JP2002283757A - Planographic printing original plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a planographic printing original plate capable of printing without execution of development treatment after exposure, having improved printing durability and excellent in non-staining properties. SOLUTION: This planographic printing plate has a hydrophilic layer containing a hydrophobic precursor, a photothermal converting agent and a three-dimensional crosslinked hydrophilic binder and becoming hydrophobic by heat on a supporting body. The hydrophobic precursor is fine particles having a core-shell structure containing a lipophilic resin in the core part and cationic substituent groups in the shell part.

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 printing the image 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.

[0003] For example, Japanese Patent No. 2938397,
JP-A-9-127683 and WO99-101
No. 86 discloses a heat-sensitive lithographic printing original plate having a hydrophilic image forming layer in which thermoplastic polymer fine particles are dispersed in a matrix such as a hydrophilic resin, on a substrate having a hydrophilic surface. In these publications, when heat is applied to an image forming layer by infrared exposure or the like, thermoplastic polymer fine particles are melted and united, and the surface of the hydrophilic image forming layer is converted into an lipophilic image area, and this image area is formed. A method in which a lithographic printing plate is mounted on a printing press and the printing plate is supplied with dampening water and ink while rotating the plate cylinder, thereby removing unheated portions as if they were developed (on-machine development). Method), it is described that the development processing using a conventional automatic developing machine or the like is omitted.

Japanese Patent Application Laid-Open No. 2000-238452 discloses a lithographic printing material containing, in an image forming layer, a microgel having on its surface a group capable of decomposing by at least one of light and heat, and an infrared light absorbing agent. It is described that the above can be developed.

[0005] However, the removal of the unexposed portion is affected by the starting conditions of the printing press, or the removed material containing a large amount of lipophilic component is dampened in the above-mentioned on-press development type unprocessed lithographic printing plate. Since the water roller and the dampening water are contaminated, there are problems that cost and labor are required, for example, tens to hundreds of prints are required to obtain a good printed matter, and the roller needs to be washed.

Research Disclosure N, January 1992
No. 33303 and the like describe a heat-sensitive lithographic printing plate having a heat-sensitive layer in which a thermoplastic polymer fine particle is dispersed in a hydrophilic resin crosslinked. Further, Japanese Patent Application Laid-Open No. 7-1849
Nos. 7-1850, 10-6468 and 1
No. 1-70756 describes a heat-sensitive lithographic printing plate precursor having a hydrophilic layer in which microcapsules containing lipophilic components as lipophilic fine particles are dispersed in a crosslinked hydrophilic binder polymer. These heat-sensitive lithographic printing original plates do not require on-press development by using the surface configuration of the lipophilic image area formed by heat from exposure and the hydrophilic non-image area of the unexposed area as the printing surface, It describes that lithographic printing using a fountain solution can be performed without any treatment.

[0007]

However, the completely unprocessed lithographic printing plate of the prior art has a problem in that it is difficult to stain in printing and the printing durability is insufficient. An object of the present invention is to solve this problem, and there is provided a lithographic printing original plate which can be printed without performing development processing after exposure, and has improved printing durability and good stain resistance. To provide a lithographic printing plate.

[0008]

Means for Solving the Problems The present inventor has found that the above object can be achieved by the following constitution. That is, the present invention is as follows.

1. A lithographic printing plate precursor having a hydrophilic layer which becomes hydrophobic by heat, comprising a hydrophobizing precursor, a photothermal conversion agent and a three-dimensionally cross-linked hydrophilic binder, on a support, comprising: A lithographic printing plate, wherein the body is fine particles having a core-shell structure containing a lipophilic resin in a core portion and a resin having a cationic substituent in a shell portion.

[0010] 2. 2. The lithographic printing plate as described in 1 above, wherein the cationic substituent is an ammonium group or a phosphonium group.

3. Wherein the lipophilic resin of the core is at least one resin selected from acrylic resin, styrene resin, vinyl ester resin, epoxy resin, urethane resin, phenol resin, and derivatives thereof. 3. The lithographic printing original plate as described in 2 above.

According to the present invention, a hydrophilic binder is prepared by using a core-shell type fine particle as a hydrophobizing precursor in a hydrophilic layer, a lipophilic resin for a core portion, and a resin having a cationic substituent for a shell portion. Excellent interaction (adhesion), as a result,
It has been found that the hydrophilicity of the non-image area is not reduced, the ink receptivity of the film converted into the lipophilic image area by heating can be maintained, and that the printing durability is excellent by improving the strength of the entire film. Based on repeated studies.

[0013]

Embodiments of the present invention will be described below in detail. In the present invention,% means mass% unless otherwise specified.

[Hydrophilic Layer] The hydrophobizing precursor used in the hydrophilic layer of the present invention is fine particles capable of converting the hydrophilic layer to hydrophobic when heated, and has a core-shell structure.
Fine particles containing a component having a lipophilic resin in the core and a cationic substituent in the shell.

The fine particles having a core-shell structure used in the present invention are composed of fine particles of a lipophilic resin which is softened or melted by the action of heat obtained by emulsification (including the phase inversion emulsification method) or dispersion polymerization. Composite fine particles or hetero-phase structure fine particles having a component having a cationic substituent as a shell portion.

As the lipophilic resin constituting the core portion, an acrylic resin, a styrene resin, a vinyl ester resin and other polymers or copolymers made from monomers selected from the following (A) to (J): Coalescence is preferred. Further, an epoxy resin, a urethane resin, and a phenol resin are also preferable. Further, derivatives of these resins, polymers or copolymers are also suitable.

