-2)) for synthesizing resin particles having the structure described in Table 2 below are used, and ( b-2) Except for using a dispersant having a nucleophilic group, using the same method as the method for synthesizing the specific dispersed resin particle (X-16), (B-2) the specific dispersed resin particle (X -17) to (X-25) were synthesized.

[(B-2) Synthesis of specific dispersed resin particles (X-26)]
(B-2) 20 g of a dispersant (C-VI) having a nucleophilic group, 20 g of methyl methacrylate, 40 g of dimethylaminoethyl methacrylate, and (a-2) a monomer having an electrophilic group: A mixed solution of 40 g of glycidyl methacrylate and 800 g of Isopar G as a non-aqueous solvent was heated to 70 ° C. while stirring under a nitrogen stream. As a polymerization initiator, A.I. I. V. N. Was added and reacted for 3 hours. In addition, initiator A.I. I. B. N. 1.0 g was added, and the mixture was heated to 80 ° C. and reacted for 4 hours. Subsequently, the temperature was raised to 100 ° C. and stirred for 1 hour to distill off unreacted monomers. After cooling, it was passed through a 200-mesh nylon cloth. The resulting white dispersion had a polymerization rate of 88.1%, a volume average particle size of 0.36 μm, and Mw containing 12.5 × 10 ⁴ particles.
The particle size was measured with CAPA-500 (manufactured by Horiba, Ltd.).

[(B-2) Synthesis of specific dispersed resin particles (X-27) to (X-30)]
Monomers (including a monomer having an electrophilic group (a-2)) for synthesizing resin particles having the structure described in Table 2 below are used, and ( b-2) Except that a dispersant having a nucleophilic group was used, a method similar to the method for synthesizing the specific dispersed resin particle (X-26) was used. -27) to (X-30) were synthesized.

[Synthesis of Comparative Dispersion Resin Particles (N-1) to (N-6)]
Monomers (including a monomer having (a-1) nucleophilic group) for synthesizing resin particles having the structure described in Table 3 below, and comparison in Table 3 below are used. Comparative dispersion resin particles (N-1) to (N-6) were synthesized using the same method as the synthesis method of the specific dispersion resin particles (X-1) except that the dispersant for use was used.

[Synthesis of Comparative Dispersion Resin Particles (N-7) to (N-12)]
Using monomers for synthesizing resin particles having the structures described in Table 3 below (including monomers having (a-2) electrophilic groups), and further comparing in Table 3 below Comparative dispersion resin particles (N-7) to (N-12) were synthesized using the same method as the synthesis method of the specific dispersion resin particles (X-16) except that the dispersant for use was used.

Example 1
[Preparation of Ink Composition (Y-1)]
The dispersion containing the (B-1) specific dispersion resin particles (X-1) obtained as described above is obtained by using Isopar G, and the solid content of the specific dispersion resin particles (X-1) is 50 g. And it diluted so that it might become the dispersion liquid containing 20 mass% of specific dispersion resin particles (X-1), 5 g of Victoria pure blues were added there, and it was made to react at 50 degreeC for 4 hours. After completion of the reaction, the specific dispersed resin particles were colored blue by filtering through a 4 μm filter.
Subsequently, the dispersion containing the colored specific dispersed resin particles was diluted with Isopar G so that the solid content concentration was 7.0% by mass. Thereto, an octadecene-half-maleic acid octadecylamide copolymer was added as a charge control agent so as to be 0.02% by mass.
The blue colored ink (Y-1) of Example 1 was obtained as described above.

<< Examples 2 to 30, Comparative Examples 1 to 12 >>
[Preparation of Ink Compositions (Y-2) to (Y-30), (Q-1) to (Q-12)]
In the preparation of the ink composition (Y-1), the specific dispersed resin particles (X-1) used are the specific dispersed resin particles (X-2) to (X-20) and (M-1) shown in Table 4 below. ) To (M-10) and comparative dispersed resin particles (N-1) to (N-12), respectively, except that the ink compositions (Y- 2) to (Y-30) and ink compositions (Q-1) to (Q-12) of Comparative Examples 1 to 12 were produced.
Here, dispersed resin particles ((B) specific dispersed resin particles or comparative dispersed resin contained in ink compositions (Y-1) to (Y-30) and (Q-1) to (Q-12) Particles) are as shown in Table 4 below.

<Evaluation>
About the obtained ink composition: 1. redispersibility, 2. dispersion stability; 3. discharge performance, and Each evaluation of the printing durability of the planographic printing plate was performed.

1. Evaluation of redispersibility The obtained ink composition was filled in a glass bottle and allowed to stand at 30 ° C. for 2 weeks, and then the ink composition shaken 50 times up and down by hand was filtered with a filter having a pore diameter of 4 μm. The degree of particles remaining on the top was visually evaluated.
The case where no particles were observed on the filter paper was indicated as “◯”, the case where slight particles were observed as “Δ”, and the case where many particles remained on the filter paper as “X”. The results are shown in Table 4.

