JP2002192846A - Original plate for planographic printing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an original plate for planographic printing capable of being printed in a state directly mounted on a printing press without being treated after scanning exposure based on a digital signal and improved in antistaining properties and printing durability. SOLUTION: The original plate for paleographic printing is obtained by providing a hydrophilic layer, which contains self-water dispersible hydrophobilized resin fine particles, a photothermal converting agent and a hydrophilic binder and can be made hydrophobic by heat, on a support.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a negative-working negative planographic printing plate having a hydrophilic layer for forming an image on a support. More specifically, the present invention relates to a lithographic printing original plate capable of recording an image by infrared scanning exposure based on a digital signal and mounting the image-recorded image directly on a printing machine without development processing.

[0002]

2. Description of the Related Art In recent years, computer-to-computer
Numerous studies have been made on plate printing plates. Among them, the aim is to further streamline the process and solve the problem of waste liquid treatment. As a result, lithographic printing original plates that can be mounted directly on a printing press without exposure and development processing, or exposed on a printing press and printed directly Possible lithographic printing plates have been studied and various methods have been proposed.

One promising method is a heat-sensitive lithographic plate having a hydrophilic layer (image forming layer) in which fine particles such as thermoplastic polymer fine particles and microcapsules containing a lipophilic substance are dispersed in a matrix such as a hydrophilic resin. An original plate for printing is used. When heat is applied to the hydrophilic layer, the thermoplastic polymer particles melt and coalesce, or the contained lipophilic substance scatters out of the microcapsules, converting the hydrophilic layer surface into a lipophilic image area. It is known that lithographic printing using a fountain solution can be performed without any treatment by using the surface configuration of the lipophilic image area and the hydrophilic non-image area composed of an unexposed hydrophilic matrix as a printing surface. ing.

[0004] In addition, such an unprocessed lithographic printing plate is directly mounted on a printing machine placed in a bright room.
It is necessary to have a property that does not cause problems even when exposed to room light (light room handling), but it is also known that the use of a thermal recording head or infrared exposure as a recording means enables light room handling. ing.

For example, Japanese Unexamined Patent Publication No. 59-174394, Research Disclosure No. 333, January 1992,
No. 03 and the like disclose a heat-sensitive lithographic printing original plate having a heat-sensitive layer in which thermoplastic polymer fine particles are dispersed in a hydrophilic resin, and describe that printing can be performed without treatment after thermal recording.

Further, for example, Japanese Patent No. 2938397, Japanese Patent Application Laid-Open No. 9-127683 and WO99-
No. 10186 discloses a lithographic printing original plate in which a photosensitive layer (image recording layer) in which fine particles of a thermoplastic hydrophobic polymer are dispersed in a hydrophilic binder polymer is provided on a hydrophilic support. According to this publication, the lithographic printing original plate is subjected to infrared laser exposure to form an image by heat-bonding thermoplastic hydrophobic polymer fine particles to form an image. Then, the plate is mounted on a printing press cylinder, and dampening water and / or Alternatively, it is described that on-press development can be performed with ink.

[0007]

However, these lithographic printing original plates according to the prior art have a problem in that they are difficult to stain in printing and have insufficient printing durability. Therefore,
It is an object of the present invention to solve this problem. That is, it is an object of the present invention to provide a lithographic printing original plate which can be directly mounted on a printing machine for printing after exposure without any processing, and has improved stain resistance and printing durability.

[0008]

In order to solve the above-mentioned problems, the present inventor has studied in detail the polarity conversion behavior of the hydrophobized resin fine particles in the hydrophilic binder to heat. By introducing a hydrophilic group into the molecular structure, self-water dispersion becomes possible, and the compatibility with the hydrophilic binder is improved, so that the film strength is reduced without lowering the hydrophilicity of the non-image area. It has been found that the printing durability is improved and the ink receptivity of the film converted into the lipophilic image area by heating can be maintained. Further, it has been found that this tendency is remarkable in the hydrophobic resin fine particles having a core / shell structure in which the core portion is a lipophilic resin and the shell portion is a hydrophilic component. Based on these findings, the present inventors have further studied and completed the present invention. That is, the present invention is as follows.

1. A lithographic printing plate comprising a support and a heat-hydrophobizable hydrophilic layer containing self-water dispersible hydrophobic resin fine particles, a photothermal conversion agent and a hydrophilic binder.

[0010] 2. The resin of the hydrophobized resin particles has, in the molecule, an acrylic resin, an epoxy resin, a styrene resin, a urethane resin, a phenol resin, a structural portion of at least one lipophilic resin selected from the group consisting of vinyl ester resins and derivatives thereof. A resin having a structural portion having at least one hydrophilic group selected from a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a hydroxyl group, an amide group, a sulfonamide group and an amino group. The lithographic printing plate as described.

3. 2. The lithographic printing original plate as described in 1 above, wherein the hydrophobic resin fine particles have a core / shell structure, the core portion is a lipophilic resin, and the shell portion is fine particles comprising a hydrophilic component.

4. The lipophilic resin of the core portion is at least one resin selected from the group consisting of an acrylic resin, an epoxy resin, a styrene resin, a urethane resin, a phenol resin, a vinyl ester resin and a derivative thereof. Lithographic printing plate.

5. The hydrophilic component of the shell portion is a resin having at least one hydrophilic group selected from a carboxylic acid group, a phosphoric acid group, a phosphonic acid group, a hydroxyl group, an amide group, a sulfonamide group, and an amino group. 5. The lithographic printing original plate as described in 3 or 4 above.

Japanese Patent Application Laid-Open No. 11-348446 discloses a heat-sensitive composition containing a substance that absorbs light and generates heat, an anionic self-water-dispersible resin fine particle, and a fluorine-containing surfactant. A negative planographic printing plate precursor coated on a support having a surface is disclosed. However,
This lithographic printing plate precursor is, after exposure, removes unexposed portions by performing wet development, and relates to a printing plate having a hydrophilic surface of a support as a non-image portion, and after exposure, as in the present invention,
There is no disclosure or suggestion for a lithographic printing original plate which can be printed without processing and in which an unexposed portion of the hydrophilic layer provided on the support becomes a non-image portion.

[0015]

Embodiments of the present invention will be described below in detail. In the lithographic printing plate precursor of the present invention, the basic layer configuration is to have a hydrophilic layer on the support, and if necessary, a heat-insulating layer between the support and the hydrophilic layer, and a water-soluble layer on the hydrophilic layer. It can have a protective layer.

[Hydrophilic layer] The hydrophilic layer of the present invention contains hydrophobic particles of a self-dispersible hydrophobic resin, a photothermal conversion agent and a hydrophilic binder.

The self-water dispersible hydrophobized resin particles of the present invention are heat-softening or heat-fusing resin particles, which are fused or united when a certain amount of heat is applied to the hydrophilic layer. Self-dispersible resin fine particles having the function of converting phenol into hydrophobic. As preferred self-water dispersible hydrophobized resin fine particles, (1) a starting resin having a lipophilic resin portion and a hydrophilic group in a molecule is described in JP-A-3-221137 and JP-A-5-66600. Resin fine particles dispersed in water without an emulsifier or protective colloid by the phase inversion emulsification method as described above, and (2) having a core / shell structure, a core portion comprising a lipophilic resin, and a shell portion comprising a hydrophilic component. Resin fine particles can be used.

Examples of the hydrophilic group in the raw material resin molecule used in the phase inversion emulsification method include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a hydroxyl group, an amide group, a sulfonamide group and an amino group. Specific examples of the monomer having a hydrophilic group, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monobutyl itaconate, monobutyl maleate, acid phosphooxyethyl methacrylate, acid phosphooxypropyl Examples thereof include methacrylate, 3-chloro-2-acrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl methacrylate, acrylamide, N-vinylpyrrolidone, N-vinylimidazole, and hydroxyethyl acrylate.

As an example of the lipophilic resin portion in the raw material resin molecule used in the phase inversion emulsification method, a polymer portion obtained by polymerizing or copolymerizing the following polymerizable monomers (A) to (J) is exemplified. be able to.

(A) Acrylic esters. Examples of this monomer group include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, cyclohexyl acrylate,
Octyl acrylate, phenyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, o-, m- and p-hydroxyphenyl acrylate, glycidyl acrylate, N -Dimethylaminoethyl acrylate and the like.

(B) Methacrylic esters. Examples of this monomer group include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, phenyl methacrylate, benzyl methacrylate, Methacrylic acid-2-
Chloroethyl, 2-hydroxyethyl methacrylate,
4-Hydroxybutyl methacrylate, o-, m- and p-hydroxyphenyl methacrylate, glycidyl methacrylate, N, N-dimethylaminoethyl methacrylate and the like.