(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-acrylate acrylate (Substituted) acrylates such as hydroxybutyl, glycidyl acrylate, N-dimethylaminoethyl acrylate, o-, m- and p-hydroxyphenyl acrylate.

(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, benzyl methacrylate. -2
(Substituted) methacrylates such as -chloroethyl, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, glycidyl methacrylate, N-dimethylaminoethyl methacrylate, o-, m- and p-hydroxyphenyl methacrylate. Can be

(C) Styrenes. Examples of this group of monomers include styrene, methylstyrene, chloromethylstyrene, o-, m- and p-hydroxystyrene, and the like.

(D) Vinyl esters. Examples of this group of monomers include vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate, and the like.

(E) Acrylamide and methacrylamide. Examples of this monomer group include acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, N-hexylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide , N-cyclohexyl methacrylamide, N-hydroxyethylacrylamide, N-
Hydroxyethylacrylamide, N-phenylacrylamide, N-phenylmethacrylamide, N-benzylacrylamide, N-benzylmethacrylamide, N
-Nitrophenylacrylamide, N-nitrophenylmethacrylamide, N-ethyl-N-phenylacrylamide and N-ethyl-N-phenylmethacrylamide, N- (4-hydroxyphenyl) acrylamide,
Acrylamide such as N- (4-hydroxyphenyl) methacrylamide or methacrylamide is exemplified.

(F) 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.

(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 group of monomers include ethylene, propylene, isobutylene, butadiene, isoprene and the like.

(I) N-containing monomers. Examples of this group of monomers include N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile, and the like.

(J) Unsaturated sulfonamide. Examples of this group of monomers include N- (o-aminosulfonylphenyl)
Acrylamide, N- (m-aminosulfonylphenyl) acrylamide, N- (p-aminosulfonylphenyl) acrylamide, N- [1- (3-aminosulfonyl) naphthyl] acrylamide, N- (2-aminosulfonylethyl) acrylamide, etc. Acrylamides, N- (o-aminosulfonylphenyl) methacrylamide, N- (m-aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonylphenyl) methacrylamide, N- [1- (3-aminosulfonyl) )
Naphthyl] methacrylamides, methacrylamides such as N- (2-aminosulfonylethyl) methacrylamide, and o-aminosulfonylphenyl acrylate;
m-aminosulfonylphenyl acrylate, p-aminosulfonylphenyl acrylate, 1- (3-aminosulfonylphenylnaphthyl) acrylate, o-aminosulfonylphenyl methacrylate, m-aminosulfonylphenyl methacrylate, p-aminosulfonylphenyl methacrylate, 1- ( Acrylic acid and methacrylic acid esters such as (3-aminosulfonylphenylnaphthyl) methacrylate.

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 having a polymerizable unsaturated group in some cases. 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, endmethylenetetrahydromaleic anhydride, α-terpinene maleic anhydride adduct, monoallyl ether of triol, pentaerythritol diallyl ether or allyl glycidyl ether. Polymerizable unsaturated bonds (vinyl groups) are introduced by polycondensation or addition of various compounds.

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 carboxyl group at a terminal can be obtained. Alternatively, one having an acid group in the main chain can be obtained by using trimellitic anhydride.

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

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.

The organic polymer compound obtained from these monomers has a weight average molecular weight of 500 to 500,000,
Preferably, the number average molecular weight is from 200 to 60,000.

The shell portion of the core-shell fine particles of the present invention contains a resin having a cationic group. The cationic group is preferably an onium group having a central atom of an atom belonging to Group 15 or 16 of the periodic table, more preferably an onium group having a nitrogen atom, a phosphorus atom or a sulfur atom as a central atom, particularly preferably. Is an onium group having a nitrogen atom or a phosphorus atom as a central atom. Also,
The resin having a cationic group is preferably a polymer whose main chain structure is a vinyl-based polymer such as an acrylic resin or a styrene resin, or a urethane resin, a polyester, or a polyamide. Among them, a vinyl polymer having a main chain structure such as an acrylic resin or a styrene resin is more preferable. Particularly preferred resins include at least one polymerizable compound in which a component having an onium group is represented by the following general formula (1), (2), (3) or (4). It is a polymer or a copolymer.

[0035]

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In the formula, J represents a divalent linking group. K represents an aromatic group or a substituted aromatic group. M each independently represents a divalent linking group. Y ₁ represents an atom belonging to Group 15 of the periodic table, and Y ₂ represents an atom belonging to Group 16. X ^- represents a counter anion. R ₁ represents a hydrogen atom, an alkyl group or a halogen atom. R ₂ , R ₃ , R ₄ and R ₆ each independently represent a hydrogen atom or an alkyl group, an aromatic group or an aralkyl group to which a substituent may be bonded, and R ₅ represents an alkylidene group or a substituted alkylidene group. Represent. R ₂ and R ₃ or R ₅
And R ₆ may combine with each other to form a ring. Z represents a nonmetallic atom group necessary for forming an unsaturated heterocyclic ring.
j, k, and m each independently represent 0 or 1. u represents an integer of 1 to 3.