2. Evaluation of Dispersion Stability The ink composition obtained by allowing the obtained ink composition to stand at 30 ° C. for 3 days was filtered with a filter having a pore diameter of 4 μm, and the degree of particles remaining on the filter paper was visually evaluated.
The case where no particles were observed on the filter paper was indicated as “◯”, the case where slight particles were observed as “Δ”, and the case where many particles remained on the filter paper as “X”. The results are shown in Table 4.

3. Evaluation of ejectability The obtained ink composition was fed into an ink jet recording apparatus having the configuration shown in FIGS. After removing dust on the surface of the coated recording paper as a recording medium by air pump suction, the ejection head was brought close to the coated recording paper to the drawing position, and ink was ejected and drawn at a drawing resolution of 600 dpi. At this time, a pulse voltage of 500 V was applied to the first ejection electrode 46 and the second ejection electrode 56, and the ejected dot diameter was evaluated as an ejection index. This discharge index indicates that the larger the number, the higher the electric field response of the particles and the better the performance. The results are shown in Table 4.

4). Evaluation of printing durability of a lithographic printing plate Using the following electrostatic ink jet recording apparatus and ink jet recording method, an image portion of a lithographic printing plate is formed from the obtained ink composition, and the printing durability is evaluated. evaluated. The results are shown in Table 4.

-Electrostatic inkjet recording apparatus and inkjet 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. A fine coated paper for offset printing was used as a 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 when discharging, and a pulse voltage of +500 V is applied (pulse width 50 μsec) when discharging, and an image is formed on the recording medium at a driving frequency of 15 kHz. Went. Thereafter, the image was fixed by heating in an oven at 120 ° C. for 20 seconds.

Using the electrostatic inkjet recording apparatus and inkjet recording method described above, the obtained ink composition is jetted onto an aluminum support described later, and then fixed by heating in a 120 ° C. oven for 20 seconds. Got a version. The obtained lithographic printing plate was used as a printing machine using Lislon manufactured by Komori Corporation, and used as graph G (N) manufactured by Dainippon Ink Co., Ltd. On the 5,000th sheet from the start of printing, PS plate cleaner CL-2 manufactured by Fuji Photo Film Co., Ltd. was soaked in a printing sponge, the fine line portion was wiped off, and the ink on the printing plate was washed.
Thereafter, the printed matter of the image line fine line (10 μm) was observed, and the thin line printing durability was relatively compared according to the number of images where the image began to fade.
The evaluation result was expressed as a printing durability index based on a lithographic printing plate produced using the ink composition of Example 1 as a reference (100). The larger the printing durability index is, the higher printing durability is preferable.

<Preparation of lithographic printing plate support>
[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.

As apparent from Table 4, the ink compositions of Examples 1 to 30 (the ink composition of the present invention) are excellent in redispersibility and dispersion stability of the dispersed resin particles, and thus stable over time as the ink composition. It turns out that it is excellent also in property. Moreover, it turns out that the ink composition of Examples 1-40 is also excellent in dischargeability compared with the ink composition of Comparative Examples 1-12.
Furthermore, when a lithographic printing plate is prepared using the ink compositions of Examples 1 to 40, the printing durability may be excellent as compared with the case where the ink compositions of Comparative Examples 1 to 12 are used. 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 adsorbing means 10 Static eliminating 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 40 Support rod Part 42 Ink meniscus 44 Insulating layer 46 First ejection electrode 48 Insulating layer 50 Guard electrode 52 Insulating layer 56 Second ejection 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 Opening 76, 76A, 7 6B Discharge unit 78 Ink guide unit 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 Electrolyte 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 device 412 Power feeding tank 414 Electrolytic treatment tank 416 Aluminum plate 418, 426 Electrolytic solution 420 Power feeding electrode 422, 428 Roller 424 Nip roller 430 Electrolytic electrode 432 Tank wall 434 DC power supply

Claims (3)

  (A) a non-aqueous dispersion medium, (B-1) dispersed resin particles obtained by reacting a resin particle having a nucleophilic group and a dispersant having an electrophilic group, and (B-2) An ink-jet ink composition comprising at least one selected from the group consisting of dispersed resin particles obtained by reacting a dispersant having a nucleophilic group and resin particles having an electrophilic group.   The inkjet ink composition according to claim 1, which is an ink composition for a lithographic printing plate used when an image is drawn on the lithographic printing plate support by an inkjet recording method.   A method for producing a lithographic printing plate, comprising forming an image portion on a recording medium for a lithographic printing plate by an ink jet recording method using the ink composition for ink jet according to claim 1 or 2.

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