(C) Substituted acrylamides and substituted methacrylamides. Examples of this monomer group include N-methylol acrylamide, N-methylol methacrylamide,
-Ethylacrylamide, N-ethylmethacrylamide, N-hexylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-
Cyclohexyl methacrylamide, N-hydroxyethyl acrylamide, N-hydroxyethyl acrylamide, N-phenyl acrylamide, N-phenyl methacrylamide, N-benzyl acrylamide, N-benzyl methacrylamide, N-nitrophenyl acrylamide, N-nitrophenyl methacrylamide , N-ethyl-N-phenylacrylamide and N-ethyl-N-
Examples include phenylmethacrylamide, N- (4-hydroxyphenyl) acrylamide, and N- (4-hydroxyphenyl) methacrylamide.

(D) Vinyl ethers. Examples of this monomer group include ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether and the like. (E) Vinyl esters. Examples of this group of monomers include vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate, and the like. (F) Styrenes. Examples of this group of monomers include styrene,
Examples include methylstyrene, t-butylstyrene, chloromethylstyrene, o-, m- and p-hydroxystyrene.

(G) Vinyl ketones. Examples of this monomer group include methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, phenyl vinyl ketone, and the like. (H) olefins. Examples of this monomer group include ethylene, propylene, isobutylene, butadiene, isoprene and the like. (I) N-containing monomers. Examples of this monomer group include N-vinylcarbazole, acrylonitrile, methacrylonitrile, and the like.

(J) Unsaturated sulfonamide. Examples of this monomer group include N- (o-aminosulfonylphenyl) acrylamide, N- (m-aminosulfonylphenyl)
Acrylamides such as acrylamide, N- (p-aminosulfonylphenyl) acrylamide, N- [1- (3-aminosulfonyl) naphthyl] acrylamide, N- (2-aminosulfonylethyl) acrylamide, N- (o-aminosulfonyl) Phenyl) methacrylamide, N- (m-aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonylphenyl) methacrylamide, N- [1- (3-aminosulfonyl)
Naphthyl] methacrylamides such as methacrylamide and N- (2-aminosulfonylethyl) methacrylamide; o-aminosulfonylphenyl acrylate; m-aminosulfonylphenyl acrylate;
Unsaturated sulfonamides such as acrylates such as aminosulfonylphenyl acrylate and 1- (3-aminosulfonylphenylnaphthyl) acrylate; o
-Aminosulfonylphenyl methacrylate, m-aminosulfonylphenyl methacrylate, p-aminosulfonylphenyl methacrylate, 1- (3-aminosulfonylphenylnaphthyl) methacrylate and the like.

In some cases, the lipophilic resin portion in the raw material resin molecule used in the phase inversion emulsification method may be a copolymer of the above-mentioned polymerizable monomers and an oligomer containing a polymerizable unsaturated group. Good. Examples of such a polymerizable unsaturated group-containing oligomer include vinyl-modified polyester, vinyl-modified polyurethane, vinyl-modified epoxy resin, and vinyl-modified phenol resin. Specific examples include maleic anhydride, fumaric acid, tetrahydrophthalic anhydride, endomethylene tetrahydromaleic anhydride,
Polymerizable unsaturated bonds (vinyl groups) are introduced by polycondensation or addition of various compounds such as α-terpinene maleic anhydride adduct, triallyl monoallyl ether, pentaerythritol diallyl ether or allyl glycidyl ether.

Further, in order to introduce an acid group into the polyester, for example, an excess of a dibasic acid such as phthalic acid may be used, whereby a product having a terminal carboxyl group can be obtained. Alternatively, one having an acid group in the main chain can be obtained by using trimellitic anhydride.

The vinyl-modified polyurethane can be obtained by, for example, addition polymerization of various polyols and diisocyanate such as glycerin monoallyl ether or butadiene polyol having a 1,2-bond. Alternatively, a vinyl bond is also introduced by an addition reaction of urethane having an isocyanate group at a terminal with a polymerizable monomer having a hydroxyl group. Also, by adding dimethylolpropionic acid or the like as a polyol component,
An acid component can be introduced into the polyurethane.

Examples of the vinyl-modified epoxy resin include those obtained by reacting a terminal epoxy group of an epoxy resin with a carboxyl group of acrylic acid or methacrylic acid.

Examples of the vinyl-modified phenol resin include those obtained by reacting a hydroxyl group of a phenol resin with a (meth) acrylic halide or glycidyl (meth) acrylate.

Further, an oligomer of a polymerizable monomer having a polymerizable vinyl group obtained by adding a glycidyl group-containing polymerizable monomer to a carboxyl group-containing vinyl copolymer is obtained. The polymerizable monomers used here are selected from those described above. However, if it is an oligomer having a polymerizable vinyl group, it is not limited to the above-described types and methods.

By copolymerizing at least one selected from these monomers and oligomers having a polymerizable unsaturated group with the above-mentioned monomer having a hydrophilic group, a self-water-dispersible resin fine particle is obtained by a phase inversion emulsification method. A raw resin is obtained. This raw material resin has a weight average particle size of 500 to 500,000,
The number average molecular weight is preferably from 200 to 60,000.

Further, the raw material resin of the self-water dispersible resin fine particles may have a heat-reactive functional group. Examples of the heat-reactive functional group include an ethylenically unsaturated group that performs a polymerization reaction (for example, an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, and the like), an epoxy group that performs an addition reaction, an isocyanate group, and a block body thereof. be able to. The introduction of a heat-reactive functional group is effective in increasing the strength of the image area after exposure and improving printing durability. The introduction of the heat-reactive functional group can be performed, for example, by a polymer reaction described in WO 96-34316.

In addition to the above, as the self-dispersible resin fine particles used in the present invention, urethane resin, for example, urethane resin dispersion disclosed in JP-A-1-287183, epoxy resin, for example, Kaisho 53-
No. 1228, No. 55-3481 or No. 55-9433
And various epoxy compounds as described in the above item.

The hydrophobic resin fine particles of the present invention can contain a hydrophobic organic low-molecular compound in the fine particles in order to enhance the action of melting, diffusing and leaching due to the heat generated by light irradiation to make the vicinity hydrophobic. .

Examples of such organic low molecular weight compounds include printing ink components, plasticizers, other high-boiling aliphatic and aromatic hydrocarbons, carboxylic acids, alcohols, esters, ethers, amines and derivatives thereof. And the like.

Specific examples include fats and oils such as linseed oil, soybean oil, poppy oil, and safflower oil; plasticizers such as tributyl phosphate, tricresyl phosphate, dibutyl phthalate, butyl laurate, and dioctyl phthalate; carnauba wax; Custer wax, microcrystalline wax, paraffin wax, shellac wax, palm wax,
Fine particle dispersions such as waxes such as beeswax and metal salts of long chain fatty acids such as low molecular weight polyethylene, silver behenate, calcium stearate, magnesium palmitate,
n-nonane, n-decane, n-hexadecane, octadecane, eicosane, caproic acid, capric acid, stearic acid, oleic acid, dodecyl alcohol, octyl alcohol, n-octadecyl alcohol, 2-octanol, lauryl alcohol, lauryl methyl ether, Examples include stearyl methyl ether, stearylamide and the like.

The above-mentioned inclusion of the hydrophobic organic compound in the hydrophobic resin fine particles can be carried out by adding the hydrophobic organic compound to an organic solvent in which the hydrophobic resin is dissolved and performing phase inversion emulsification. it can.

The solidification temperature of the self-water dispersible hydrophobized resin fine particles is preferably 70 ° C. or higher, and more preferably 100 ° C. or higher in consideration of stability over time.

The self-water-dispersible resin fine particles having a core-shell structure used in the present invention comprise fine particles of a hydrophobic polymer softened or melted by the action of heat obtained by emulsification (including the phase inversion emulsification method) or dispersion polymerization. As the part, core-shell type composite fine particles having a polymer layer of a hydrophilic polymer formed therearound or hetero-phase structure fine particles simply referred to as core-shell type fine particles. The formation of the polymer layer of the hydrophilic polymer is performed by adding a hydrophilic monomer to a dispersion of core particles (seed) and polymerizing the hydrophilic monomer on the surface of the core particles.

The polymer constituting the core phase is at least one lipophilic resin selected from the group consisting of acrylic resin, epoxy resin, styrene resin, urethane resin, phenol resin, vinyl ester resin and derivatives thereof.
Specifically, it can be selected from the resins described as the raw material resin used in the phase inversion emulsification method and the resin fine particles obtained by the phase inversion emulsification method.

The hydrophilic resin forming the shell phase includes carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, hydroxyl groups, amide groups,
It is a resin having at least one hydrophilic group selected from a sulfonamide group and an amino group. Examples of such a resin include these monomers having a hydrophilic group and the above-mentioned (A) to (A).
Examples of the resin described in the method of synthesizing the raw material resin molecules used in the phase inversion emulsification method, such as a copolymer with the polymerizable monomer or the oligomer having a polymerizable unsaturated group (J). In addition, for example, various epoxy resins having a core-shell structure described in JP-A-5-9431 are also suitable as the self-water-dispersible resin fine particles of the present invention.