Among the components having an onium group, more preferred
Preferably, J represents -COO- or -CONH-,
K represents a phenylene group or a substituted phenylene group;
Substituent is hydroxyl group, halogen atom or alkyl
Group. M is an alkylene group or a molecular formula of C_nH
_2nO, C_nH_2nS or C_nH_{2n + 1}N-valent
Represents a linking group. Here, n represents an integer of 1 to 12.
You. Y₁Represents a nitrogen atom or a phosphorus atom;_TwoIs sulfur
Represents an atom. X^-Is a halogen ion, PF₆ ^-, BF _Four ^-Ma
Or R₇SO_Three ^-Represents R₁Is a hydrogen atom or an alkyl group
Represents R_Two, R_Three, R_FourAnd R₆Are each independently water
A carbon atom having 1 to 1 carbon atoms to which an element atom or a substituent may be bonded;
0 represents an alkyl group, an aromatic group or an aralkyl group.
Then R_FiveIs an alkylidene group having 1 to 10 carbon atoms or substituted
Represents an alkylidene group. R_TwoAnd R_ThreeOr R_FiveAnd R₆Is it
Each may combine to form a ring. R₇Is a substituent
And an alkyl group having 1 to 10 carbon atoms, an aromatic group,
Represents an aralkyl group. Z is imidazole, pyridine, pyro
Group necessary to form a phenolic or morpholine ring
Represent. j, k and m each independently represent 0 or 1
, But j and k are not simultaneously 0.

Particularly preferred among the constituent components having an onium group.
Preferably, K represents a phenylene group or a substituted phenylene group.
Represents a hydroxyl group or a group having 1 to 3 carbon atoms.
Is an alkyl group. M is an alkylene group having 1 to 2 carbon atoms
Or an alkylene group having 1 to 2 carbon atoms linked by an oxygen atom
Represents X^-Is chlorine ion or R₇SO_Three ^-Represents R ₁
Represents a hydrogen atom or a methyl group. j is 0 and k is
It is one.

Specific examples of the constituent having an onium group are shown below. However, the present invention is not limited to this specific example.

[0040]

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[0041]

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As a method for forming a shell portion containing a resin having a cationic substituent, the above-mentioned monomer having a cationic substituent is added to a dispersion of core particles (seed) and the surface of the core particles is coated with the monomer. There is a method in which a monomer is polymerized. As another method, a monomer having a substituent (for example, an amino group) capable of forming a cation by reacting with an acid is added to a dispersion of core particles (seed), and the monomer is polymerized on the surface of the core particles. Then, a method of reacting with an acid or a method of introducing a compound capable of forming a cation by reacting with an acid into a shell portion by a polymer reaction and then reacting the acid can be used, but the method is not limited thereto.

As a monomer having an amino group useful in a method of introducing a cationic group into the shell portion by polymerizing a monomer having an amino group on the surface of the core particle and then reacting with an acid, for example, N- (3 -Aminopropyl) methacrylamide, N- (2-aminoethyl) methacrylamide, 2-aminoethyl methacrylate, 2-aminoethyl acrylate, 3-aminopropyl acrylate,
3-amino-2-hydroxypropyl methacrylate,
Allylamine, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate,
N, N-diethylaminoethyl acrylate, N, N-
Diethylaminoethyl methacrylate, N, N-dimethylaminopropylacrylamide, diallylamine, N
-Methylallylamine and the like.

Examples of amino compounds for introducing an amino group into a shell having a carboxyl group or the like by a polymer reaction and then reacting with an acid to form an ammonium salt include ethyleneimine and propyleneimine.

Examples of the acid used for the reaction with the amino group of the shell include hydrohalic acid, sulfuric acid, phosphoric acid, sulfonic acid, and carboxylic acid. Examples of the carboxylic acid include formic acid, acetic acid, propionic acid, and the like. Oxalic acid, malonic acid,
Succinic acid, oxaloacetic acid, lactic acid, tartaric acid, aldaric acid,
Examples include, but are not limited to, citric acid.

The average particle size of the core-shell 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.

As the three-dimensionally cross-linked hydrophilic binder suitable for the hydrophilic layer of the present invention, a hydrophilic organic polymer binder resin cross-linked with a cross-linking agent and a hydrophilic sol-gel conversion type inorganic binder resin can be used. Can be mentioned. 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 will be described.

Specific examples of the organic polymer binder resin include gum arabic, polyvinyl alcohol (PVA), starch and its derivatives, carboxymethylcellulose and its sodium salt, cellulose derivatives such as hydroxyethylcellulose and cellulose acetate, and 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.

Glyoxal, melamine formaldehyde resin, and the like,
Aldehydes such as urea formaldehyde resin, methylol compounds such as N-methylol urea, N-methylol melamine, methylolated polyamide resin, active vinyl compounds such as divinyl sulfone and bis (β-hydroxyethyl sulfonic acid), epichlorohydrin and polyethylene glycol Glycidyl ether, adducts of polyamide / polyamine / epichlorohydrin, epoxy compounds such as polyamide epichlorohydrin resin, ester compounds such as monochloroacetate and thioglycolate, polyacrylic acid, methyl vinyl ether / maleic acid copolymer And inorganic crosslinkers such as salts of boric acid, boric acid, titanyl sulfate, Cu, Al, Sn, V, and Cr; 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.

Particularly preferred binders for the hydrophilic layer of the present invention include:
It is a sol-gel conversion type binder resin described below. The system capable of sol-gel conversion, which is preferably applicable to the present invention, is a system in which the bond coming out of a polyvalent element forms a network structure via an oxygen atom, and the polyvalent element also has an unbonded hydroxyl group or alkoxy group. These are polymers that have a resin-like structure in which these are mixed, and are in a sol state at the stage where there are many alkoxy groups and hydroxyl groups. The structure becomes 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 the hydroxyl group 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 that undergoes sol-gel conversion is aluminum, silicon, titanium, zirconium, etc., and any of them can be used in the present invention. A sol-gel conversion system using a siloxane bond that can be used will be described. The sol-gel conversion using aluminum, titanium, and zirconium can be performed by substituting silicon for each element described below.