In the case of the above-mentioned core-shell structure self-water-dispersible resin fine particles, similarly to the case of the above-mentioned resin fine particles by phase inversion emulsification, a hydrophilic compound can be adsorbed on the resin surface,
A hydrophobic organic compound can be included in the resin.
Compounds suitable for adsorption or inclusion include the same compounds as described for the resin fine particles by phase inversion emulsification.

The average particle size of the hydrophobic resin fine particles used in the present invention is preferably 0.01 to 20 μm, more preferably 0.05 to 2.0 μm, and particularly preferably 0.1 to 2.0 μm.
1.0 μm is optimal. Within this range, good resolution and long-term stability can be obtained.

The hydrophilic layer of the present invention contains a photothermal converting agent for converting light into heat in order to increase the sensitivity. Further, in the present invention, a light conversion agent may be contained in a heat insulating layer or a water-soluble protective layer described below. The photothermal conversion agent may be any substance that absorbs light of 700 nm or more, and various metal fine particles, pigments, and dyes (also referred to as pigments) can be used.

As the metal fine particles, A1, Si, Ti,
V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y,
Zr, Mo, Ag, Au, Pt, Pd, Rh, In, S
Examples thereof include simple substances of n, W, Te, Pb, Ge, Re, and Sb, alloys thereof, and oxides, nitrides, sulfides, or azides thereof, which can be dispersed in the binder resin of the hydrophilic layer. Among them, Fe, Ag, Au, Pt,
Fine particles of Pd and Cu are particularly preferred.

As pigments, commercially available pigment and color index (CI) handbook, “Latest Pigment Handbook” (edited by Japan Pigment Technical Association, 1977), “Latest Pigment Application Technology”
(CMC Publishing, 1986), "Printing Ink Technology"
(CMC Publishing, 1984) can be used.

Examples of the type of the pigment include a black pigment, a brown pigment, a red pigment, a violet pigment, a blue pigment, a green pigment, a fluorescent pigment, a metal powder pigment, and a polymer-bound pigment. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelated azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments Quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, graphite (graphite), bone charcoal (bone black), and the like. Those commercially available under the names of titanium black, iron black, molybdenum red, emerald green, cadmium red, cobalt blue, dark blue, ultramarine and the like can also be used. Among the above, carbon black is particularly preferred.

Dyes used as photothermal conversion agents are commercially available dyes and literatures (for example, "Kensen Binran (Handbook of Dyes)" edited by The Society of Synthetic Organic Chemistry, published in 1970, "Kagaku Kogyo", May 1986, p. Infrared absorbing dyes "," Developments and market trends of functional dyes in the 1990s ", Chapter 2, section 2.3 (1990)
Or known dyes described in Patents.

Specifically, it is a dye selected from a polymethine dye, a cyanine dye, a squarylium dye, a pyrylium dye, a diimmonium dye, a phthalocyanine compound, a triarylmethane dye, and a metal dithiolene. Of these, polymethine dyes, cyanine dyes, squarylium dyes, pyrylium dyes, diimmonium dyes, and phthalocyanine compounds are more preferable. Among them, polymethine dyes, cyanine dyes, and phthalocyanine compounds are most preferable from the viewpoint of synthesis suitability. The dye described above may be a water-soluble dye having a water-soluble group in the molecule. Preferred water-soluble groups of the water-soluble dye include a sulfonic acid group, a carboxyl group and a phosphonic acid group. Specific examples of the dye used as the photothermal conversion agent for the hydrophilic layer are shown below, but are not limited thereto.

[0051]

Embedded image

[0052]

Embedded image

[0053]

Embedded image

The content of the photothermal conversion agent contained in the hydrophilic layer should be sufficient to cause the vicinity of the hydrophobic precursor to be thermally fused by the heat generated by the light absorption of the photothermal conversion agent to become hydrophobic. Good, 2-50% by mass of solid content of hydrophilic layer
You can choose widely between. Within this range, good sensitivity can be obtained without reducing the film strength of the hydrophilic layer.

In the hydrophilic layer of the present invention, the self-water-dispersible hydrophobic resin fine particles and the photothermal conversion agent are dispersed in a hydrophilic binder. As a suitable hydrophilic binder,
Examples thereof include a hydrophilic organic polymer binder resin and a hydrophilic sol-gel conversion type inorganic binder resin. Among them, a sol-gel conversion type binder resin having a property of forming a polysiloxane gel structure is preferable as a binder resin having high hydrophilicity and withstanding the destruction of the hydrophilic layer due to a thermal reaction. Hereinafter, the hydrophilic binder resin of the hydrophilic layer will be described.

Specific examples of the organic polymer binder resin include gum arabic, polyvinyl alcohol (PVA), starch and its derivatives, carboxymethyl cellulose and its sodium salt, and cellulose derivatives such as hydroxyethyl cellulose and cellulose acetate; Sodium alginate, casein, gelatin, polyvinylpyrrolidone, vinyl acetate-maleic acid copolymer, styrene-
Maleic acid copolymer, alginic acid and its alkali metal salt, alkaline earth metal salt or ammonium salt, polyacrylic acid and their salts, polymethacrylic acid and their salts, poly (ethylene oxide), water-soluble urethane resin, water-soluble Polyester resin, hydroxyethyl acrylate homopolymer and copolymer, hydroxyethyl methacrylate homopolymer and copolymer, hydroxypropyl acrylate homopolymer and copolymer, hydroxypropyl methacrylate homopolymer and copolymer, hydroxybutyl acrylate homopolymer and copolymer, hydroxy Butyl methacrylate homopolymer and copolymer, polyethylene glycol diacrylate polymer, hydroxypropyl methacrylate Moporima and copolymers, polyethylene glycols, poly (hydroxypropylene)
And other hydrophilic resins.

Preferably, the hydrophilic resin may be cross-linked to be used. In this case, examples of the water-resistant agent for cross-linking the resin include aldehydes such as glyoxal, melamine formaldehyde resin, and urea formaldehyde resin;
-Methylol urea, N-methylol melamine, methylol compounds such as methylolated polyamide resins, active vinyl compounds such as divinyl sulfone and bis (β-hydroxyethyl sulfonic acid), epichlorohydrin and polyethylene glycol diglycidyl ether, polyamide / polyamine / epichloro Hydrin adducts, epoxy compounds such as polyamide epichlorohydrin resin, ester compounds such as monochloroacetate and thioglycolate, polycarboxylic acids such as polyacrylic acid and methyl vinyl ether / maleic acid copolymer, boric acid, titanyl Examples include inorganic crosslinking agents such as sulfate, Cu, Al, Sn, V, and Cr salts, and modified polyamide polyimide resins. In addition, a crosslinking catalyst such as ammonium chloride, a silane coupling agent, and a titanate coupling agent can be used in combination.

The particularly preferred binder for the hydrophilic layer of the present invention is a sol-gel conversion type binder resin described below. The sol-gel conversion system that can be preferably applied to the present invention is such that the bond coming out of the polyvalent element forms a network structure via an oxygen atom, and at the same time, the polyvalent element also has an unbonded hydroxyl group or alkoxy group. It is a polymer having a resin-like structure in which these are mixed, and is in a sol state at a stage where there are many alkoxy groups and hydroxyl groups, and a network-like resin structure is formed as dehydration condensation bonding proceeds. Be strong. Further, in addition to the property of changing the degree of hydrophilicity of the resin structure, it also has a function of modifying the surface of the solid fine particles by binding a part of hydroxyl groups to the solid fine particles, thereby changing the degree of hydrophilicity.

The polyvalent bonding element of the compound having a hydroxyl group or an alkoxy group which undergoes sol-gel conversion is aluminum, silicon, titanium, zirconium or the like, and any of them can be used in the present invention. A description will be given of a sol-gel conversion system using a siloxane bond. The sol-gel conversion using aluminum, titanium, and zirconium can be performed by substituting silicon for each element described below.

That is, a system containing a silane compound having at least one silanol group capable of sol-gel conversion is particularly preferably used.

Hereinafter, a system utilizing the sol-gel conversion will be further described. The inorganic hydrophilic binder resin formed by the sol-gel conversion is preferably a resin having a siloxane bond and a silanol group, and the hydrophilic layer of the lithographic printing plate precursor according to the present invention is a silane compound having at least one silanol group. The coating solution is a sol-based coating solution containing, during the elapse of time after application, hydrolytic condensation of silanol groups proceeds to form a siloxane skeleton structure and gelation proceeds.

The layer formed by the sol-gel conversion may be added with an organic hydrophilic polymer or a cross-linking agent, which will be described later, for the purpose of improving physical properties such as film strength and flexibility, and improving coatability. It is also possible. The siloxane resin forming a gel structure is represented by the following general formula (I):
The silane compound having at least one silanol group is represented by the following general formula (II). The substance system contained in the hydrophilic layer does not necessarily have to be a silane compound of the general formula (II) alone, and may generally be composed of an oligomer obtained by partially hydrolyzing the silane compound, or The mixture composition of the oligomer may be used.

[0063]

Embedded image

The siloxane resin represented by the general formula (I) is
It is formed by a sol-gel conversion from a dispersion containing at least one silane compound represented by the following general formula (II), and at least one of R ^{01 to} R ^{03 in} the general formula (I) represents a hydroxyl group; Others represent an organic residue selected from the symbols R ⁰ and Y in the following general formula (II).

Formula (II) (R ⁰ ) _n Si (Y) _4-n

In the general formula (II), R ⁰ represents a hydroxyl group, a hydrocarbon group or a heterocyclic group. Y is a hydrogen atom, a halogen atom, —OR ¹ , —OCOR ² , or —N (R ³ ) (R ⁴ )
(R ¹ and R ² each represent a hydrocarbon group, and R ³ and R ⁴
May be the same or different and represent a hydrogen atom or a hydrocarbon group). n represents 0, 1, 2 or 3.

The hydrocarbon group or heterocyclic group represented by R ^{0 in} the general formula (II) is, for example, a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted (for example, methyl group, Ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group and the like. Fluorine atom, bromine atom, hydroxy group, thiol group, carboxy group, sulfo group, cyano group, epoxy group, -OR 'group (R' 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-dimethyl Tylaminoethyl group, 2-bromoethyl group, 2- (2-methoxyethyl) oxyethyl group, 2-methoxycarbonylethyl group, 3-carboxypropyl group, benzyl group, etc.),

-OCOR 'group, -COOR' group, -CO
R 'group, -N (R ") (R") (R "represents the same content as hydrogen atom or R' and may be the same or different), -NHCONHR 'group, -NHCOOR'
Group, -Si (R ') ₃ group, -CONHR "group, -NHC
An OR 'group and the like; these substituents may be substituted with a plurality of alkyl groups; a linear or branched alkenyl group having 2 to 12 carbon atoms which may be substituted (for example, vinyl group, A propenyl group, a butenyl group, a pentenyl group, a hexenyl group, an octenyl group, a decenyl group, a dodecenyl group, and the like, and the groups substituted with these groups include those having the same contents as the groups substituted with the alkyl group. ),
Aralkyl groups having 7 to 14 carbon atoms which may be substituted (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, etc. Is the same as the group substituted with the alkyl group, and may be substituted plurally.)

An optionally substituted alicyclic group having 5 to 10 carbon atoms (for example, cyclopentyl, cyclohexyl, 2
A cyclohexylethyl group, a 2-cyclopentylethyl group, a norbornyl group, an adamantyl group and the like, and the groups substituted with these groups include those having the same contents as the substituents of the alkyl group. And a substituted or unsubstituted aryl group having 6 to 12 carbon atoms (e.g., a phenyl group or a naphthyl group, and examples of the substituent include those having the same contents as the group substituted with the alkyl group.
A heterocyclic group containing at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom which may be condensed (for example, a pyran ring , Furan ring, thiophene ring, morpholine ring, pyrrole ring, thiazole ring, oxazole ring, pyridine ring, piperidine ring, pyrrolidone ring, benzothiazole ring, benzoxazole ring, quinoline ring, tetrahydrofuran ring, etc. Examples of the substituent include those having the same content as the substituent in the alkyl group, and may be substituted plurally.

In the general formula (II), -OR ¹ group of Y, -OCO
Examples of the substituent of the R ² group or the —N (R ³ ) (R ⁴ ) group include the following substituents. In the —OR ¹ group, R ¹ is an aliphatic group having 1 to 10 carbon atoms which may be substituted (for example,
Methyl, ethyl, propyl, butyl, heptyl, hexyl, pentyl, octyl, nonyl,
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, cyclooctyl, chlorocyclohexyl, methoxycyclohexyl, benzyl, phenethyl, dimethoxybenzyl, methylbenzyl, bromobenzyl, etc.).

In the —OCOR ² group, R ² is an aliphatic group having the same contents as R ¹ or an aromatic group having 6 to 12 carbon atoms which may be substituted (the aromatic group is the aryl group in the aforementioned R). And the same as those exemplified for the group). In the —N (R ³ ) (R ⁴ ) group, R ³ and R ⁴ may be the same or different from each other.
10 optionally substituted aliphatic groups (for example, the above-mentioned -O
R ¹ has the same contents as R ¹ ). More preferably, the total number of carbon atoms of R ³ and R ⁴ is 16 or less. Specific examples of the silane compound represented by the general formula (II) include the following, but are not limited thereto.

Tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra-n-propylsilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrichlorosilane, ethyltrimethoxysilane, Ethyltriethoxysilane, n-propyltrichlorosilane, n-propyltribromosilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-decyltrimethoxysilane, n-hexyltrichlorosilane, n-hexyltri Methoxysilane,
n-hexyltrimethoxysilane, phenyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxydiethoxysilane, dimethyldichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldiethoxysilane, phenylmethyldimethoxysilane , Triethoxyhydrosilane, trimethoxyhydrosilane, vinyltrichlorosilane, vinyltrimethoxysilane, trifluoropropyltrichlorosilane, trifluoropropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane Silane, γ-glycidoxypropyltrimethoxysilane, γ
-Glycidoxypropyltriethoxysilane, γ-methacryloylpropylmethyltrimethoxysilane, γ-
Methacryloxypropyltri-t-butoxysilane, γ
-Aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ -Mercaptopropyltriethoxysilane, β-
(3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like.

In addition to the silane compound represented by the general formula (II) used for forming the inorganic hydrophilic binder resin of the hydrophilic layer of the present invention, the resin is used in the sol-gel conversion of Ti, Zn, Sn, Zr, Al, etc. Can be used in combination with a metal compound capable of forming a film. As the metal compound used, for example,
Ti (OR ¹⁰ ) ₄ (R ¹⁰ is a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, etc.), TiC
l ₄ , Zn (OR ¹⁰ ) ₂ , Zn (CH ₃ COCHCOC)
H ₃ ) ₂ , Sn (OR ¹⁰ ) ₄ , Sn (CH ₃ COCHCOC)
H ₃ ) ₄ , Sn (OCOR ¹⁰ ) ₄ , SnCl ₄ , Zr (OR
_{^{1 0) 4, Zr (CH}} 3 COCHCOCH 3) 4, Al (OR
¹⁰ ) ₃ , Al (CH ₃ COCHCOCH ₃ ) _{3 and the} like.

Further, in order to accelerate the hydrolysis and polycondensation reaction of the silane compound represented by the general formula (II), and the metal compound used in combination, it is preferable to use an acidic catalyst or a basic catalyst in combination. As the catalyst, an acid or basic compound used as it is or in a state of being dissolved in a solvent such as water or alcohol (hereinafter referred to as an acidic catalyst or a basic catalyst, respectively) is used. The concentration at that time is not particularly limited, but when the concentration is high, hydrolysis,
The polycondensation rate tends to increase. However, when a highly concentrated basic catalyst is used, a precipitate may be formed in the sol solution. Therefore, the concentration of the basic catalyst is preferably 1 N (concentration conversion in an aqueous solution) or less.

The type of the acidic catalyst or the basic catalyst is not particularly limited, but when it is necessary to use a catalyst having a high concentration, a catalyst composed of an element which hardly remains in the catalyst crystal grains after sintering is used. Good. Specifically, examples of the acidic catalyst include hydrogen halides such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, carbonic acid,
Examples of basic catalysts include carboxylic acids such as formic acid and acetic acid, substituted carboxylic acids obtained by substituting R in the structural formula represented by RCOOH with other elements or substituents, sulfonic acids such as benzenesulfonic acid, and the like. Examples include ammoniacal bases and amines such as ethylamine and aniline.

As described above, the hydrophilic layer formed by the sol-gel method is particularly preferable for the lithographic printing plate precursor according to the invention. For further details of the above sol-gel method, see Sakuhana Saio, "Science of the sol-gel method", Agne Shofusha Co., Ltd. (published)
(1988), Takashi Hirashima, "Functional thin film production technology by latest sol-gel method", General Technology Center (published) (1992)
It is described in detail in written documents such as year).

In the hydrophilic layer, in addition to the photothermal conversion agent, the hydrophobized resin fine particles, and the hydrophilic binder resin, improvement in sensitivity, control of the degree of hydrophilicity, improvement in physical strength of the hydrophilic layer. Various compounds for various purposes such as improvement of dispersibility between compositions constituting a layer, improvement of applicability, improvement of printability, and convenience of plate making operation, for example, hydrophilic sol-like fine particles, surfactant, coloring Agents and the like can be added. These additives include, by way of example, the following:

The hydrophilic sol-like fine particles are not particularly limited, but are preferably silica sol, alumina sol, magnesium oxide, magnesium carbonate, and calcium alginate. It can be used for strengthening a film. More preferably, it is a silica sol, an alumina sol, a calcium alginate sol or a mixture thereof. The content as a preferable solid content is 1.0 to 1.0 of the solid content of the hydrophilic layer.
70 mass%, preferably 5.0 to 50 mass%. The total addition amount of the photothermal conversion agent, the hydrophobized resin fine particles and the hydrophilic sol-like fine particles is 2 to 9 of the solid component of the hydrophilic layer.
5 mass%, preferably 5 to 85 mass%.