The inorganic hydrophilic binder resin formed by 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 has at least one silanol group. The coating solution, which is a sol-based coating solution containing a silane compound, is formed by the progress of hydrolytic condensation of silanol groups to form a siloxane skeleton structure and gelation during the lapse of time after coating.

The layer formed by the sol-gel conversion may be added with an organic hydrophilic polymer or a crosslinking 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 (5):
The silane compound having at least one silanol group is represented by the following general formula (6). Further, the substance system contained in the hydrophilic layer does not necessarily need to be a silane compound of the general formula (6) alone, and may generally be composed of an oligomer obtained by partially hydrolyzing the silane compound. The mixture composition of the oligomer may be used.

[0054]

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The siloxane resin represented by the general formula (5) is
It is formed by sol-gel conversion from a dispersion containing at least one silane compound represented by the following general formula (6), and at least one of R ^{11 to} R ^{13 in} the general formula (5) represents a hydroxyl group. And others represent organic residues selected from R ¹⁰ Q in the following general formula (6).

Formula (6) (R ¹⁰ ) _n Si (Q) _4-n

In the general formula (6), R ¹⁰ is a hydroxyl group,
Represents a hydrocarbon group or a heterocyclic group. Q represents a hydrogen atom, a halogen atom, —OR ¹⁴ , —OCOR ¹⁵ , or —N
(R ¹⁶ ) represents (R ¹⁷ ) (R ¹⁴ and R ¹⁵ each represent a hydrocarbon group, and R ¹⁶ and R ¹⁷ may be the same or different and each represent a hydrogen atom or a hydrocarbon group). n represents 0, 1, 2 or 3.

The hydrocarbon group or heterocyclic group represented by R ^{10 in} the general formula (6) is, for example, a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted, for example, a methyl group , Ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group,
A decyl group, a dodecyl group, or the like, and a group substituting these groups includes a halogen atom (a chlorine atom, a fluorine atom,
Bromine atom, hydroxyl group, thiol group, carboxyl 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-dimethylaminoethyl group, 2-bromoethyl group, 2- (2-methoxyethyl)
Oxyethyl group, 2-methoxycarbonylethyl group, 3
-Carboxypropyl group, benzyl group, etc.), -O
A COR ″ group (R ″ represents the same content as R ′),
-COOR "group, -COR" group, -N (R "") (R "")
(R ′ ″ represents a hydrogen atom or the same content as R ′, and may be the same or different), —NHCONH
R "group, -NHCOOR" group, -Si (R ") ₃ group,-
CONHR ′ ″ group, —NHCOR ″ group, etc.],

A linear or branched alkenyl group having 2 to 12 carbon atoms which may be substituted (for example, vinyl, propenyl, butenyl, pentenyl, hexenyl, octenyl, decenyl, dodecenyl, etc.) Wherein the group substituted with these groups includes 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. Examples of the group include those having the same contents as the group substituted with the alkyl group, and may be substituted with a plurality of groups.)

An optionally substituted alicyclic group having 5 to 10 carbon atoms (for example, cyclopentyl, cyclohexyl, 2
-Cyclohexylethyl group, 2-cyclopentylethyl group, norbornyl group, adamantyl group and the like, examples of the group substituted with these groups include those having the same contents as the substituents of the alkyl group. May be used),

An optionally substituted aryl group having 6 to 12 carbon atoms (for example, a phenyl group or a naphthyl group, examples of the substituent include those having the same contents as the above-mentioned groups substituted with the alkyl group. Or a condensed heterocyclic group containing at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom (for example, a pyran ring, a furan ring, A 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., which may contain a substituent. Examples of the group include those having the same contents as the substituents in the alkyl group, and a plurality of groups may be substituted.

In the general formula (6), -OR ¹⁴ group of Q, -OC
Examples of the substituent of the OR ¹⁵ group or ^{-N (R 16) (R 17} ) group, for example, the following substituents. -OR ¹⁴ groups,
R ¹⁴ is an aliphatic group having 1 to 10 carbon atoms which may be substituted (for example, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, pentyl group, octyl group, nonyl group, decyl group, Propenyl, butenyl, heptenyl, hexenyl, octenyl, decenyl, 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, chlorocyclohexyl group, methoxycyclohexyl group, benzyl group, phenethyl group, dimethoxybenzyl group, methyl Benzyl group, bromobenzyl group, etc.).

In the —OCOR ¹⁵ group, R ¹⁵ is an aliphatic group having the same contents as R ¹⁴ or an aromatic group which may be substituted and has 6 to 12 carbon atoms (aromatic groups include the above-mentioned R ¹⁰ in R ¹⁰ ). And the same as those exemplified for the aryl group).
In the —N (R ¹⁶ ) (R ¹⁷ ) group, R ¹⁶ and R ¹⁷ 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 (eg, And those having the same contents as those of R ¹⁴ in the above-mentioned —OR ¹⁴ group)
Represents More preferably, the sum of R ¹⁶ and R ¹⁷ primes is 16
It is within the number. Specific examples of the silane compound represented by the general formula (6) include the following, but are not limited thereto.

[0065] 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-hexyltriethoxysilane, 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-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltri-t-butoxysilane,
γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β
-(3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like.