The silica sol has many hydroxyl groups on the surface, and the inside of the sol forms a siloxane bond (—Si—O—Si). Since ultrafine silica particles having a particle diameter of 1 to 100 nm exist in a state of being dispersed in water or a polar solvent due to surface hydroxyl groups, they are also called colloidal silica. Specifically, it is described in "Applied Technology of High Purity Silica", Vol. 3, supervised by Yoshitoshi Kaga and Ei Hayashi, CMC Corporation (1991).

Alumina sol is an alumina hydrate (boehmite) having a colloidal size of 5 to 200 nm.
And an anion (for example, a halogen ion such as a fluorine ion or a chloride ion, or a carboxylate anion such as an acetate ion) in water is dispersed as a stabilizer.

The hydrophilic sol fine particles have an average particle diameter of 1
The average particle size is preferably from 0 to 50 nm, more preferably from 10 to 40 nm. All of these hydrophilic sol-like fine particles can be easily obtained as commercial products.

In the hydrophilic layer of the lithographic printing plate precursor according to the present invention, in addition to nonionic and anionic surfactants, JP-A-2-1953
No. 56, cationic surfactants, fluorine-containing surfactants, and JP-A-59-12104.
No. 4 and JP-A-4-13149 can be added.

Specific examples of nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether and polyoxyethylene oleyl ether, and polyoxyethylene nonylphenyl. Polyoxyethylene alkylaryl ethers such as ethers, polyoxyethylene / polyoxypropylene block copolymers, and aliphatic groups having 5 to 24 carbon atoms were ether-bonded to hydroxyl groups at the terminals of polyoxyethylene / polyoxypropylene block copolymers. Complex polyoxyalkylene alkyl ethers, also complex polyoxyalkylene alkyl aryl ethers in which alkyl-substituted aryl groups are ether-bonded, sorbitan mono Urate, sorbitan monostearate, sorbitan tristearate, sorbitan monopalmitate, sorbitan monooleate, sorbitan triolate and other sorbitan fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene Examples include polyoxyethylene sorbitan fatty acid esters such as sorbitan monostearate, polyoxyethylene sorbitan tristearate, and polyoxyethylene sorbitan triolate.

Specific examples of the amphoteric surfactant include alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N , N-betaine type (for example, trade name Amogen K, manufactured by Daiichi Kogyo Co., Ltd.) and the like.

Specific examples of the anionic activator include alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids, alkylnaphthalenesulfonic acids, alkylnaphthalenesulfonic acids or condensation type of naphthalenesulfonic acid and formaldehyde, and those having 9 carbon atoms. To 26-26 aliphatic sulfonic acids, alkylbenzene sulfonic acids, polyoxyethylene-containing sulfuric acid such as lauryl polyoxyethylene sulfate, cetyl polyoxyethylene sulfonic acid, oleyl polyoxyethylene phosphonic acid, and polyoxyethylene-containing phosphoric acid.

Specific examples of the cationic activator include laurylamine acetate, lauryltrimethylammonium chloride, distearyldimethylammonium chloride, alkylbenzyldimethylammonium chloride and the like.

For the hydrophilic layer, a fluorine-based surfactant may be further used in the range of the amount of the above-mentioned surfactant. Specifically, a surfactant having a perfluoroalkyl group is preferable, and an anionic surfactant having any of carboxylic acid, sulfonic acid, sulfate ester and phosphate ester, or an aliphatic amine,
Cationic surfactants such as quaternary ammonium salts, or betaine-type amphoteric surfactants, or aliphatic esters of polyoxy compounds, polyalkylene oxide condensation type,
Nonionic surfactants such as polyethyleneimine condensed type are exemplified.

The proportion of the surfactant in the total solids in the hydrophilic layer is preferably from 0.05 to 15% by mass, more preferably from 0.1 to 5% by mass.

[Heat Insulating Layer] Although not essential for the lithographic printing plate of the present invention, it is preferable to provide a heat insulating layer between the support and the hydrophilic layer. Hereinafter, the heat insulating layer will be described. The heat-insulating layer provided as a lower layer of the photosensitive layer is a layer having a low thermal conductivity and a function of suppressing heat diffusion to the support.
Further, the heat insulating layer may contain a photothermal conversion agent. In this case, heat is generated by light irradiation, which contributes to improvement of the heat fusion sensitivity.

Such a heat insulating layer contains an organic or inorganic resin as a main component. The organic or inorganic resin can be widely selected from hydrophilic or hydrophobic resins.

For example, hydrophobic resins include polyethylene, polypropylene, polyester, polyamide, acrylic resin, vinyl chloride resin, pinylidene chloride resin, polyvinyl butyral resin, nitrocellulose, polyacrylate, polymethacrylate, polycarbonate, polyurethane, polystyrene, and the like. Vinyl chloride resin-vinyl acetate copolymer, vinyl chloride-vinyl acetate-vinyl alcohol copolymer, vinyl chloride-resin vinyl-maleic acid copolymer, vinyl chloride-acrylate copolymer, polyvinylidene chloride, vinylidene chloride-acrylonitrile And copolymers.

In the present invention, as the resin having hydrophobicity, a resin composed of an aqueous emulsion can be used. Specific examples of the aqueous emulsion include vinyl polymer latex (polyacrylate, vinyl acetate,
Ethylene-vinyl acetate-based), conjugated cyanene-based polymer latex (methyl methacrylate-butadiene-based, styrene-butadiene-based, aggrilonitrile-butadiene-based, chloroprene-based, etc.), and polyurethane resin.

Next, examples of the hydrophilic resin include polyvinyl alcohol (PVA), modified PVA such as carboxy-modified PVA, starch and derivatives thereof, cellulose derivatives such as carboxymethylcellulose and hydroxyethylcellulose, and alginic acid. Ammonium,
Polyacrylic acid, polyacrylate, polyethylene oxide, water-soluble urethane resin, water-soluble polyester resin, polyhydroxyethyl acrylate, polyethylene glycol diacrylate polymer, N-vinyl carboxylic acid amide polymer, casein, gelatin, polyvinyl pyrrolidone, acetic acid Water-soluble resins such as vinyl-crotonic acid copolymer and styrene-maleic acid copolymer are exemplified.

The hydrophilic resin is preferably crosslinked and cured before use. As the crosslinking agent (also referred to as a waterproofing agent), the same waterproofing agent as used for the hydrophilic layer can be used. .

Further, as the inorganic polymer, an inorganic matrix formed by sol-gel conversion is preferable. Specifically, the same sol-gel conversion system suitable for the above-mentioned hydrophilic layer can be used.

Among the resins used for these heat insulating layers,
From the viewpoint of adhesion to the hydrophilic layer, a hydrophilic resin is particularly preferable.

The heat-insulating layer can contain a light-to-heat converting agent. As the light-to-heat converting agent, the same substance as the light-to-heat converting agent used for the hydrophilic layer can be used. The content of the light-to-heat conversion agent in the heat insulating layer is 2% of the solid content of the heat insulating layer.
It can be widely selected between ９５95% by mass.

In addition to the above-mentioned resin and light-to-heat conversion agent, the heat-insulating layer may have an improved physical strength of the heat-insulating layer, an improved dispersibility between the constituent components of the layer, an improved applicability, and a hydrophilic layer. Various objective compounds, for example, hydrophilic sol-like fine particles, a surfactant and the like can be added for reasons such as improvement in adhesiveness. The same hydrophilic sol fine particles and surfactant as those added to the hydrophilic layer described above can be used in the same amount range.

[Water-soluble protective layer] The lithographic printing plate precursor according to the present invention, when the hydrophilic layer is the outermost surface, is used when the plate is transported or stored in a product form, or when it is handled before use. It is susceptible to hydrophobization due to the influence of the environment atmosphere, temperature and humidity, mechanical scratches and dirt. In order to prevent this, the lithographic printing plate precursor of the present invention can be provided with a water-soluble surface protective layer. The water-soluble protective layer is dissolved in dampening water at the initial stage of printing and is washed away, so that there is no need to take extra steps for removal and does not hinder printing. Hereinafter, the components contained in the water-soluble protective layer will be described.

The water-soluble protective layer contains a water-soluble polymer as a main component. Examples of the water-soluble polymer include a hydroxyl group,
A polymer having a sufficient group such as a carboxyl group or a basic nitrogen-containing group is exemplified. Specifically, modified PV such as polyvinyl alcohol (PVA) and carboxy-modified PVA
A, gum arabic, polyacrylamide and its copolymer, acrylic acid copolymer, vinyl methyl ether / maleic anhydride copolymer, vinyl acetate / maleic anhydride copolymer, styrene / maleic anhydride copolymer, Baked dextrin, oxygenated dextrin, enzymatically degraded etherified dextrin, starch and its derivatives, carboxymethylcellulose, carboxyethylcellulose, methylcellulose, cellulose derivatives such as hydroxyethylcellulose, casein, gelatin, polyvinylpyrrolidone,
Vinyl acetate-crotonic acid copolymer, styrene-maleic acid copolymer, alginic acid and its alkali metal salts, alkaline earth metal salts or ammonium salts, polyacrylic acid,
Examples include poly (ethylene oxide), a water-soluble urethane resin, a water-soluble polyester resin, polyhydroxyethyl acrylate, polyethylene glycol, polypropylene glycol, and N-vinyl carboxylic acid amide polymer. Among them, it is preferable to use modified PVA such as polyvinyl alcohol (PVA) and carboxy-modified PVA, gum arabic, polyacrylamide, polyacrylic acid, acrylic acid copolymer, polyvinylpyrrolidone, alginic acid and alkali metal salts thereof.

The content of the water-soluble resin in the coating solution for the protective layer is as follows:
3 to 25% by mass is appropriate, and a preferable range is 10 to 2%.
5% by mass. In the present invention, two or more of the above water-soluble resins may be used in combination.

A surfactant may be added to the coating solution for the protective layer. Surfactants that can be used include anionic or nonionic surfactants. As a specific example, the same surfactant as that used for the hydrophilic layer can be used. The amount of the surfactant added is preferably 0.01 to 1% by mass of the solid content of the protective layer, and more preferably 0.05 to 0.5% by mass.

If necessary, lower polyhydric alcohols such as glycerin, ethylene glycol and triethylene glycol can be added as a wetting agent. The use amount of these wetting agents is suitably 0.1 to 5.0% by mass in the protective layer, and a more preferred range is 0.5 to 3.0% by mass.

In addition to the above, a preservative and an antifoaming agent can be added to the coating solution for the protective layer. As preservatives, for example, benzoic acid and its derivatives, phenol, formalin,
0.005 to 2.0% by mass of sodium dehydroacetate
Can be added in the range. Preferred antifoaming agents include an organosilicone compound, the amount of which is 0.0001 to 0.1.
The range of mass% is preferred.

Further, a light-to-heat conversion agent may be added to the water-soluble protective layer. As the light-to-heat conversion agent, the light-to-heat conversion agent described above, which may be added to the hydrophilic layer, can be used in the range of the addition amount described above.

[Coating] The above-mentioned hydrophilic layer, heat insulating layer and protective layer are prepared by mixing the respective constituent components and applying a prepared coating solution on a support by any of conventionally known coating methods.
Coating and drying to form a coating layer. As a method of coating, various known methods can be used, and examples thereof include bar coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating. .

The coating amount (solid content) of each layer obtained after coating and drying varies depending on the application, but for a general lithographic printing plate precursor, 0.1 to 30 g / m 2 for the hydrophilic layer.
² is preferred, and 0.3 to 10 g / m ² is more preferred. In the heat insulating layer, 0.1 to 10 g / m ² is preferable, and 0.3 to
5 g / m ² is more preferred. 0.1 to 5 g for the protective layer
/ M ² is preferable, 0.2 to 3 g / m ² is more preferable.
The application is usually performed in the order of a heat insulating layer, a hydrophilic layer, and a protective layer.

[Support] Next, a support on which a hydrophilic layer or a heat insulating layer is provided will be described. A dimensionally stable plate is used for the support. Examples of the support that can be used in the present invention include paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, aluminum, zinc, copper, nickel, stainless steel, etc.), plastic Films (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), and the above metals are laminated or deposited Paper or plastic film.

Preferred supports are polyester film, aluminum, or SUS which is not easily corroded on a printing plate.
It is a steel plate, and among them, an aluminum plate which has good dimensional stability and is relatively inexpensive is preferable. Suitable aluminum plates are a pure aluminum plate and an alloy plate containing aluminum as a main component and a trace amount of a different element, and may be a plastic film on which aluminum is laminated or vapor-deposited. The foreign elements contained in the aluminum alloy include:
Silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, titanium and the like. The content of the foreign element in the alloy is at most 10% by mass or less. Particularly preferred aluminum in the present invention is pure aluminum. However, completely pure aluminum is difficult to produce due to refining technology, and therefore may contain a slightly different element.
As described above, the composition of the aluminum plate applied to the present invention is not specified, and an aluminum plate of a conventionally known material can be appropriately used. The thickness of the support used in the present invention is approximately 0.05 mm to 0.1 mm.
It is about 6 mm, preferably 0.1 mm to 0.4 mm, particularly preferably 0.15 mm to 0.3 mm.

Prior to use, the aluminum plate is subjected to a degreasing treatment with, for example, a surfactant, an organic solvent or an alkaline aqueous solution to remove rolling oil on the surface, and then to a surface treatment such as surface roughening and anodic oxidation. Is preferred. The surface treatment facilitates securing the adhesiveness to the hydrophilic layer.

The surface roughening treatment of the aluminum plate is performed by various methods. For example, a method of mechanically roughening the surface, a method of electrochemically dissolving and roughening the surface, and a method of chemically roughening the surface. Is selectively dissolved. Known mechanical methods such as a ball polishing method, a brush polishing method, a blast polishing method, and a buff polishing method can be used as the mechanical method. The chemical method is described in JP-A-54-31187.
The method of immersion in a saturated aqueous solution of an aluminum salt of a mineral acid as described in Japanese Patent Application Laid-Open Publication No. H10-157, 1988 is suitable. As an electrochemical surface roughening method, there is a method in which an alternating current or a direct current is used in an electrolytic solution containing an acid such as hydrochloric acid or nitric acid. Also, an electrolytic surface roughening method using a mixed acid as disclosed in JP-A-54-63902 can be used. Among such surface roughening methods, in particular, JP-A-55-1
A surface roughening method combining mechanical surface roughening and electrochemical surface roughening as described in 37993 is preferable because the adhesive force of the oil-sensitive image to the support is strong.

The surface roughening by the above-mentioned method is performed when the center line surface roughness (Ra) of the surface of the aluminum plate is 0.3-1.
It is preferable that the coating be performed within a range of 0 μm. The roughened aluminum plate is subjected to an alkali etching treatment using an aqueous solution of potassium hydroxide or sodium hydroxide as required, and further neutralized, and then anodized to enhance abrasion resistance if desired. Processing is performed.

As the electrolyte used for the anodic oxidation treatment of the aluminum plate, various electrolytes forming a porous oxide film can be used. Generally, sulfuric acid, hydrochloric acid, oxalic acid, chromic acid or a mixed acid thereof is used. Can be The concentration of these electrolytes is appropriately determined depending on the type of the electrolyte. Anodizing treatment conditions vary depending on the electrolyte to be used, and thus cannot be specified unconditionally.
~ 80 mass% solution, liquid temperature 5 ~ 70 ° C, current density 5 ~ 6
0 A / dm ² , a voltage of 1 to 100 V, and an electrolysis time of 10 seconds to 5 minutes are appropriate. The amount of oxide film formed is
It is preferably from 1.0 to 5.0 g / m ² , particularly preferably from 1.5 to 4.0 g / m ² . 1.0 g / m of anodic oxide film
^If it is less than ² , the printing durability will be insufficient or it will be easily scratched.

Among these anodizing treatments, in particular, a method of anodizing at a high current density in sulfuric acid described in British Patent No. 1,412,768 and US Pat. No. 3,511,661. The method of anodizing using phosphoric acid as an electrolytic bath described in above is preferable.

When the heat insulating layer is a resin having hydrophobicity, it is desirable to make the surface of the support hydrophobic. The surface of the support is hydrophobized by applying an undercoating liquid containing, for example, a silane coupling agent or, in some cases, a titanium coupling agent. The silane coupling agent is mainly represented by the general formula (R ¹¹ O) ₃ SiR ¹² (R ¹¹ and R ¹² are an alkyl group or a substituted alkyl group), and the R ¹¹ O group is hydrolyzed to an OH group to form a support. bound at the surface and an ether bond, R ¹² group provides a hydrophobic surface for receiving ink.

Examples of the silane coupling agent include γ-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, and γ-glycoxide. Examples thereof include propyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptotrimethoxysilane, γ-ureidopropyltriethoxysilane, and N- (β-aminoethyl)-(β-aminopropyl) dimethoxysilane. In the case of a plastic support, in order to secure adhesion to the hydrophilic layer, a charging treatment is performed by a known method before coating.

[Plate Making and Printing] The lithographic printing original plate of the present invention forms an image by heat. Specifically, direct image-like recording using a thermal recording head or the like, scanning exposure using an infrared laser, high-illuminance flash exposure such as a xenon discharge lamp, or infrared lamp exposure is used.
Exposure with a solid-state high-output infrared laser such as a semiconductor laser or a YAG laser that emits 0-nm infrared light is preferable.
The lithographic printing plate of the present invention has a laser output of 0.1 to 3
Irradiation can be performed with a 00W laser. When a pulse laser is used, the peak output is 1000
It is preferable to irradiate a laser beam of W, preferably 2000 W. In this case, the exposure amount is preferably in the range of 0.1 to 10 J / cm ² , more preferably in the range of 0.3 to 1 J / cm ² , before the surface exposure intensity is modulated in the print image. preferable. If the support is transparent, it can be exposed through the support from the back side of the support.