Inorganic hydrophilic binder resin type of hydrophilic layer of the present invention
With the silane compound represented by the general formula (6) used for the synthesis
Sol-gel conversion of Ti, Zn, Sn, Zr, Al, etc.
Use a metal compound that binds to the resin during film formation
be able to. As the metal compound used, for example,
Ti (OR¹⁸)_Four(R¹⁸Represents a methyl group, an ethyl group,
Group, butyl group, pentyl group, hexyl group, etc.), TiC
l_Four, Zn (OR¹⁸)_Two, Zn (CH_ThreeCOCHCOC
H_Three)_Two, Sn (OR¹⁸)_Four, Sn (CH_ThreeCOCHCOC
H_Three)_Four, Sn (OCOR¹⁸)_Four, SnCl_Four, Zr (OR
^{1 8})_Four, Zr (CH_ThreeCOCHCOCH_Three)_Four, Al (OR
¹⁸)_Three, Al (CH_ThreeCOCHCOCH_Three)_ThreeEtc.
You.

Further, in order to promote the hydrolysis and polycondensation reaction of the silane compound represented by the general formula (6) 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 a basic compound may be 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). The concentration at that time is not particularly limited, but when the concentration is high, the rate of hydrolysis and polycondensation tends to increase. However, if a concentrated basic catalyst is used, a precipitate may be formed in the sol solution,
The concentration of the basic catalyst is desirably 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 dried coating film is preferable. . Specifically, acidic catalysts are represented by hydrogen halides such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, carbonic acid, carboxylic acids such as formic acid and acetic acid, and their RCOOH. Examples of basic catalysts include carboxylic acids such as substituted carboxylic acids in which R in the structural formula is substituted by other elements or substituents, sulfonic acids such as benzenesulfonic acid, and ammonia bases such as aqueous ammonia and amines such as ethylamine and aniline. Can be

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).

The hydrophilic layer of the present invention contains a light-to-heat 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.

Examples of pigments include 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 types of pigments include black pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and polymer-bound pigments. 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 the photothermal conversion agent are commercially available dyes and literatures (for example, "Ken 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 sulfo 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.

[0077]

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[0078]

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[0079]

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The content of the photothermal conversion agent contained in the hydrophilic layer is an amount sufficient for the vicinity of the hydrophobizing precursor to be thermally fused by the heat generated by the light absorption of the photothermal conversion agent to be hydrophobized. It can be selected widely from 2 to 50% of the solid content of the hydrophilic layer. 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, in addition to the above, other than the above, improvement in sensitivity, control of the degree of hydrophilicity, improvement in the physical strength of the hydrophilic layer, improvement in the dispersibility of the compositions constituting the layer, Additives for various purposes such as improvement of coating property, improvement of printing suitability, and convenience of plate making operation, for example, hydrophilic sol-like fine particles, surfactant, and coloring agent can be added. These additives include, by way of example, the following:

The hydrophilic sol-shaped 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 70%, preferably 5.0 to 50% of the hydrophilic layer solid content. The total addition amount of the photothermal conversion agent, the hydrophobizing precursor and the hydrophilic sol-like fine particles is 2% of the solid component of the hydrophilic layer.
~ 95%, preferably 5-85%.

The silica sol has many hydroxyl groups on the surface and has a siloxane bond (-Si-O-Si
-). Since ultrafine silica particles having a particle diameter of 1 to 100 nm are present in a state of being dispersed in water or a polar solvent due to surface hydroxyl groups, they are also called colloidal silica. Specifically, Toshiro Kaga and Ei Hayashi supervised “Applied Technology of High Purity Silica” Volume 3,
Co., Ltd. (1991).

The 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-like fine particles have an average particle size 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 from Nissan Chemical Industries, Ltd. or the like.

In the hydrophilic layer of the lithographic printing plate precursor according to the present invention, in addition to nonionic and anionic surfactants, in order to enhance stability under printing conditions, Japanese Patent Application Laid-Open No. 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 the nonionic surfactant 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 are ether-bonded to the terminal hydroxyl groups of the polyoxyethylene / polyoxypropylene block copolymer. Complex polyoxyalkylene alkyl ethers, also complex polyoxyalkylene alkyl aryl ethers having alkyl-substituted aryl groups ether-bonded, sorby Emissions monolaurate, sorbitan monostearate, sorbitan tristearate, sorbitan monopalmitate, sorbitan monooleate, sorbitan fatty acid esters such as sorbitan trioleate,
Polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan triolate and the like. Can be

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 anionic surfactants 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.

In 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 above surfactant in the total solid content of the hydrophilic layer is preferably from 0.05 to 15%, more preferably from 0.1 to 5%.

[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, examples of the hydrophobic resin 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, aggrynitrile-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 above-mentioned hydrophilic resin is preferably crosslinked and cured before use. As the crosslinker, the above-mentioned crosslinker 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 in 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.
You can choose widely from ~ 95%.

[0103] 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. Additives for various purposes, for example, hydrophilic sol-like fine particles, a surfactant and the like can be added for reasons such as improvement in adhesion. 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] When the hydrophilic layer is the outermost surface, the lithographic printing original plate of the present invention is used when the original 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. Since the water-soluble protective layer is mainly composed of a water-soluble polymer, it is dissolved in dampening water at the initial stage of printing and can be washed away. Not be. Hereinafter, the components contained in the water-soluble protective layer will be described.

As the water-soluble polymer used for the water-soluble protective layer, for example, a polymer having a sufficient group such as a hydroxyl group, a carboxyl group, or a basic nitrogen-containing group can be used.
Specifically, polyvinyl alcohol (PVA), modified PVA such as carboxy-modified PVA, gum arabic, polyacrylamide and its copolymer, polyacrylic acid, acrylic acid copolymer, vinyl methyl ether / maleic anhydride copolymer , Vinyl acetate / maleic anhydride copolymer, styrene / maleic anhydride copolymer, roasted dextrin,
Oxygen-decomposed dextrin, enzyme-decomposed 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, poly ( Ethylene oxide), water-soluble urethane resin, water-soluble polyester resin, polyhydroxyethyl acrylate, polyethylene glycol, polypropylene glycol, N-vinyl carboxylic acid amide polymer and the like. Above all, polyvinyl alcohol (PVA), carboxy-modified PVA
Such as modified PVA, gum arabic, polyacrylamide,
Preference is given to using polyacrylic acid, acrylic acid copolymers, polyvinylpyrrolidone, alginic acid and their alkali metal salts.

The content of the water-soluble resin in the coating solution for the protective layer is as follows:
3 to 25% is appropriate, and a preferable range is 10 to 25%.
It is. 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 addition amount of the surfactant is preferably 0.01 to 1% of the solid content of the protective layer, and more preferably 0.05 to 0.5%.

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

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,
Sodium dehydroacetate or the like can be added in the range of 0.005 to 2.0%. Preferred antifoaming agents include an organic silicone compound, and the amount of addition is preferably in the range of 0.0001 to 0.1%.

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 that can be used for the hydrophilic layer is the same as the solid matter of the protective layer.
It can be used in an addition amount range of ５０50%.

[Coating] The hydrophilic layer, the heat-insulating layer and the protective layer described above were prepared by mixing the respective constituent components and applying a prepared coating solution to a support by using any of the 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 having good dimensional stability and relatively low cost is preferable. Suitable aluminum plates are a pure aluminum plate and an alloy plate containing aluminum as a main component and containing 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 foreign elements in the alloy is at most 10% 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 and used material can be appropriately used. The thickness of the support used in the present invention is approximately 0.05 mm to
About 0.6 mm, preferably 0.1 mm to 0.4 mm,
Particularly preferably, it is 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 aqueous alkaline solution to remove rolling oil on the surface, and then 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 carried out 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 surface roughening. Is selectively dissolved. As a mechanical method, a known method such as a ball polishing method, a brush polishing method, a blast polishing method, and a buff polishing method can be used. 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. Further, as an electrochemical surface roughening method, there is a method of carrying out an alternating current or a direct current 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 necessary, and further neutralized, and then, if necessary, anodized to enhance abrasion resistance. Processing is performed.

As the electrolyte used for the anodic oxidation treatment of the aluminum plate, various electrolytes for 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.

The anodizing treatment conditions vary depending on the electrolyte to be used and cannot be specified unconditionally. However, in general, the concentration of the electrolyte is 1 to 80% solution, the liquid temperature is 5 to 70 ° C., and the current density is 5 to 70%. 60A / dm ² , voltage 1-100V, electrolysis time 1
A range of 0 seconds to 5 minutes is appropriate.

The amount of the formed oxide film is 1.0 to 5.0.
g / m ^2, it is particularly preferably 1.5 to 4.0 g / m ^2. If the amount of the anodic oxide film is less than 1.0 g / m ² , the printing durability will be insufficient or the film will be easily scratched.

Among these anodic oxidation treatments, in particular, a method of anodic oxidation 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 made hydrophobic by applying an undercoat 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 ²¹ O) ₃ SiR ²² (R ²¹ and R ²² are an alkyl group or a substituted alkyl group), and the R ²¹ O group is hydrolyzed to an OH group to form an OH group. bound at the surface and an ether bond, R ²² group provides a hydrophobic surface for receiving ink.

Examples of the silane coupling agent include γ-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ-glycoxydoxysilane. Propyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptotrimethoxysilane, γ-
Ureidopropyltriethoxysilane, N- (β-aminoethyl)-(β-aminopropyl) dimethoxysilane and the like. In the case of a plastic support, in order to ensure adhesion to the hydrophilic layer, a corona 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 original plate for lithographic printing of the present invention can be irradiated with a laser having a laser output of 0.1 to 300 W. When a pulse laser is used, it is preferable to irradiate a laser having a peak output of 1000 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.

[0127]

The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.

Fine particle preparation example 1 [Core-shell fine particles 1 containing an ammonium group in the shell part] A liquid epoxy resin DER333 (a catalyst-added epoxy resin manufactured by Dow Chemical Co., epoxy equivalent: about 200) was placed in a reaction vessel.
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 attached to the reaction vessel, and the inside of the system was sealed. Then, 153 g of n-butanol was added.
Was injected using a pump to obtain a solution of the epoxy resin, which was kept at 117 ° C.

In another container, 25 g of methacrylic acid, 15 g of styrene, 15 g of methyl methacrylate, 4.6 g of benzoyl peroxide and 10 g of acryloyloxyethyltrimethylammonium chloride were mixed. This monomer mixture was added to the epoxy resin solution at a constant rate over 180 minutes. The reaction temperature is 116-117 ° C
, And after the addition of the monomer mixture is completed,
Stirring was continued for another 3 hours. The reaction product is n-
It was dispersed in butanol and became semi-turbid.

This resin dispersion was gradually added to 500 g of deionized water 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 remaining aqueous dispersion was washed with an ultrafiltration module (ACP-1050 manufactured by Asahi Kasei Corporation).