The lithographic printing plate precursor of the present invention, which has been image-exposed, can be mounted on a printing press without any further processing, and can be printed by an ordinary procedure using ink and fountain solution. Also, after these lithographic printing original plates are mounted on a printing press cylinder, they can be exposed by a laser mounted on the printing press, and can be printed as they are using ink and fountain solution in a normal procedure. That is, the lithographic printing original plate of the present invention can start printing without exposure after exposure, without any particular development processing.

[0119]

Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. The dry solid content ratio of the resin fine particle dispersion was determined by weighing about 1 g of the sample solution, weighing the sample after drying at 120 ° C. for 1 hour, and determining the mass ratio. The number average molecular weight was measured by GPC, and described in terms of the molecular weight in terms of polystyrene. The acid value was determined by weighing a predetermined amount of a sample solution and titrating with a methanol solution of potassium hydroxide having a known concentration. The particle size was measured with a laser Doppler particle size distribution analyzer ELS-800, Otsuka Electronics Co., Ltd.

[Production Example 1 of Self-Water-Dispersible Hydrophobized Resin Fine Particles] Acrylic polymer fine particles 400 g of methyl ethyl ketone was placed in a 1-L four-necked flask equipped with a stirrer, a reflux device, a nitrogen inlet tube, a dropping device, and a thermometer. And heated to 80 ° C. 80 of styrene
g, 300 g of methyl methacrylate, 2 of methacrylic acid
4.5 g, 2,2′-azobis (isobutyric acid) dimethyl (V-
601 (a polymerization initiator manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 2 hours. After stirring for 8 hours,
By adding 0.5 g of V-601 and further stirring for 8 hours, the dry solid content ratio was 50%, the acid value was 39.2,
An acrylic polymer having a number average molecular weight of 20,000 was obtained. 100 g of the above acrylic polymer solution was neutralized with 2.71 g of triethylamine, and water was added dropwise with stirring. The solution gradually increased in viscosity, and the viscosity was remarkably reduced around the time when about 150 g of water was dropped, whereby the phase inversion was completed. One more
After adding 50 g of water, the obtained dispersion is heated to 40 ° C., and the organic solvent and excess water are removed under reduced pressure, whereby the dry solid content ratio is 33.7%, and the average particle size is 0.12 μm.
Thus, an aqueous dispersion of acrylic polymer fine particles of m was obtained.

[Preparation Example 2 of Self-Water-Dispersible Hydrophobized Resin Fine Particles] Polyurethane fine particles “Varnock DN-980” was placed in a 1 L four-necked flask equipped with a stirrer, a reflux device, a dry nitrogen inlet tube and a thermometer.
533 g of [trade name of polyisocyanate manufactured by Dainippon Ink and Chemicals, Inc.], 33.5 g of 2,2-bis (hydroxymethyl) propionic acid, 0.05 g of dibutyltin dilaurate and 300 g of ethyl acetate were added. , 80
Stirring at 3 ° C. for 3 hours resulted in a dry solids ratio of 50.
A solution of a polyurethane prepolymer having 0% and an isocyanate group content of 6.80% was obtained. To 100 g of the above polyurethane prepolymer solution, add 3
0 g, neutralized with 3.50 g of triethylamine,
Water was added dropwise with stirring. The prepolymer solution gradually thickened, and after adding about 300 g of water, an aqueous solution in which 2.51 g of diethylenetriamine was dissolved in 50 g of water was slowly added with stirring. Next, the obtained dispersion was heated to 40 ° C., and an organic solvent and excess water were removed under reduced pressure, whereby an aqueous dispersion of urethane fine particles having a dry solid content ratio of 33.5% and an average particle size of 0.08 μm was obtained. was gotten. The acid value was 31.0.

[Production Example 3 of Self-Water-Dispersible Hydrophobized Resin Fine Particles] Core-shell type (styrene-glycidyl methacrylate core / acrylate copolymer shell) condenser, mechanical stirrer, thermometer, nitrogen inlet / outlet and 2 In a 500 ml flask equipped with two monomer supply tubes, 25 g of methacrylic acid, 10 g of styrene, 2 g of ethyl acrylate, 3 g of benzoyl peroxide (BPO),
40 ml of a mixture obtained by uniformly mixing each material of 70 g of n-butanol was added and heated at 110 ° C. for 2 hours while stirring. After cooling to room temperature, 200 ml of distilled water and 25 ml
10 ml of aqueous ammonia was added and the mixture was stirred until it became clear. Thereafter, 0.9 g of ascorbic acid and 1.48 g of potassium persulfate were added. Styrene (7
1.21 g), glycidyl methacrylate (3.744)
g) and bromotrichloromethane (3 g),
The temperature was increased to 35 ° C. under a nitrogen atmosphere. Temperature for 7 hours 3
Maintained at 5 ° C. The solids content was 25%. The core is a styrene / glycidyl methacrylate copolymer and a carboxylated acrylate copolymer associated with the core as a shell material.

[Preparation Example 4 of Self-Water-Dispersible Hydrophobized Resin Fine Particles] A core-shell type (epoxy core / acrylate copolymer shell) liquid epoxy resin DER333 (a catalyst-added epoxy resin manufactured by Dow Chemical Company, epoxy equivalent: about 200) )
To 105 g, 54 g of bisphenol A was added and heated to 190 ° C. over about 2 hours with stirring.
Hold for hours. The reaction product has an epoxy equivalent of about 300
0 was obtained. Then, a reflux condenser was set in the reaction vessel, and the inside of the system was closed.
3 g were introduced by means of a pump, whereby a solution of the epoxy resin was obtained, which was kept at 117.degree. In another container, 29 g of methacrylic acid, 18 g of styrene, 20 g of ethyl acrylate and 4.6 g of benzoyl peroxide were put and mixed. This monomer mixture was added at a constant rate over 180 minutes to the reaction vessel containing the epoxy resin. The reaction temperature was maintained at 116 to 117 ° C., and after the addition of the monomer mixture was completed, stirring was continued for another 3 hours. The reaction product was dispersed in n-butanol and became semi-turbid.

This resin dispersion was gradually added to a mixed solution of 500 g of deionized water and 26 g of dimethylethanolamine heated to 50 ° C., and after stirring for about 1 hour, 330 g of deionized water was added. In this state, the resin of the reaction product was finely dispersed and turned milky white. Subsequently, the above-mentioned dispersion in water was distilled under reduced pressure at 50 to 60 ° C. to remove 260 g. The aqueous dispersion is passed through an ultrafiltration module (ACP-10).
(Asahi Kasei Kogyo Co., Ltd.). In the obtained aqueous dispersion, the resin was finely dispersed and turned milky white. The aqueous dispersion was stable for three months without aggregation or precipitation of the resin, and the dispersion was stable. The non-volatile content of this dispersion was 23%, and n-butanol in this dispersion was not detected as a result of analysis by gas chromatography.

[Preparation Example 5 of Self-Water-Dispersible Hydrophobized Resin Fine Particles] Core-shell type (styrene-butadiene core / carboxyl group-containing epoxy shell) n-butanol 1 was placed in a four-necked flask purged with nitrogen gas.
20 g and 150 g of bisphenol F-type epoxy resin were charged and dissolved by heating. To this solution, methacrylic acid 25
g, 10 g of styrene, 2 g of ethyl acrylate, 3 g of benzoyl peroxide (BPO), and 10 g of n-butanol were uniformly mixed, and gradually stirred over 2 hours while stirring at 110 ° C. while maintaining the inside of the flask at 110 ° C. It was dropped.
After the completion of the dropwise addition, the mixture was further stirred at the same temperature for 4 hours to obtain a solution of a carboxyl group-containing self-emulsifying epoxy resin having a solid content of 58%. The self-emulsifying epoxy resin 100 obtained above was placed in a four-necked flask filled with nitrogen gas.
g, heated to 100 ° C., and a mixed liquid of 4 g of dimethylethanolamine and 260 g of ion-exchanged water was added dropwise over 10 minutes with stirring to have a carboxyl group and to have self-emulsifiability. To obtain an aqueous dispersion of epoxy resin. Further, under reduced pressure, 130 g of n-butanol and water were distilled off by azeotropic distillation, and a non-solvent-containing aqueous dispersion of a carboxyl group-containing self-emulsifiable epoxy resin (A) having a nonvolatile content of 25% was obtained. I got 100 g of the above aqueous dispersion, 4 g of butadiene, 3 g of styrene, B
0.35 g of PO was charged into an autoclave equipped with a stirrer purged with nitrogen gas, and the mixture was heated to 50 ° C. while stirring, and stirring was continued until the internal pressure became 0 kg / cm ² . The desired aqueous resin composition having a solid content of 29.8% was obtained. This aqueous resin composition showed no change in viscosity even after 20 days.