The aqueous dispersion of the ammonium group surface-modified epoxy resin fine particles thus obtained had a finely dispersed resin and turned milky white. The aqueous dispersion was stable for three months without aggregation or precipitation of the resin, and the dispersion was stable. This dispersion had a non-volatile content of 23%. As a result of gas chromatography, n-butanol was not detected. Otsuka Electronics Co., Ltd. Laser Doppler Particle Size Analyzer E
The average particle size of the fine particles measured by LS-800 is 0.21 μm.
m.

Preparation Example 2 of Fine Particles [Core-shell Fine Particles 2 Containing Ammonium Group in Shell Part] 29 g of methacrylic acid and 18 parts of styrene were added to the epoxy resin solution maintained at 117 ° C. described in Preparation Example 1 of the above fine particles.
g, 20 g of methyl methacrylate and 4.6 g of benzoyl peroxide were added at a constant rate over a period of 180 minutes. The reaction temperature is 116-117 ° 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 remaining aqueous dispersion was washed with an ultrafiltration module in the same manner as in Preparation Example 1.

The resulting epoxy / acrylic resin core /
68.16 g of the shell fine particle aqueous dispersion (A) and 64 g of distilled water were placed in a condenser 2 equipped with a condenser, a dropping funnel and a stirrer.
Put in a 00 ml round bottom three-necked flask,
Heated for 0 minutes. After confirming that the temperature became constant, an aqueous solution in which 0.28 g of propyleneimine was dissolved in 4.0 g of water was dropped from the dropping funnel. After supply is completed, 5
The mixture was heated and stirred at 5 ° C. for 2 hours. After leaving overnight at room temperature, 70 g of citric acid aqueous solution having a solid concentration of 10% was added at room temperature,
Stirring was performed. After the contents once aggregated, one hour later,
Again a good dispersion was obtained. After leaving at room temperature for half a day, the excess citric acid was removed with an ultrafilter, and the solid content concentration was 10
% Of a dispersion of ammonium group surface-modified epoxy resin fine particles. The average particle size of the fine particles was 0.17 μm.

Preparation Example 3 of Fine Particles [Core-shell Fine Particles Containing Phosphonium Group in Shell Part] In the epoxy resin solution kept at 117 ° C. described in Preparation Example 1 of fine particles, 60 g of methacrylic acid and Cydaps PM were added.
-4CMS (m-vinylbenzyl-tributylphosphonium chloride and p-vinylbenzyl manufactured by Nippon Chemical Industry)
Mixture of -tributylphosphonium chloride) 40
g, 40 g of ethyl acrylate and 4.6 g of benzoyl peroxide. 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. Such a resin dispersion was gradually added to 500 g of deionized water 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. Next, the above-mentioned dispersion in water was added to 50-60.
Distillation under reduced pressure was carried out at 260 ° C. to remove 260 g. The remaining aqueous dispersion was washed using an ultrafiltration module in the same manner as in Preparation Example 1. 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. This dispersion had a non-volatile content of 30%, and as a result of gas chromatography, n-butanol was not detected.
The average particle size of the fine particles was 0.19 μm.

Preparation Example 1 of Comparative Fine Particles [Non-Core-Shell Polymer Fine Particles Having Phosphonium Group] 600 g of distilled water was placed in a 2 L four-necked flask equipped with a stirrer, a reflux device, a nitrogen inlet tube, a dropping device, and a thermometer. 300 g of isopropyl alcohol and 5 g of Emulgen 905 (a surfactant manufactured by Kao Corporation) were charged and heated to 80 ° C. 80 g of styrene and 300 of methyl methacrylate
g, Cydapps PM-4CMS (Nippon Chemical Industry Co., Ltd.)
267 g, dimethyl 2,2'-azobis (isobutyrate)
(V-601, polymerization initiator manufactured by Wako Pure Chemical Industries, Ltd.) 8 g
Was added dropwise over 2 hours. After stirring for 8 hours, 0.5 g of V-601 was added and further stirred for 8 hours to obtain a solution of an acrylic polymer having a dry solid content ratio of 50% and a number average molecular weight of 20,000. Water was added dropwise to 100 g of the acrylic polymer solution while 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. After further adding 150 g of water, the resulting dispersion was heated to 40 ° C., and the organic solvent and excess water were removed under reduced pressure to obtain a dry solid content ratio of 33.7% and an average particle size of 0.05 μm. Aqueous dispersion of acrylic polymer fine particles was obtained. Here, the dry solid content ratio 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 weight ratio. The number average molecular weight was measured by GPC and indicated as a molecular weight in terms of polystyrene.

Comparative Fine Particles 2 [Core-shell type polymer fine particles having no cationic group] The aqueous dispersion of core / shell fine particles (A) of the epoxy / acrylic resin obtained in the course of Preparation Example 2 of fine particles was used as comparative fine particles 2 did. In this aqueous dispersion, the resin was finely dispersed and became milky white. Even after standing for 3 months, the resin was not aggregated or precipitated, and the dispersion system was stable. This dispersion has a non-volatile content of 2
At 3%, n-butanol was not detected as a result of gas chromatography. The average particle size of the fine particles is 0.17μ
m.

Production Example of Support: 99.5% or more of aluminum, 0.30% of Fe,
Si 0.10%, Ti 0.02%, Cu 0.013%
The molten metal of JIS A1050 alloy containing Ni was cleaned and cast. In the cleaning treatment, a degassing treatment was performed to remove unnecessary gas such as hydrogen in the molten metal, and a ceramic tube filter treatment was performed. The casting was performed by DC casting. A solidified ingot with a thickness of 500 mm
A 0 mm face was ground, and a homogenization treatment was performed at 550 ° C. for 10 hours so that the intermetallic compound was not coarsened. Then
After hot rolling at 400 ° C. and intermediate annealing at 500 ° C. for 60 seconds in a continuous annealing furnace, cold rolling was performed to obtain a sheet pressure of 0.30 mm.
Aluminum rolled plate. The center line average surface roughness Ra after cold rolling is controlled by controlling the roughness of the rolling roll.
Was controlled to 0.2 μm. Then, it was subjected to a tension leveler to improve the flatness. Next, a surface treatment for forming a lithographic printing plate support was performed. First, in order to remove the rolling oil on the surface of the aluminum plate, a degreasing treatment was performed with a 10% aqueous sodium aluminate solution at 50 ° C. for 30 seconds, and a 30% sulfuric acid aqueous solution was neutralized at 50 ° C. for 30 seconds, and a smut removal treatment was performed. Next, a so-called graining treatment for improving the adhesion between the support and the image forming layer and roughening the surface of the support was performed. While maintaining an aqueous solution containing 1% nitric acid and 0.5% aluminum nitrate at 45 ° C. and flowing an aluminum web into the aqueous solution, an alternating waveform having a current density of 20 A / dm ² and a duty ratio of 1: 1 by an indirect power supply cell. And the amount of electricity on the anode side is 24
Electrolytic graining was performed by giving 0 C / dm ² . Thereafter, an etching treatment is performed with a 10% aqueous sodium aluminate solution at 50 ° C. for 30 seconds, and with a 30% aqueous sulfuric acid solution at 50 ° C. for 30 seconds.
Neutralization and smut removal treatment were performed for seconds. Further, an oxide film was formed on the support by anodic oxidation. A 20% aqueous solution of sulfuric acid was used as the electrolyte at 35 ° C., and the aluminum web was passed through the electrolyte while the 14 A / dm 2 was supplied by the indirect power supply cell.
A support having an anodic oxide film of 2.5 g / m ² was produced by performing the electrolytic treatment with a direct current of ² . The surface roughness Ra is 0.
It was 25 μm.

Examples 1 to 3 and Comparative Examples 1 and 2 On the anodized aluminum support obtained in the above Production Examples, a coating solution of a heat insulating layer having the following composition was applied and dried at 100 ° C. for 3 minutes to obtain a dry film mass of 1 A heat insulating layer of 0.0 g / m ² was provided.

(Heat Insulating Layer Coating Solution) Butyral Resin BM-S (manufactured by Sekisui Chemical Co., Ltd.) 10% MEK solution 59 g carbon black dispersion (CB # 5765M manufactured by Mikuni Pigment Co., Ltd., solid content 21%) 13 0.5g Methyl ethyl ketone 62.7g

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 Colloidal silica (MA silica manufactured by Nissan Chemical Industries, Ltd., average particle diameter 20 nm, 20% aqueous solution) 4.0 g Fine particles (11% aqueous solution) of preparation example 10.0 g 1.5% aqueous solution of photothermal conversion agent (IR-1 described in this specification) 10.0 g 5 g ion-exchanged water

Here, the fine particles of the production examples were used in each example 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 original plate for printing prepared in this manner was output by a Creo Trendsetter 3244VFS equipped with a water-cooled 40 W infrared semiconductor laser at an output of 12 W, an outer drum rotation speed of 94 rpm, and a plate surface energy of 300 mJ / cm.
^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 printing durability. The printing durability evaluation was completed at 20,000 sheets. Printing durability: 100% dot area ratio
The evaluation was made based on the ink density of each portion, and small dots were visually evaluated for 175 LPI halftone dots on the printed matter at the time of printing 20,000 sheets, and represented by the minimum halftone dot area ratio reproduced. A printing durability of 20,000 sheets or more (> 2) in Table 1 indicates that there was still room for 20,000 sheets.

[0147]

[Table 1]

[0148]

According to the present invention, there is provided a lithographic printing original plate which can be printed without being subjected to a developing process after exposure, and which has improved printing durability and good stain resistance. We can provide a master plate.

 ──────────────────────────────────────────────────の Continued on the front page F term (reference) 2H025 AA00 AA12 AB03 AC08 AD01 AD03 BH03 CB32 CC20 FA10 2H096 AA00 AA07 AA08 BA16 BA20 EA04 2H114 AA04 AA14 AA22 AA24 BA01 BA10 DA47 DA52 DA55 DA59 DA60 DA75 FA16EA02

Claims (3)

[Claims] 1. A lithographic printing original plate having a hydrophilic layer which becomes hydrophobic by heat, comprising a support, a hydrophobizing precursor, a photothermal conversion agent, and a three-dimensionally cross-linked hydrophilic binder. An original plate for lithographic printing, wherein the hydrophobizing precursor is fine particles having a core-shell structure containing a lipophilic resin in a core portion and a resin having a cationic substituent in a shell portion. 2. The lithographic printing plate according to claim 1, wherein the cationic substituent is an ammonium group or a phosphonium group. 3. The lipophilic resin of the core part is an acrylic resin,
3. The lithographic printing plate according to claim 1, wherein the lithographic printing plate is at least one resin selected from styrene resin, vinyl ester resin, epoxy resin, urethane resin, phenol resin, and derivatives thereof. .