[Production Example a of Non-self-dispersible Resin Fine Particles for Comparison] As an oil phase component, 30 g of polystyrene and 0.5 g of Pionin A41C (manufactured by Takemoto Oil & Fat) were mixed with 75 g of ethyl acetate.
0 g of methyl ethyl ketone was dissolved in a mixed solvent of 30.0 g. As an aqueous phase component, a 4% aqueous solution of PVA205 (polyvinyl alcohol having a saponification degree of 88%, manufactured by Kuraray Co., Ltd.) was used in an amount of 10%.
0 g was produced. The oil phase component and the water phase component were emulsified at 10,000 rpm using a homogenizer. Thereafter, 80 g of water was added, and the mixture was stirred at room temperature for 30 minutes and further at 40 ° C. for 3 hours. The solid content concentration of the polymer fine particle dispersion thus obtained was 16%, and the average particle size was 0.21 μm.
m.

[Preparation Example b of Non-self-dispersible Hydrophobized Resin Fine Particles for Comparison] As an oil phase component, 30 g of polymethyl methacrylate, 0.5 pionin A41C (manufactured by Takemoto Yushi)
g of ethyl acetate 75.0 g methyl ethyl ketone 30.0
g of the mixed solvent. As an aqueous phase component, PVA20
100 g of a 4% aqueous solution of No. 5 (88% saponification, manufactured by Kuraray Co., Ltd.) was prepared. The oil phase component and the aqueous phase component were emulsified at 10,000 rpm using a homogenizer. Thereafter, 80 g of water was added, and the mixture was stirred at room temperature for 30 minutes and further at 40 ° C. for 3 hours.
The solid content concentration of the polymer fine particle dispersion thus obtained was 16%, and the average particle size was 0.23 μm.

[Production Example c of Non-self-dispersible Hydrophobized Resin Fine Particles for Comparison] As an oil phase component, 30 g of an epoxy resin (Epicoat 1004, manufactured by Yuka Shell Epoxy Co., Ltd.) was used.
0.5 g of Pionein A41C was dissolved in a mixed solvent of 75.0 g of ethyl acetate and 30.0 g of methyl ethyl ketone. As an aqueous phase component, 100 g of a 4% aqueous solution of PVA205 was prepared. The oil phase component and the water phase component were emulsified at 10,000 rpm using a homogenizer. Then add water to 80
g was added and the mixture was stirred at room temperature for 30 minutes and further at 40 ° C. for 3 hours. The solid content concentration of the polymer fine particle dispersion thus obtained was 16%, and the average particle size was 0.5 μm.

Examples 1 to 3 and Comparative Examples 1 to 3 [Preparation of aluminum support] 99.5% by weight of aluminum, 0.01% by weight of copper, 0.03% by weight of titanium, and 0.3% by weight of iron A 0.24 mm-thick rolled sheet of JISA105 aluminum material containing 0.1% by mass of silicon and 0.1% by mass of silicon was coated with a 400-mesh aqueous suspension of 20% by mass of pumistone (manufactured by Kyoritsu Ceramics) and a rotating nylon brush (6, 1
0-nylon) and the surface is grained,
Washed well with water. Next, after immersing in a 10% by mass aqueous solution of sodium hydroxide at 70 ° C. for 60 seconds for etching,
It was washed with running water. Furthermore, it was neutralized with a 20% by mass aqueous solution of nitric acid and washed with water. The obtained aluminum plate was placed in a 1.0% by mass aqueous nitric acid solution (containing 0.5% by mass of aluminum nitrate) and the voltage at the anode was 12.7 volts, and the ratio of the amount of electricity at the cathode to the amount of electricity at the anode was 0.1%. 9. Electrolytic surface roughening treatment was performed using a current having a rectangular wave alternating waveform under the condition of an electric quantity at the anode of 160 clones / dm ² . The surface roughness of the obtained substrate was 0.1.
It was 6 μm (Ra indication). Following this processing, 40
It was immersed in a 1% by mass aqueous solution of sodium hydroxide at 30 ° C. for 30 seconds, etched, and then washed with water. Next, at 55 ° C, 3
It was immersed in a 0% by mass aqueous sulfuric acid solution for 1 minute. In addition, 3
Anodizing treatment was performed in a 20% by mass aqueous sulfuric acid solution (containing 0.8% by mass of aluminum) at 5 ° C. using a direct current so that the mass of the anodic oxide film became 2.5 g / dm ² .
This was washed with water and dried to prepare a support.

[Preparation of a lithographic printing plate] A heat insulating layer and a hydrophilic layer were applied in this order on the anodized aluminum support thus prepared to prepare a lithographic printing plate.

On the above support, a heat insulating layer coating solution having the following composition was applied at a thickness of 1.0 g / m ² to form a heat insulating layer.

(Coating Solution for Thermal Insulation Layer) Butyral resin BM-S (manufactured by Sekisui Chemical Co., Ltd.) 10% MEK solution 59 g Carbon black dispersion (solid content 21%) 13.5 g MEK (methyl ethyl ketone) 62.7 g

A dry film weight of 3.0 g / m ² was applied on the heat insulating layer by a bar coater using a hydrophilic layer coating solution having the following composition.
It was applied so that Drying in oven at 45 ° C 20
Minutes. Thereafter, the film was left for 3 days under conditions of a temperature of 45 ° C. and a humidity of 40% to form a hardened film, thereby producing a lithographic printing original plate.

(Composition of hydrophilic layer coating solution) Sol-gel preparation solution 7.0 g 20% aqueous solution of colloidal silica (average particle diameter 20 nm) 4.0 g Hydrophobized resin fine particles (11% aqueous solution) 10.0 g Photothermal conversion agent (this specification) Of 1.5% aqueous solution of IR-1) described in the description 10.0 g of ion-exchanged water

Here, the hydrophobic resin fine particles were used in each of the examples in combinations shown in Table 1 below. The sol-gel preparation solution was prepared by preparing a solution having the following composition and aging at room temperature for 2 hours.

(Sol-gel preparation liquid) Tetramethoxysilane 9.2 g Ethanol 16.2 g Deionized water 10.2 g 0.1 mol / L nitric acid aqueous solution 6.0 g

The printing plate thus prepared was subjected to an output of 12 W, an outer drum rotation speed of 94 rpm, a plate surface energy of 300 mJ / cm by a Creo Trendsetter 3244 VFS equipped with a water-cooled 40 W infrared semiconductor laser.
^2. Exposure was performed under the conditions of a resolution of 2400 dpi to form an image area thermally fused on the exposed surface. The contact angles of water droplets in the air were measured for the non-image portion and the image portion surface after the exposure, and the results are shown in Table 1. Further, the exposed printing plate was mounted on a printing machine as it was without being subjected to development processing, and printing was performed. Use RYOBI-3200MCD for the printing press and EU
-3 (manufactured by Fuji Photo Film Co., Ltd.) in 1% by volume aqueous solution, and the ink used was GEOS (N) black (manufactured by Dainippon Ink and Chemicals, Inc.). Table 1 shows the evaluation results of the difficulty in printing and the printing durability. The printing durability evaluation was completed at 20,000 sheets. A printing durability of 2 or more in Table 1 indicates that there was still room at 20,000 sheets.

[0138]

[Table 1]

The above results show that the original plate for printing using self-water dispersible hydrophobic resin fine particles has a lower contact angle with water in the non-image area, is more resistant to stains in printing, and It shows that the properties are also excellent.

[0140]

According to the present invention, after exposure, it is possible to directly mount the printing apparatus on a printing machine without the need for a developing process and to perform printing. A lithographic printing plate can be provided.

Claims (5)

[Claims] Claims 1. A self-dispersible hydrophobic resin fine particle, a photothermal conversion agent and a hydrophilic binder are contained on a support.
A lithographic printing plate having a hydrophilic layer that can be rendered hydrophobic by heat. 2. The resin of said hydrophobized resin particles, wherein at least one lipophilic resin selected from the group consisting of acrylic resin, epoxy resin, styrene resin, urethane resin, phenol resin, vinyl ester resin and derivatives thereof in the molecule. A resin having a structural portion of a resin and a structural portion having at least one hydrophilic group selected from a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a hydroxyl group, an amide group, a sulfonamide group, and an amino group. 2. The lithographic printing original plate according to claim 1, wherein: 3. The lithographic plate according to claim 1, wherein the hydrophobic resin fine particles have a core / shell structure, the core portion is a lipophilic resin, and the shell portion is fine particles comprising a hydrophilic component. Original plate for printing. 4. The lipophilic resin of the core portion is an acrylic resin,
The lithographic printing plate according to claim 3, wherein the plate is at least one resin selected from the group consisting of an epoxy resin, a styrene resin, a urethane resin, a phenol resin, a vinyl ester resin, and derivatives thereof. 5. The resin according to claim 5, wherein the hydrophilic component in the shell has at least one hydrophilic group selected from a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a hydroxyl group, an amide group, a sulfonamide group and an amino group. The original plate for lithographic printing according to claim 3 or 4, wherein: