JP2006088582A - Original lithographic printing plate and lithographic printing method using the original plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an original lithographic printing plate which allows the formation of a successfully visible color image and a lithographic printing method using the original plate. <P>SOLUTION: This original lithographic printing plate has a photosensitive/heat-sensitive layer which enables the recording of an image by laser exposure, formed on a support, and is characterized in that a layer containing a polymer compound which discolors by a heat effect. The lithographic printing method is to print an image by mounting the original lithographic printing plate on a printing machine without passing through a development process after the recording of an image on the plate by laser exposure or recording an image after the mounting of the plate on the printing machine. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a lithographic printing plate precursor and a lithographic printing method using the same. Specifically, the present invention relates to a lithographic printing plate precursor capable of forming a color image with good visibility.

In general, a lithographic printing plate is composed of an oleophilic image portion that receives ink in the printing process and a hydrophilic non-image portion that receives dampening water. Conventional lithographic printing plates are made by exposing a non-image area to a PS plate having a lipophilic photosensitive resin layer on a hydrophilic support through a lith film and then dissolving and removing the non-image area with a developer. It was normal to do.
In recent years, computers electronically process, store, and output images as digital information. Therefore, the image forming process according to the digital image information is to directly form an image on the lithographic printing plate precursor without using a lith film by scanning exposure using a highly directional active radiation such as laser light. Is desirable. A technique for making a printing plate from digital image information without using a lith film is called computer-to-plate (CTP).
If the conventional plate-making method using a PS plate is to be carried out by computer-to-plate (CTP) technology, there is a problem that the wavelength region of the laser beam does not match the photosensitive wavelength region of the photosensitive resin.

Further, in the conventional PS plate, a step (development process) for dissolving and removing the non-image portion after exposure is indispensable. Furthermore, a post-processing step of washing the developed printing plate with water, treating it with a rinsing liquid containing a surfactant, or treating with a desensitizing liquid containing gum arabic or starch derivatives is also necessary. The point that these additional wet treatments are indispensable is a big problem for the conventional PS plate. Even if the first half (image forming process) of the plate making process is simplified by the digital processing, the effect of the simplification is insufficient in the wet process where the second half (development process) is complicated.
Particularly in recent years, consideration for the global environment has become a major concern for the entire industry. In consideration of the environment, it is desirable to simplify the wet post-treatment or change to a dry treatment.

Therefore, one way to eliminate the processing process is to remove the non-image area of the printing original plate by mounting the exposed printing original plate on the cylinder of the printing press and supplying dampening water and ink while rotating the cylinder. There is a method called on-press development. That is, after the printing original plate is exposed, it is mounted on a printing machine as it is, and the processing is completed in a normal printing process.
A lithographic printing plate precursor suitable for such on-press development has a photosensitive layer soluble in dampening water or an ink solvent, and is suitable for development on a printing press placed in a bright room. It is necessary to have light room handling.
In the conventional PS plate, it is practically impossible to satisfy such a requirement.

Therefore, in order to satisfy such requirements, a lithographic printing plate precursor in which a photosensitive layer in which thermoplastic hydrophobic polymer fine particles are dispersed in a hydrophilic binder polymer is provided on a hydrophilic support has been proposed ( For example, see Patent Document 1). In making the plate, it is exposed with an infrared laser, and the thermoplastic hydrophobic polymer fine particles are coalesced (fused) with heat generated by photothermal conversion to form an image. On-press development can be performed by supplying at least one of water and ink. This lithographic printing plate precursor also has handleability in a bright room because the photosensitive region is an infrared region.
However, an image formed by coalescence (fusion) of thermoplastic hydrophobic polymer fine particles has insufficient strength and has a problem in printing durability as a printing plate.

In addition, a lithographic printing plate precursor including microcapsules encapsulating a polymerizable compound in place of the thermoplastic fine particles has been proposed (see, for example, Patent Documents 2 to 7). The original plate according to such a proposal has an advantage that the polymer image formed by the reaction of the polymerizable compound is superior in strength to the image formed by fusing fine particles.
In addition, since a polymerizable compound has high reactivity, many methods for isolating it using microcapsules have been proposed (see, for example, Patent Documents 2 to 7). It has been proposed to use a thermally decomposable polymer for the shell of the microcapsule.

Japanese Patent No. 2938397 JP 2000-2111262 A JP 2001-277740 A JP 2002-29162 A JP 2002-46361 A JP 2002-137562 A JP 2002-326470 A

However, in the conventional lithographic printing plate precursors described in Patent Documents 2 to 7, it is difficult to confirm (plate inspection) an image formed by laser exposure on the printing plate. For this reason, there is a possibility that a problem arises in that it is not possible to determine whether the printing plate is upside down on the printing machine or whether the image is shifted until printing is performed. For this reason, it is desired to further improve the visibility.
A color image forming material for plate inspection usually comprises a low-molecular discoloration compound or a low-molecular discoloration aid. However, when these compounds are added to the printing plate image forming overcoat layer, they are low molecular weight compounds, so that there is a problem that the oxygen blocking ability is lowered and the printing durability is deteriorated. The present invention is for solving the above-mentioned problems.
Accordingly, an object of the present invention is to provide a lithographic printing plate precursor capable of forming a color image with good visibility.

That is, the present invention is as follows.
(1) A lithographic printing plate precursor having a photosensitive-thermosensitive layer capable of recording an image by laser exposure on a support, and a polymer compound that changes color by the action of heat or light on the photosensitive-thermosensitive layer. A lithographic printing plate precursor comprising a layer containing the lithographic printing plate precursor.
(2) The polymer compound that changes color by the action of heat or light is (a1) a polymer compound having a unit that imparts a heat or photochromic function to the polymer compound. Lithographic printing plate precursor.
(3) The lithographic printing plate precursor as described in (1) or (2), wherein the photosensitive-thermosensitive layer contains (D) a radical polymerizable compound and (E) a radical polymerization initiator.
(4) The lithographic printing plate precursor as described in any one of (1) to (3), wherein the polymer compound that changes color by the action of heat or light is a water-soluble polymer compound.
(5) The lithographic printing plate precursor is a lithographic printing plate precursor that can be printed by mounting it in a printing machine without passing through a development step after image recording by laser exposure, or by recording an image after mounting the printing machine. The lithographic printing plate precursor as described in any one of (1) to (4), wherein
(6) The lithographic printing plate precursor according to any one of (1) to (4) is mounted on a printing machine without passing through a development processing step after image recording by laser exposure, or image recording is performed after mounting the printing machine. A lithographic printing method for printing.

  An embodiment of the present invention is a lithographic printing plate precursor having a photosensitive-thermosensitive layer capable of recording an image by laser exposure on a support, and discolors on the photosensitive-thermosensitive layer by the action of heat or light. A lithographic printing plate precursor comprising a layer containing a polymer compound (hereinafter sometimes referred to as an upper layer of a photosensitive-thermosensitive layer or an overcoat layer).

[Layer containing a polymer compound that changes color by the action of heat or light]
<Polymer compound that changes color by the action of heat or light>
The polymer compound that changes color by the action of heat or light used in the present invention means heating by a heating device such as a thermal head, heating by a photothermal conversion process such as infrared laser exposure, or ultraviolet rays, visible rays, or infrared rays. It is a polymer compound that changes color when exposed to an oscillating laser. The discoloration of the polymer compound may be caused by the polymer compound alone or may be caused by the interaction with a decomposed product of the compound that is decomposed by the action of heat or light. In the present invention, any polymer compound as described above can be suitably used. However, a preferred polymer compound has a unit that imparts a thermal or photochromic function to the polymer compound (a1). It is a polymer compound.

  The unit (a1) that imparts a thermal or photochromic function to the polymer compound that is preferably used for the polymer compound that changes color by the action of heat or light used in the present invention is preferably the following general formula (A1) ).

In the formula, R _{1 to} R ₃ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom. L represents a divalent linking group selected from the group consisting of -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aromatic group, and combinations thereof.

Specific examples of L composed of combinations are given below. In the following examples, the left side is bonded to the main chain, and the right side is bonded to X.
L1: -CO-NH-divalent aliphatic group -O-CO-
L2: —CO—divalent aliphatic group —O—CO—
L3: -CO-O-divalent aliphatic group -O-CO-
L4: -Divalent aliphatic group -O-CO-
L5: -CO-NH-divalent aromatic group -O-CO-
L6: -CO-divalent aromatic group -O-CO-
L7: -Divalent aromatic group -O-CO-
L8: -CO-divalent aliphatic group-CO-O-divalent aliphatic group-O-CO-
L9: -CO-divalent aliphatic group-O-CO-divalent aliphatic group-O-CO-
L10: -CO-Divalent aromatic group -CO-O-Divalent aliphatic group -O-CO-
L11: -CO-Divalent aromatic group -O-CO-Divalent aliphatic group -O-CO-
L12: -CO-divalent aliphatic group-CO-O-divalent aromatic group-O-CO-
L13: -CO-Divalent aliphatic group -O-CO-Divalent aromatic group -O-CO-
L14: -CO-divalent aromatic group-CO-O-divalent aromatic group-O-CO-
L15: -CO-Divalent aromatic group -O-CO-Divalent aromatic group -O-CO-

The divalent aliphatic group means an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group or a polyalkyleneoxy group. Of these, an alkylene group, a substituted alkylene group, an alkenylene group, and a substituted alkenylene group are preferable, and an alkylene group and a substituted alkylene group are more preferable.
The divalent aliphatic group is preferably a chain structure rather than a cyclic structure, and more preferably a linear structure than a branched chain structure.
The number of carbon atoms in the divalent aliphatic group is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 12, and further preferably 1 to 10. It is preferably 1 to 8, and most preferably.
Examples of the substituent of the divalent aliphatic group include a halogen atom (F, Cl, Br, I), a hydroxyl group, a carboxyl group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, and an acyl group. , Alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, monoalkylamino group, dialkylamino group, arylamino group and diarylamino group.

The divalent aromatic group means an aryl group or a substituted aryl group. Preferable are phenylene, substituted phenylene group, naphthylene and substituted naphthylene group.
Examples of the substituent for the divalent aromatic group include an alkyl group in addition to the examples of the substituent for the divalent aliphatic group.

  X is a functional group whose absorption property to light in the visible region is changed by the action of heat or light, or by interacting with a compound generated from another molecule by heat or light. Such a functional group is preferably a functional group derived from a dye or a dye precursor. Although the specific example of a pigment | dye or a pigment | dye precursor is shown below, this invention is not limited to these.

Leuco crystal violet, leuco opal blue, leuco berberine blue I, leuco malachite green, leuco triarylmethane compounds such as leuco rosaniline, 3,6-bis (dimethylamino) -9- (p-dimethylaminophenyl) xanthene, etc. Leuco xanthene compounds such as leuco xanthene compounds and 3,6-bis (dimethylamino) -9- (p-dimethylaminophenyl) thioxanthene;
Triarylmethanelactone (phthalide) compounds such as crystal violet lactone, phenolphthalein, o-cresolphthalein, bromophenol blue, bromocresol purple, chlorophenol red, bromocresol green, bromothymol blue, phenol red, cresol red, Triarylmethane sultone compounds such as xylenol blue and thymol blue, triarylcarbinol compounds such as alkali blue 6B, pentamethoxy red, malachite green carbinol hydrochloride, bisarylmethane compounds such as auramine base, crystal violet, malachite Triarylmethane compounds such as green, ethyl violet, victoria pure blue, brilliant green, fluoresce , Eosin B, rose bengal lactone, rhodamine B base, pyrogallol red, fluorane compound such as 3-diethylamino-6-methyl-7-anilinofluorane, thiazine compound such as methylene violet, methylene blue, toluidine blue O, 1, 3,3-trimethylindolinobenzopyrospirane, 1,3,3-trimethylindolino-8′-methoxybenzopyrrirospirane, 1,3,3-trimethylindolino-6′-nitrobenzopyrospirane, Spiro compounds such as 1,3,3-trimethylindolinonaphthospiroxazine, 1,3,3-trimethylindolino-8′-piperidinonaphthospiroxazine, methyl yellow, methyl orange, Congo red, methyl red, alizarin Azo compounds such as yellow Over Tsentralnyi Red, indocyanine B, azine compounds such as aniline black, oxazine compounds such as Nile blue;
STAINS-ALL, sulfopropylsulfopropyl-naphthothiazoylidenemethylbutynylnaphthothiazole, 3,3′-diethyloxacarbocyanine iodide, 2- {4- (dimethylamino) styryl} -1 -Cyanine dyes such as methylquinarinium iodide, quinalidine red, thiazole orange, new indocyanine green, 3,3'-diethylthiocarbocyanine iodide;
In addition, an ethylidene succinic acid derivative (fulgide compound), a diarylethene compound, an oxonol compound, and the like can be given.

  Specific examples of (a1) are described below, but the present invention is not limited thereto.

The unit represented by (a1) may be present in any form in the polymer compound, but it is preferably present as a repeating unit.
The content of the unit represented by (a1) in the polymer compound that changes color by the action of heat or light is preferably 3 mol% or more, and more preferably 5 mol% or more. By setting it as this content rate or more, favorable visible image formability is obtained.

  The polymer compound that changes color by the action of heat or light used in the present invention may be composed of the unit represented by (a1) alone or may be composed of other units. Examples of such other units include a unit represented by (a2) having a hydrophilic functional group in the side chain. By containing such a unit, a polymer compound that changes color by the action of heat or light can be used as a water-soluble polymer compound. By using a water-soluble polymer compound, non-image area removal is facilitated during development, particularly on-press development. Further, when preparing a printing plate, water can be used as a coating solvent for coating on the light-sensitive layer.

  The unit represented by (a2) is preferably represented by the following formula (A2).

In formula, R < ₁ > -R < ₃ > and L are synonymous with what is represented by said Formula (A1). W represents the following group.

However, M ₁ is a hydrogen atom, a metal atom or an ammonium group.
R ₇ and R ₈ each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms.
R ₉ represents a linear or branched alkylene group having 1 to 6 carbon atoms.
R ₁₀ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
n represents an integer of 1 to 100.

  When the unit represented by (a2) is contained in a polymer compound that changes color by the action of heat or light, the content is preferably 10 mol% or more, and more preferably 15 mol% or more. When the content is 10 mol% or more, the on-press developability is improved and the contamination of the printing press is reduced. In addition, as an upper limit, 97 mol% or less is preferable and 95 mol% or less is more preferable.

  Other units that can be used in the polymer compound that changes color by the action of heat or light used in the present invention include (a3) acrylic acid esters, methacrylic acid esters, N, N-2 substituted acrylamides, Examples thereof include units derived from radically polymerizable compounds selected from N, N-2 substituted methacrylamides, styrenes, acrylonitriles, methacrylonitriles and the like.

  Specific examples of the radical polymerizable compound include acrylic acid esters such as alkyl acrylate (the alkyl group preferably has 1 to 20 carbon atoms) (specifically, for example, acrylic acid). Methyl, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, ethyl hexyl acrylate, octyl acrylate, tert-octyl acrylate, chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl Acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.) Methacrylates (eg, phenyl acrylate) and alkyl methacrylates (preferably those having 1 to 20 carbon atoms in the alkyl group) (eg, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate) , Hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, Pentaerythritol monomethacrylate, glycidyl methacrylate, furfurylme Acrylate, tetrahydrofurfuryl methacrylate, etc.), aryl methacrylate (eg, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.), styrene such as styrene, alkyl styrene (eg, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene) , Isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, etc.), alkoxy styrene (eg methoxy styrene, 4-methoxy-3) -Methylstyrene, dimethoxystyrene, etc.), halogen styrene (eg chlorostyrene, Dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, prom styrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3- Trifluoromethylstyrene, etc.), acrylonitrile, methacrylonitrile and the like. Of these radical polymerizable compounds, acrylic acid esters, methacrylic acid esters, and styrenes are preferably used. These can be used alone or in combination of two or more.

  The content of the unit represented by (a3) in the polymer compound that changes color by the action of heat or light is preferably 0 to 95 mol%, particularly preferably 20 to 90 mol%.

  The molecular weight of the polymer compound that changes color by the action of heat or light of the present invention is preferably in the range of 500 to 1,000,000, more preferably in the range of 1,000 to 500,000 in terms of mass average molecular weight.

  The content of the polymer compound that changes color by the action of heat or light of the present invention in the upper layer of the photosensitive-thermosensitive layer is preferably 20% by mass to 99% by mass, and more preferably 30% by mass to 95% by mass.

  Specific examples of the polymer compound that changes color by the action of heat or light used in the present invention are described below, but the present invention is not limited thereto.

  In the lithographic printing plate precursor according to the invention, the layer containing the polymer compound may contain a substance that assists the discoloration of the polymer compound in addition to the polymer compound. Examples of such substances include (1) a radical polymerization initiator, (2) an acid generator and, if necessary, an acid proliferating agent, and (3) a base generator and, if necessary, a base proliferating agent.

<Radical polymerization initiator>
The radical polymerization initiator used in the present invention is a compound that generates radicals by light, heat, or both, and initiates and accelerates polymerization of a compound having a polymerizable unsaturated group. As the radical polymerization initiator that can be used in the present invention, a known thermal polymerization initiator, a compound having a bond having a small bond dissociation energy, a photopolymerization initiator, and a known photooxidizer or bake-out agent are known. A radical generator can be mentioned. Among these, the radical polymerization initiator suitably used in the present invention is a compound that generates radicals by thermal energy.
Hereinafter, although the radical polymerization initiator used by this invention is demonstrated more concretely, this radical polymerization initiator can be used individually or in combination of 2 or more types.

  Examples of such radical polymerization initiators include organic halogen compounds, carbonyl compounds, organic peroxides, azo compounds, azide compounds, metallocene compounds, hexaarylbiimidazole compounds, organic boron compounds, disulfone compounds, and oxime ester compounds. And onium salt compounds.

  Specific examples of the organic halogen compound include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605, JP 48-36281, JP 53-133428, JP 55-3070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62- 58241, JP-A 62-212401, JP-A 63-70243, JP-A 63-298339, P. Examples thereof include compounds described in Hutt "Journal of Heterocyclic Chemistry" 1 (No 3), (1970) ". Of these, oxazole compounds and S-triazine compounds substituted with a trihalomethyl group are preferred.

  More preferably, an s-triazine derivative having at least one mono, di, or trihalogen-substituted methyl group bonded to the s-triazine ring, specifically, for example, 2,4,6-tris (monochloromethyl)- s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl)- s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, -(3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- [1 -(P-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- ( p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p -Tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-natoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2-pheni Thio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6-bis (tribromomethyl) -S-triazine and the like.

Examples of the carbonyl compound include benzophenone, Michler ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone and other benzophenone derivatives, 2,2-dimethoxy- 2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1- Hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) Acetophenone derivatives such as ketones, thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, p- Examples thereof include benzoic acid ester derivatives such as ethyl dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

  As the azo compound, for example, an azo compound described in JP-A-8-108621 can be used.

  Examples of the organic peroxide include trimethylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butyl). Peroxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydro Peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2, -Oxanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate , Dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, tert- Butyl peroxyoctanoate, tert-butyl peroxylaurate, tersyl carbonate, 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4 ′ − Tra- (t-hexylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate), carbonyl And di (t-hexylperoxydihydrogen diphthalate).

  Examples of the metallocene compound include JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, JP-A-2-4705, Various titanocene compounds described in JP-A-5-83588, such as di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, Di-cyclopentadienyl-Ti-bis-2,4-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl, di- -Cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-penta Fluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4,6-trifluoropheny -1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4 , 5,6-pentafluorophen-1-yl, iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109, and the like.

Examples of the hexaarylbiimidazole compound include those described in Japanese Patent Publication No. 6-29285, US Pat. Nos. 3,479,185, 4,311,783, and 4,622,286. And the like, specifically, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-
Bromophenyl)) 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2, 2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5 , 5′-tetraphenylbiimidazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl)- Examples include 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

  Examples of the organoboron compound include JP-A-62-143044, JP-A-62-1050242, JP-A-9-188585, JP-A-9-188686, JP-A-9-188710, JP-A 2000-. 131837, JP-A-2002-107916, JP-A-2766769, JP-A-2002-116539, and Kunz, Martin "Rad Tech'98. Proceeding April 19-22, 1998, Chicago", etc. Organoboron salts described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561, and organic boron oxosulfonium complexes, No. 175554, JP-A-6-175553 The organoboron iodonium complex described in JP-A-9-188710, the organoboron phosphonium complex described in JP-A-9-188710, JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP Examples thereof include organoboron transition metal coordination complexes such as 7-306527 and JP-A-7-292014.

  Examples of the disulfone compound include compounds described in JP-A Nos. 61-166544 and 2002-328465.

  Examples of the oxime ester compound include JCS Perkin II (1979) 1653-1660), JCSPerkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, and JP-A 2000-66385. Compounds, compounds described in JP-A No. 2000-80068, specifically, compounds represented by the following structural formulas may be mentioned.

  Examples of the onium salt compound include S.I. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), T.A. S. Diazonium salts described in Bal et al, Polymer, 21, 423 (1980), ammonium salts described in US Pat. No. 4,069,055, JP-A-4-365049, etc., US Pat. No. 4,069 , 055, 4,069,056, phosphonium salts described in European Patent Nos. 104,143, U.S. Pat. Nos. 339,049, 410,201, The iodonium salts described in the publications of Kaihei 2-150848 and JP-A-2-296514, European Patents 370,693, 390,214, 233,567, 297,443, No. 297,442, U.S. Pat. Nos. 4,933,377, 161,811, 410,201, 339,049, 4,760,0 No. 13, No. 4,734,444, No. 2,833,827, German Patent No. 2,904,626, No. 3,604,580, No. 3,604,581 A sulfonium salt described in each specification; V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello et al, J.A. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), a selenonium salt described in C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and onium salts such as arsonium salts.

  Particularly preferred from the standpoint of reactivity and stability are the oxime ester compounds or onium salts (diazonium salts, iodonium salts or sulfonium salts).

The onium salts suitably used in the present invention are represented by the following general formulas (RI-I) to (RI-III)
It is an onium salt represented by.

In the formula (RI-I), Ar ₁₁ represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferred substituents include an alkyl group having 1 to 12 carbon atoms and a carbon number. 1-12 alkenyl group, C1-C12 alkynyl group, C1-C12 aryl group, C1-C12 alkoxy group, C1-C12 aryloxy group, halogen atom, C1-C1 12 alkylamino groups, C1-C12 dialkylamino groups, C1-C12 alkylamide groups or arylamide groups, carbonyl groups, carboxyl groups, cyano groups, sulfonyl groups, C1-C12 thioalkyl groups And a thioaryl group having 1 to 12 carbon atoms. Z ₁₁ ^- represents a monovalent anion, specifically a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, a sulfate ion Can be mentioned. Among these, from the viewpoint of stability, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion and sulfinate ion are preferable.

In the formula (RI-II), Ar ₂₁ and Ar ₂₂ each independently represent an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferred substituents include 1 to 1 carbon atoms. 12 alkyl groups, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, Halogen atom, C1-C12 alkylamino group, C1-C12 dialkylamino group, C1-C12 alkylamide group or arylamide group, carbonyl group, carboxyl group, cyano group, sulfonyl group, carbon Examples thereof include a thioalkyl group having 1 to 12 carbon atoms and a thioaryl group having 1 to 12 carbon atoms. Z ₂₁ ^- represents a monovalent anion, a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, stability, From the viewpoint of reactivity, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, and carboxylate ion are preferable.

In the formula (RI-III), R ₃₁ , R ₃₂ and R ₃₃ are each independently an aryl group having a carbon number of 20 or less, an alkyl group, an alkenyl group or an alkynyl group which may have 1 to 6 substituents. Represents. Among them, an aryl group is preferable from the viewpoint of reactivity and stability. Examples of the substituent include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, Aryloxy group having 1 to 12 carbon atoms, halogen atom, alkylamino group having 1 to 12 carbon atoms, dialkylamino group having 1 to 12 carbon atoms, alkylamide group or arylamide group having 1 to 12 carbon atoms, carbonyl group, carboxyl Group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z ₃₁ ^- represents a monovalent anion. Specific examples include halogen ions, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, thiosulfonate ions, and sulfate ions. Among these, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, and carboxylate ion are preferable from the viewpoints of stability and reactivity. More preferred are the carboxylate ions described in JP-A No. 2001-343742, and particularly preferred are the carboxylate ions described in JP-A No. 2002-148790.
Specific examples of the onium salts represented by the above formulas (RI-I) to (RI-III) are shown below, but the present invention is not limited thereto.

  These radical polymerization initiators are 0.1 to 100% by mass, preferably 1 to 90% by mass, and particularly preferably 5 to 80% by mass with respect to the polymer compound that changes color by the action of heat or light. Can be added. Within this range, the printing durability is further improved. These radical polymerization initiators may be used alone or in combination of two or more.

<Acid generator>
The acid generator used in the present invention is a compound that generates an acid by light or heat, and examples thereof include compounds described in [0039] to [0063] of JP-A-10-282644. .

  Specifically, the diazonium salts described in SI Schlesinger, Photogr. Sci. Eng., 18, 387 (1974), TS Bal et al, Polymer, 21, 423 (1980), etc., US Pat. No. 4,069,055 No. 4,069,056, JP-A-3-140,140, etc., ammonium salts, DC Necker et al, Macromolecules, 17, 2468 (1984), CS Wen et al, Teh , Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat. Nos. 4,069,055, 4,069,056, etc., JV Crivello et al , Macromolecules, 10 (6), 1307 (1977), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent No. 104,143, US Pat. No. 339,049, No. 410,201, JP-A-2-150,848, JP-A-2-296,514, etc., iodonium salts, JV Crivello et al, Polymer J. 17, 73 (1985), JV Crivello et al. J. Org. Chem., 43, 3055 (1978), WR Watt et al, J. Polymer Sci., Polymer Chem. Ed., 22, 1789 ( 1984), JV Crivello et al, Polymer Bull., 14, 279 (1985), JV Crivello et al, Macromolecules, 14 (5), 1141 (1981), JV Crivello et al, J. Polymer Sci., Polymer Chem. Ed., 17, 2877 (1979), European Patent 370,693, US Pat. No. 3,902,114, European Patent 233,567, 297,443, No. 297,442, U.S. Pat.Nos. 4,933,377, 410,201, 339,049, 4,760,013, 4,734, No. 444, No. 2,833,827, Yasukuni Patent No. 2,904,626, No. 3,604,580, No. 3,604,581, etc. Sulphonium salts described, Selenonium described in JV Crivello et al, Macromolecules, 10 (6), 1307 (1977), JV Crivello et al, J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979), etc. Salt, onium salts such as arsonium salts described in CS Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), US Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605, JP-A 48-36281, JP-A 55-32070, JP-A 60-239736, JP-A 61-169835, JP-A 61-169837 Organic halogen compounds described in JP-A-62-258241, JP-A-62-212401, JP-A-63-70243, JP-A-63-298339, etc., K. Meier et al, J. Rad. Curing, 13 (4), 26 (1986), TP Gill et al, Inorg. Chem., 19, 3007 (19 80), D. Astruc, Acc. Chem. Res., 19 (12), 377 (1896), JP-A-2-161445, and the like, S. Hayase et al, J. Polymer Sci., 25, 753 (1987), E. Reichmanis et al, J. Pholymer Sci., Polymer Chem. Ed., 23, 1 (1985), QQ Zhu et al, J. Photochem., 36, 85, 39, 317 (1987), B. Amit et al, Tetrahedron Lett., (24) 2205 (1973), DHR Barton et al, J. Chem Soc., 3571 (1965), PM Collins et al, J. Chem. Soc., Perkin I, 1695 (1975), M. Rudinstein et al, Tetrahedron Lett., (17), 1445 (1975), JW Walker et al, J. Am. Chem. Soc., 110, 7170 (1988) SC Busman et al, J. Imaging Technol., 11 (4), 191 (1985), HM Houlihan et al, Macormolecules, 21, 2001 (1988), PM Collins et al, J. Chem. Soc., Chem. Commun., 532 (1972), S. Hayaseetal, Macromolecules, 18, 1799 (1985), E. Reichmanis et al, J. Electrochem. Soc., Solid State Sci. Technol., 130 (6), FM Houlihan et al , Macromolcules, 21, 2001 (1988), Europe Patents 0290,750, 046,083, 156,535, 271,851, 0,388,343, U.S. Pat. No. 710, No. 4,181,531, JP-A-60-198538, JP-A-53-133022 and the like, a photoacid generator having an o-nitrobenzyl type protecting group, M. TUNOOKA et al, Polymer Preprints Japan, 35 (8), G. Berner et al, J. Rad. Curing, 13 (4), WJ Mijs et al, Coating Technol., 55 (697), 45 (1983) , Akzo, H. Adachi et al, Polymer Preprints, Japan, 37 (3), European Patent Nos. 0199,672, 84515, 199,672, 044,115. 0101,122, U.S. Pat. No. 4,618,564, 4,371,605 No. 4,431,774, Japanese Patent Application Laid-Open No. 64-18143, Japanese Patent Application Laid-Open No. 2-245756, Japanese Patent Application Laid-Open No. 4-365048, and the like. Compounds that decompose to generate sulfonic acid, disulfone compounds described in JP-A No. 61-166544, etc., o-naphthoquinonediazide-4 described in JP-A No. 50-36209 (US Pat. No. 3,969,118) -Sulphonic acid halides, and o-naphthoquinonediazide compounds described in JP-A-55-62444 (British Patent No. 2038801) or JP-B-1-11935 can be mentioned.

  Examples of other acid generators include sulfonic acid alkyl esters such as cyclohexyl citrate, p-acetaminobenzenesulfonic acid cyclohexyl ester, p-bromobenzenesulfonic acid cyclohexyl ester, and alkylsulfonic acid esters represented by the following structural formula. Can be used.

Of the compounds that generate acid upon decomposition by irradiation with light, heat, or radiation, those that are particularly effective are exemplified below.
(1) An oxazole derivative represented by the following general formula (PAG1) substituted with a trihalomethyl group or an S-triazine derivative represented by the general formula (PAG2).

In the formula, R ¹ represents a substituted or unsubstituted aryl group or alkenyl group, and R ² represents a substituted or unsubstituted aryl group, alkenyl group, alkyl group, or —CY ₃ . Y represents a chlorine atom or a bromine atom. Specific examples include the following compounds, but are not limited thereto.

  (2) An iodonium salt represented by the following general formula (PAG3), a sulfonium salt represented by the general formula (PAG4), or a diazonium salt.

Here, the formulas Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. Preferred substituents include alkyl groups, haloalkyl groups, cycloalkyl groups, aryl groups, alkoxy groups, nitro groups, carboxyl groups, alkoxycarbonyl groups, hydroxy groups, mercapto groups, and halogen atoms.

R ³ , R ⁴ and R ⁵ each independently represents a substituted or unsubstituted alkyl group or aryl group. Preferred are an aryl group having 6 to 14 carbon atoms, an alkyl group having 1 to 8 carbon atoms, and substituted derivatives thereof. Preferred substituents are an aryl group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a nitro group, a carboxyl group, a hydroxy group, and a halogen atom. Is an alkoxy group having 1 to 8 carbon atoms, a carboxyl group, or an alkoxycarbonyl group.
Two of R ³ , R ⁴ and R ⁵ and Ar ¹ and Ar ² may be bonded via a single bond or a substituent.

Z ⁻ represents a counter anion, such as BF ₄ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , SiF ₆ ²⁻ , ClO ₄ ⁻ , CF ₃ SO ₃ ⁻ , C ₄ F ₉ SO ₃ ^{− and the} like. Examples include, but are not limited to, bonded polynuclear aromatic sulfonate anions such as fluoroalkane sulfonate anion, pentafluorobenzene sulfonate anion, naphthalene-1-sulfonate anion, anthraquinone sulfonate anion, and sulfonate group-containing dyes. Is not to be done.

  Specific examples include the following compounds, but are not limited thereto.

  The above onium salts represented by the general formulas (PAG3) and (PAG4) are known, for example, JW Knapczyk etal, J. Am. Chem. Soc., 91, 145 (1969), ALMaycoketal, J. Org. Chem. , 35, 2532, (1970), B. Goethas etal, Bull. Soc. Chem. Belg., 73, 546, (1964), HM Leicester, J. Ame. Chem. Soc., 51, 3587 (1929), JVCrivelloetal, J. Polym. Chem. Ed., 18, 2677 (1980), U.S. Pat. Nos. 2,807,648 and 4,247,473, JP-A-53-101331, etc. It can be synthesized by this method.

  (3) A disulfone derivative represented by the following general formula (PAG5) or an iminosulfonate derivative represented by the general formula (PAG6).

In the formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group. R ⁶ represents a substituted or unsubstituted alkyl group or aryl group. A represents a substituted or unsubstituted alkylene group, alkenylene group, or arylene group.
Specific examples include the following compounds, but are not limited thereto.

  The amount of the acid generator used is usually from 0.1 to 100% by weight, preferably from 1 to 90% by weight, particularly preferably from 5 to 80% by weight, based on the polymer compound that changes color by the action of heat or light. Can be added. Within the above range, sensitivity and image intensity are good.

<Acid multiplication agent>
The acid proliferating agent used in the present invention is a compound that can further generate an acid by an acid-catalyzed reaction to increase the acid concentration in the reaction system, and is a compound that exists stably in the absence of an acid. In such a compound, since one or more acids increase in one reaction, the reaction proceeds at an accelerated rate as the reaction proceeds. However, the generated acid itself induces self-decomposition, and is generated here. The acid strength is preferably 3 or less as an acid dissociation constant, pKa, and particularly preferably 2 or less.
Specific examples of the acid proliferating agent include JP-A-10-1508 [0203] to [0223], JP-A-10-282642 [0016] to [0055] and JP-A-9-512498, page 39. The compounds described on the 12th line to the 47th line on the 2nd line can be mentioned.
The addition amount of the acid proliferating agent is preferably 0.1 to 100% by mass, more preferably 1 to 90% by mass, and particularly preferably 5 to 80% by mass with respect to the polymer compound that changes color by the action of heat or light. It can be added in proportions.

<Base generator>
Examples of the base generator used in the present invention include compounds described in JP-A-2-166450, page 6, upper left column, second row to the same page upper column, right row 15, specifically, Some compounds that release some bases by heating, such as salts of organic acids and bases decarboxylated by heating, compounds that release amines by reactions such as intramolecular nucleophilic substitution, Lossen transfer, Beckmann transfer, etc. Preferably used.
Specific examples include base acid salts. Examples of the base include guanidine, triphenylguanidine, tricyclohexylguanidine, piperidine, morpholine, p-toluidine, 2-picoline, and the acid. Examples thereof include acetic acid, trichloroacetic acid, phenylsulfonylacetic acid, 4-methylsulfonylphenylsulfonylacetic acid, 4-acetylaminomethylpropionic acid, succinic acid, maleic acid, succinic acid, fumaric acid, carbonic acid, and bicarbonate.
These base generators may be dispersed in the form of a solid and introduced into the layer as particulate matter, or may be introduced in a state of being encapsulated in microcapsules described later.
The addition amount of the base generator is preferably 0.1 to 100% by mass with respect to the polymer compound that changes color by the action of heat or light, from the viewpoint of visibility of the exposed portion, and 1 to 90% by mass. Is more preferable.

<Base proliferating agent>
The above-mentioned base proliferating agent used in the present invention has the property of decomposing by the action of a base to generate a base, and decomposing to generate a base when the same base as that generated at this time is allowed to act. Is. Therefore, the base proliferating agent decomposes in a self-propagating manner by allowing a smaller equivalent amount of base to act on the fixed amount, and finally the entire amount decomposes, corresponding to the amount of the base proliferating agent. A large amount of base can be generated. Examples of such a base proliferating agent include compounds described in JP-A 2000-330270 (0010) to (0032).

  The addition amount of the base proliferating agent is preferably 100 to 100000 parts by mass with respect to 100 parts by mass of the base generator, from the viewpoint of visibility of the exposed part, and more preferably 200 to 5000 parts by mass. preferable.

  These additives are preferably added to the layer containing a polymer compound that changes color by the action of heat or light, but may be added to an adjacent layer such as a photosensitive-thermosensitive layer.

  In addition to these compounds, compounds that can be added to the layer containing the polymer compound that changes color by the action of heat or light (photosensitive-thermosensitive layer upper layer) include infrared absorbers, sensitizing dyes, surfactants, polymerization inhibitors, Examples include inorganic fine particles.

<Infrared absorber>
In the present invention, the infrared absorber is a component used to increase sensitivity to an infrared laser. The infrared absorber has a function of converting absorbed infrared rays into heat. The infrared absorber used in the present invention is preferably a dye or pigment having an absorption maximum at a wavelength of 760 to 1200 nm.

  As the dye, commercially available dyes and known dyes described in documents such as “Dye Handbook” (edited by the Society for Synthetic Organic Chemistry, published in 1970) can be used. Specifically, dyes such as azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolate complexes, etc. Is mentioned.

  Examples of preferable dyes include cyanine dyes described in JP-A-58-125246, JP-A-59-84356, JP-A-60-78787, JP-A-58-173696, Methine dyes described in JP-A Nos. 58-181690 and 58-194595, JP-A-58-112793, JP-A-58-224793, JP-A-59-48187, JP-A Naphthoquinone dyes described in JP-A-59-73996, JP-A-60-52940, JP-A-60-63744, etc., squarylium dyes described in JP-A-58-112792, etc., British Patent No. And cyanine dyes described in the specification of 434,875.

In addition, a near infrared absorption sensitizer described in US Pat. No. 5,156,938 is also preferably used, and a substituted arylbenzo (thio) described in US Pat. No. 3,881,924 is also suitable. ) Pyrylium salt, trimethine thiapyrylium salt described in JP-A-57-142645 (US Pat. No. 4,327,169), JP-A-58-181051, 58-220143, 59- No. 41363, 59-84248, 59-84249, 59-146063, 59-146061, pyranyl compounds described in JP-A-59-216146, cyanine dyes described in US It is disclosed in the pentamethine thiopyrylium salt described in Japanese Patent No. 4,283,475, and Japanese Patent Publication Nos. 5-13514 and 5-19702. Pyrylium compounds are also preferably used. Another example of a preferable dye is a near-infrared absorbing dye described in US Pat. No. 4,756,993 as formulas (I) and (II).
Other preferable examples of the infrared absorbing dye include specific indolenine cyanine dyes described in JP-A-2002-278057 as exemplified below.

  Particularly preferred among these dyes are cyanine dyes, squarylium dyes, pyrylium salts, nickel thiolate complexes, and indolenine cyanine dyes. Further, cyanine dyes and indolenine cyanine dyes are preferred, and one particularly preferred example is a cyanine dye represented by the following general formula (I).

In the general formula (I), X ¹ represents a hydrogen atom, a halogen atom, -NPh _2, X ² -L ¹ or a group shown below.

X ² represents an oxygen atom, a nitrogen atom or a sulfur atom, and L ¹ represents a hydrocarbon group having 1 to 12 carbon atoms, an aromatic ring having a hetero atom, or a carbon atom having 1 to 12 carbon atoms including a hetero atom. Indicates a hydrogen group. In addition, a hetero atom here shows N, S, O, a halogen atom, and Se. Xa ^- the Za described later ^- is defined as for, R ^a represents a hydrogen atom, an alkyl group, an aryl group, a substituted or unsubstituted amino group, substituted or unsubstituted amino group and a halogen atom.

R ¹ and R ² each independently represents a hydrocarbon group having 1 to 12 carbon atoms. From the storage stability of the recording layer coating solution, R ¹ and R ² are preferably hydrocarbon groups having 2 or more carbon atoms, and R ¹ and R ² are bonded to each other to form a 5-membered ring or It is particularly preferable that a 6-membered ring is formed.

Ar ¹ and Ar ² may be the same or different and each represents an aromatic hydrocarbon group which may have a substituent. Preferred aromatic hydrocarbon groups include a benzene ring and a naphthalene ring. Moreover, as a preferable substituent, a C12 or less hydrocarbon group, a halogen atom, and a C12 or less alkoxy group are mentioned. Y ¹ and Y ² may be the same or different and each represents a sulfur atom or a dialkylmethylene group having 12 or less carbon atoms. R ³ and R ⁴ may be the same or different and each represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Preferred substituents include alkoxy groups having 12 or less carbon atoms, carboxyl groups, and sulfo groups. R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. From the availability of raw materials, a hydrogen atom is preferred. Za ⁻ represents a counter anion. However, Za ⁻ is not necessary when the cyanine dye represented by formula (I) has an anionic substituent in its structure and neutralization of charge is not necessary. Preferred Za ⁻ is a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, and a sulfonate ion, particularly preferably a perchlorate ion, a hexagonal salt, in view of the storage stability of the recording layer coating solution. Fluorophosphate ion and aryl sulfonate ion.

Specific examples of the cyanine dye represented by formula (I) that can be suitably used in the present invention include those described in paragraph numbers [0017] to [0019] of JP-A No. 2001-133969. be able to.
Further, other particularly preferable examples include specific indolenine cyanine dyes described in JP-A-2002-278057 described above.

  Examples of the pigment used in the present invention include commercially available pigments and color index (CI) manual, “Latest Pigment Handbook” (edited by Japan Pigment Technology Association, published in 1977), “Latest Pigment Application Technology” (CMC Publishing, 1986), “Printing Ink Technology”, CMC Publishing, 1984) can be used.

Examples of the pigment include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and other polymer-bonded dyes. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments In addition, quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like can be used. Among these pigments, carbon black is preferable.

  These pigments may be used without surface treatment, or may be used after surface treatment. The surface treatment method includes a method of surface coating with a resin or wax, a method of attaching a surfactant, a method of bonding a reactive substance (eg, silane coupling agent, epoxy compound, polyisocyanate, etc.) to the pigment surface, etc. Can be considered. The above-mentioned surface treatment methods are described in “Characteristics and Applications of Metal Soap” (Yokoshobo), “Printing Ink Technology” (CMC Publishing, 1984) and “Latest Pigment Application Technology” (CMC Publishing, 1986). Yes.

  The particle diameter of the pigment is preferably in the range of 0.01 to 10 μm, more preferably in the range of 0.05 to 1 μm, and particularly preferably in the range of 0.1 to 1 μm. Within this range, good stability of the pigment dispersion in the light-sensitive layer coating solution and good uniformity of the light-sensitive layer can be obtained.

  As a method for dispersing the pigment, a known dispersion technique used in ink production, toner production, or the like can be used. Examples of the disperser include an ultrasonic disperser, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill, and a pressure kneader. Details are described in "Latest Pigment Applied Technology" (CMC Publishing, 1986).

These infrared absorbers may be added to a layer containing a polymer compound that changes color by the action of heat or light, or may be added to other layers such as a photosensitive-thermosensitive layer. Moreover, it can also be included in a microcapsule and added.
As the addition amount, when a negative lithographic printing plate precursor is prepared, the absorbance at the oscillation wavelength of the laser used for exposure of the surface having the photosensitive-thermosensitive layer of the lithographic printing plate precursor is 0.3 by reflection measurement. It is preferable to add so that it may exist in the range of -1.5, and it is more preferable to add so that it may exist in the range of 0.4-1.1. By being added so as to be in this range, a uniform polymerization reaction in the depth direction of the photosensitive-thermosensitive layer proceeds, good film strength of the image area and adhesion to the support can be obtained, and good Plate inspection can be achieved. The absorbance of the surface of the lithographic printing plate precursor having the photosensitive-thermosensitive layer is determined by the amount of infrared absorber added to the layer containing a polymer compound that changes color by the action of heat or light, the thickness of the layer, and the photosensitive-thermosensitive layer. It can adjust with the quantity of the infrared absorber added to, and the thickness (after-mentioned) of this layer. Absorbance can be measured by a conventional method. As a measuring method, for example, on a reflective support such as aluminum, a photosensitive-thermosensitive layer having a thickness appropriately determined as a lithographic printing plate in a coating amount after drying is formed, and the reflection density is optically measured. Examples thereof include a method of measuring with a densitometer, a method of measuring with a spectrophotometer by a reflection method using an integrating sphere, and the like.

<Sensitizing dye>
Examples of the sensitizing dye used in the present invention include benzoin, benzoin methyl ether, benzoin ethyl ether, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, and 2-bromo-9. -Anthrone, 2-ethyl-9-anthrone, 9,10-anthraquinone, 2-ethyl-9, 10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone , Xanthone, 2-methylxanthone, 2-methoxyxanthone, thioxanthone, benzyl, dibenzalacetone, p- (dimethylamino) phenyl styryl ketone, p- (dimethylamino) phenyl p-methylstyryl ketone, benzophenone, p- ( Dimethylamino) benzophenone ( Others Michler's ketone), p- (diethylamino) benzophenone, and the like benzanthrone.

  Furthermore, preferred sensitizing dyes in the present invention include compounds represented by the general formula (I) described in JP-B 51-48516.

In the formula, R ¹⁴ is an alkyl group (for example, methyl group, ethyl group, propyl group, etc.) or a substituted alkyl group (for example, 2-hydroxyethyl group, 2-methoxyethyl group, carboxymethyl group, 2-carboxyethyl group) Etc.). R ¹⁵ represents an alkyl group (eg, methyl group, ethyl group, etc.) or an aryl group (eg, phenyl group, p-hydroxyphenyl group, naphthyl group, thienyl group, etc.).

Z ² is a group of nonmetallic atoms necessary for forming a heterocyclic nucleus containing nitrogen, which is usually used in cyanine dyes, such as benzothiazoles (benzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, etc.), naphtho Thiazoles (α-naphthothiazole, β-naphthothiazole, etc.), benzoselenazoles (benzoselenazole, 5-chlorobenzoselenazole, 6-methoxybenzoselenazole, etc.), naphthoselenazoles (α-naphthoselenazole) , Β-naphthselenazole, etc.), benzoxazoles (benzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole, etc.) and naphthoxazoles (α-naphthoxazole, β-naphthoxazole, etc.).

Specific examples of the compound represented by the general formula (I) are those having a chemical structure combining these Z ² , R ¹⁴ and R ¹⁵ , and many exist as known substances. Therefore, it can be used by appropriately selecting from these known ones. Furthermore, preferable sensitizing dyes in the present invention include merocyanine dyes described in JP-B-5-47095 and ketocoumarin compounds represented by the following general formula (II).

Here, R ¹⁶ represents an alkyl group such as a methyl group or an ethyl group.

  As the sensitizing dye, merocyanine dyes described in JP-A No. 2000-147763 can also be used. Specifically, the following compounds can be mentioned.

  As the addition amount of the sensitizing dye, the absorbance at the oscillation wavelength of the laser used for the exposure of the surface having the photosensitive-thermosensitive layer of the lithographic printing plate precursor when the negative lithographic printing plate precursor is prepared is a reflection measurement method. It is preferable to add so that it may exist in the range of 0.3-1.5, and it is more preferable to add so that it may exist in the range of 0.4-1.1. By being added so as to be in this range, a uniform polymerization reaction in the depth direction of the photosensitive-thermosensitive layer proceeds, good film strength of the image area and adhesion to the support can be obtained, and good Plate inspection can be achieved.

<Surfactant>
In the present invention, a layer containing a polymer compound that changes color due to the action of heat or light includes, for example, a surfactant in order to promote on-press developability at the start of printing or to improve the coating surface condition. It may be used. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and fluorosurfactants. Surfactant may be used independently and may be used in combination of 2 or more type.

  The nonionic surfactant used for this invention is not specifically limited, A conventionally well-known thing can be used. For example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid partial esters, sorbitan fatty acid partial esters, pentaerythritol Fatty acid partial esters, propylene glycol mono fatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters, polyethylene glycol fatty acid esters, polyglycerin fatty acid partial esters, Polyoxyethylenated castor oil, polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamides, N N- bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid ester, trialkylamine oxide, polyethylene glycol, copolymers of polyethylene glycol and polypropylene glycol.

  The anionic surfactant used in the present invention is not particularly limited, and conventionally known anionic surfactants can be used. For example, fatty acid salts, abietic acid salts, hydroxyalkane sulfonates, alkane sulfonates, dialkyl sulfosuccinate esters, linear alkyl benzene sulfonates, branched alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl phenoxy poly Oxyethylene propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-methyl-N-oleyl taurine sodium salt, N-alkyl sulfosuccinic acid monoamide disodium salt, petroleum sulfonates, sulfated beef oil, fatty acid alkyl esters Sulfates, alkyl sulfates, polyoxyethylene alkyl ether sulfates, fatty acid monoglyceride sulfates, polyoxyethylene alcohols Ruphenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, styrene / maleic anhydride Examples thereof include partial saponification products of polymers, partial saponification products of olefin / maleic anhydride copolymers, and naphthalene sulfonate formalin condensates.

The cationic surfactant used in the present invention is not particularly limited, and conventionally known cationic surfactants can be used. Examples thereof include alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamine salts, and polyethylene polyamine derivatives.
The amphoteric surfactant used in the present invention is not particularly limited, and conventionally known amphoteric surfactants can be used. Examples thereof include carboxybetaines, aminocarboxylic acids, sulfobetaines, aminosulfuric esters, and imidazolines.

  Of the above surfactants, the term “polyoxyethylene” can be read as “polyoxyalkylene” such as polyoxymethylene, polyoxypropylene, polyoxybutylene, etc. These surfactants can also be used.

More preferable surfactants include fluorine-based surfactants containing a perfluoroalkyl group in the molecule. Examples of such fluorosurfactants include anionic types such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and perfluoroalkyl phosphates; amphoteric types such as perfluoroalkyl betaines; Cation type such as trimethylammonium salt; perfluoroalkylamine oxide, perfluoroalkylethylene oxide adduct, oligomer containing perfluoroalkyl group and hydrophilic group, oligomer containing perfluoroalkyl group and lipophilic group, perfluoroalkyl Nonionic types such as an oligomer containing a group, a hydrophilic group and a lipophilic group, and a urethane containing a perfluoroalkyl group and a lipophilic group. Moreover, the fluorine-type surfactant described in each gazette of Unexamined-Japanese-Patent No. 62-170950, 62-226143, and 60-168144 is also mentioned suitably.

Surfactant can be used individually or in combination of 2 or more types.
The content of the surfactant is preferably 0.01 to 10% by mass, and preferably 0.1 to 5% by mass with respect to the total solid content of the layer containing the polymer compound that changes color by the action of heat or light. % Is more preferred.

<Polymerization inhibitor>
A small amount of a thermal polymerization inhibitor is added to the layer containing a polymer compound that changes color by the action of heat or light to prevent unnecessary thermal polymerization of, for example, a radical polymerizable compound during its production or storage. May be.
Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t- (Butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt are preferred.
The addition amount of the thermal polymerization inhibitor is preferably about 0.01 to 10% by mass with respect to the total solid content of the layer containing the polymer compound that changes color by the action of heat or light.

<Inorganic fine particles>
The upper layer of the photosensitive-thermosensitive layer may contain inorganic fine particles in order to improve the on-press developability and the coating strength against scratches.
As the inorganic fine particles, for example, silica, alumina, magnesium oxide, titanium oxide, magnesium carbonate, calcium alginate, or a mixture thereof is preferably exemplified. Even if they are not photothermally convertible, they can be used for strengthening the film, enhancing interfacial adhesion by surface roughening, and the like.
The inorganic fine particles preferably have an average particle size of 5 nm to 10 μm, and more preferably 0.5 to 3 μm. Within the above range, it is possible to stably disperse in the photosensitive-thermosensitive layer, sufficiently maintain the film strength of the photosensitive-thermosensitive layer, and form a non-image portion having excellent hydrophilicity that hardly causes stains during printing. it can.
The inorganic fine particles as described above can be easily obtained as a commercial product such as a colloidal silica dispersion.
The content of the inorganic fine particles is preferably 1 to 50% by mass and preferably 5 to 40% by mass or less based on the total solid content of the layer containing the polymer compound that changes color by the action of heat or light. Is more preferable.

  In the present invention, the layer containing a polymer compound that changes color by the action of heat or light is prepared by, for example, preparing a coating solution by dissolving or dispersing each of the above components in a suitable solvent, and applying the coating solution by an existing method. Formed with. Solvents used here include ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, dimethoxy Examples include ethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, γ-butyrolactone, toluene, water and the like. However, the present invention is not limited to this.

  These solvents are used alone or in combination. The solid content concentration of the coating solution is preferably 1 to 50% by mass. The layer containing the polymer compound can be formed by preparing a plurality of coating solutions in which the same or different components are dispersed or dissolved in the same or different solvents, and repeating the coating and drying a plurality of times.

  The drying temperature after coating may be any temperature as long as the above components are not decomposed, but room temperature to 200 ° C. is preferable. The drying time may be any time as long as 95% or more of the solvent used evaporates at the above-mentioned drying temperature, but is preferably 5 to 300 seconds.

Further, the coating amount (solid content) of the layer containing a polymer compound that changes color by heat on the support obtained after coating and drying varies depending on the use, but generally 0.001 to 3.0 g / m ² is preferable. 0.005-1.0 g / m ² is more preferable. Within this range, good color images and printing performance can be obtained.
Various methods can be used as a coating method. Examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating.

In the present invention, a layer containing a polymer compound that changes color by the action of heat or light is provided on the light-sensitive layer of the lithographic printing plate precursor. As a result, for example, when it is mounted on a printing machine without going through a development processing step, the visibility at the time of plate inspection is good.
The layer containing a polymer compound that changes color by the action of heat or light is a protective layer (overcoat layer) that constitutes the following lithographic printing plate precursor, using itself as a binder polymer and using the above-mentioned additives as necessary. ) Or a protective layer described below may be additionally provided on the layer containing a polymer compound that changes color by the action of heat or light.

  Hereinafter, other components of the lithographic printing plate precursor according to the invention will be described in detail.

[Protective layer (overcoat layer)]
In the lithographic printing plate precursor according to the present invention, a protective layer is formed on the photosensitive-thermosensitive layer as necessary to prevent the occurrence of scratches in the photosensitive-thermosensitive layer, to block oxygen, and to prevent ablation during high-intensity laser exposure. Can be provided.
In the present invention, the exposure is usually carried out in the atmosphere, but the protective layer is composed of low molecular weight compounds such as oxygen and basic substances present in the atmosphere that inhibit the image forming reaction caused by exposure in the light-sensitive layer. Mixing into the photosensitive-thermosensitive layer is prevented, and inhibition of image formation reaction due to exposure in the air is prevented. Therefore, the properties desired for the protective layer are low permeability of low-molecular compounds such as oxygen, furthermore, good transparency of light used for exposure, and excellent adhesion with the photosensitive-thermosensitive layer, And it is preferable that it can be easily removed in the on-press development process after exposure. Various studies have been made on the protective layer having such characteristics, and are described in detail, for example, in US Pat. No. 3,458,311 and JP-A-55-49729.

  As the material used for the protective layer, a polymer compound (binder polymer) is preferably used, and examples thereof include a water-soluble polymer compound having relatively excellent crystallinity. Specific examples include water-soluble polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, acidic celluloses, gelatin, gum arabic, and polyacrylic acid. Among these, when polyvinyl alcohol (PVA) is used as a main component, the best results are obtained for basic characteristics such as oxygen barrier properties and development removability. The polyvinyl alcohol may be partially substituted with an ester, ether or acetal as long as it contains an unsubstituted vinyl alcohol unit for providing the oxygen barrier property and water solubility necessary for the protective layer, and a part of the other You may have a copolymerization component.

  As specific examples of polyvinyl alcohol, those having a hydrolysis degree of 71 to 100 mol% and a polymerization degree of 300 to 2400 are preferably mentioned. Specifically, for example, PVA-105, PVA-110, PVA-117, PVA-117H, PVA-120, PVA-124, PVA-124H, PVA-CS, PVA-CST, PVA manufactured by Kuraray Co., Ltd. -HC, PVA-203, PVA-204, PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-217EE, PVA-217E, PVA-220E, PVA-224E, PVA-405 , PVA-420, PVA-613, and L-8.

The components of the protective layer (selection of PVA, use of additives, etc.), coating amount, etc. are appropriately selected in consideration of fogging properties, adhesion, scratch resistance, etc. in addition to oxygen barrier properties and development removability. In general, the higher the hydrolysis rate of PVA (that is, the higher the content of unsubstituted vinyl alcohol units in the protective layer), the higher the film thickness, the higher the oxygen barrier property, which is preferable in terms of sensitivity. . Further, in order to prevent unnecessary polymerization reaction during production and storage, unnecessary fogging during image exposure, and thickening of image lines, it is preferable that the oxygen permeability is not excessively high. Accordingly, the oxygen permeability A at 25 ° C. and 1 atm is preferably 0.2 ≦ A ≦ 20 (cc / m ² · day).

As another composition of the protective layer, glycerin, dipropylene glycol and the like can be added in an amount corresponding to several mass% with respect to the water-soluble polymer compound, and flexibility can be imparted. Anionic surfactants such as sodium acid salts; amphoteric surfactants such as alkylaminocarboxylates and alkylaminodicarboxylates; nonionic surfactants such as polyoxyethylene alkylphenyl ethers to the (co) polymer Mass% can be added.
The thickness of the protective layer is suitably from 0.1 to 5 μm, particularly preferably from 0.2 to 2 μm.

  In addition, adhesion to the image area, scratch resistance, and the like are extremely important in handling the lithographic printing plate precursor. That is, when a photosensitive protective layer containing a water-soluble polymer compound is hydrophilic and the photosensitive-thermosensitive layer is oleophilic, the protective layer is easily peeled off due to insufficient adhesion. In the peeled portion, defects such as defective film hardening due to polymerization inhibition by oxygen may occur.

  On the other hand, various proposals have been made to improve the adhesion between the photosensitive-thermosensitive layer and the protective layer. For example, in JP-A-49-70702 and British Patent Application No. 1303578, a hydrophilic polymer mainly composed of polyvinyl alcohol, an acrylic emulsion, a water-insoluble vinylpyrrolidone-vinyl acetate copolymer, etc. It is described that sufficient adhesiveness can be obtained by mixing 20 to 60% by mass and laminating on a photosensitive-thermosensitive layer. Any of these known techniques can be used in the present invention. The method for applying the protective layer is described in detail, for example, in US Pat. No. 3,458,311 and JP-A-55-49729.

In the present invention, the above-mentioned print-out image forming component (a compound causing a color change by the action of a radical, a radical polymerization initiator, an infrared absorber, etc.) can be contained in the protective layer. An embodiment in which these print-out image forming components are put in a protective layer instead of a light- and heat-sensitive layer is preferable because the print-out image forming reaction is separated from the polymerization reaction system in the light-and heat-sensitive layer, and the mutual reaction can be avoided. . It is also a preferred embodiment that these print-out image forming components are contained in the protective layer in the form of being encapsulated in microcapsules. When enhancing the printout image, the printout image forming component can be contained in both the protective layer and the light-sensitive layer.
Furthermore, other functions can be imparted to the protective layer. For example, by adding a colorant (for example, a water-soluble dye) that is excellent in the transparency of infrared rays used for exposure and that can efficiently absorb light of other wavelengths, safe light is not caused. Suitability can be improved.

[Photosensitive-thermosensitive layer]
The photosensitive-thermosensitive layer used in the present invention is a layer of various compositions capable of drawing an image by heat or laser exposure. Examples of the lithographic printing plate precursor include the following lithographic printing plate precursors.

  (1) A specific sulfonimide group, disulfone group or sulfonate group described in JP-A-10-282642, JP-A-10-282644, JP-A-10-282646 and JP-A-10-282672 is used as a side chain. A lithographic printing plate precursor for CTP that does not require development processing, comprising an oleophilic polymer having a polar conversion material system image layer that is converted into a hydrophilic polymer having sulfonic acid by heat and / or acid .

  (2) Development processing using a polymer polarity conversion material having a group selected from a carboxylic acid group that causes decarboxylation and a carboxylate group such as an α-sulfonylacetic acid structure described in JP-A No. 2000-122272 is unnecessary. An original for lithographic printing for CTP.

  (3) When heat is applied to an associative polymer such as a novolak resin described in JP-B-46-27919, JP-A-7-285275, etc., the solubility is improved, and the portion between which no heat is applied A positive type heat-sensitive lithographic printing original plate, which has a difference in solubility, and utilizes the formation of a positive image by developing with an alkaline aqueous solution.

  (4) Infrared absorbing dyes that absorb infrared rays and generate heat as described in JP-A-7-20629 and JP-A-7-271029, latent Bronsted acids or s-triazine compounds that are acid generators, and crosslinking agents Negative type that has a thermal cross-linking layer mainly composed of a resol resin, a novolak resin that is a binder and a cross-linked polymer, and after exposure with an infrared laser, the entire plate is heated and then developed with an aqueous alkaline solution to obtain a printing plate Heat-sensitive lithographic printing original plate.

  (5) A photosensitive layer in which fine particles of a thermoplastic hydrophobic polymer are dispersed in a hydrophilic resin described in Japanese Patent No. 2938397 is provided on a hydrophilic support and exposed to an infrared laser to expose the thermoplastic hydrophobic polymer. After forming an image by coalescence (fusion) of fine particles with heat, the plate is directly attached to the printing press, and the non-image portion is removed on the printing press by supplying dampening water and / or ink. A lithographic printing plate precursor that can be developed.

  (6) A printing plate type in which a hydrophilic layer containing a colloid such as silica is provided on the lipophilic layer described in WO94 / 18005, WO98 / 40212, WO99 / 19143, etc., and this hydrophilic layer is ablated An on-press development type thermosensitive material having a water-soluble or hydrophilic overcoat layer on a hydrophilic layer in order to prevent scattering of the original plate and ablation residue described in JP-A-2001-96936 and Japanese Patent Application No. 2000-276866. An original for a lithographic printing plate.

  (7) A photosensitive layer in which microcapsules encapsulating reactive compounds described in JP-A Nos. 2001-277740, 2002-046361, and 2002-137562 are dispersed is provided on a hydrophilic support. Infrared laser exposure to break microcapsules, react the encapsulated reactive compound to form an image, attach the plate to the printing machine as it is, and supply dampening water and / or ink on the printing machine A lithographic printing plate precursor capable of so-called on-press development that removes non-image areas.

As the photosensitive-thermosensitive layer used in the lithographic printing plate precursor according to the invention, the image forming layer used in the lithographic printing plate precursor as described above can be preferably used.

[Elements for forming printed images]
The photosensitive-thermosensitive layer or other layer preferably contains an element for forming a printed image. Examples of usable elements include (a) an imaging element utilizing radical polymerization, and (b) hydrophobic An image-forming element utilizing thermal fusion or thermal reaction of the chemical precursor can be used. If the element (a) is used, a radical polymerization type photosensitive-thermosensitive layer is obtained, and if the element (b) is used, a hydrophobic precursor system photosensitive-thermosensitive layer is obtained. Hereinafter, these elements will be described with reference to other components added when each element is used.

(A) Image forming element using radical polymerization Since the radical polymerization type element has high image formation sensitivity, it is possible to effectively distribute exposure energy to printout image formation, and to produce a printout image with good visibility. And is most preferable for the photosensitive-thermosensitive layer of the present invention.
The radical polymerization element includes (D) a radical polymerizable compound and (E) a radical polymerization initiator as basic components.

<Radical polymerization initiator>
As the radical polymerization initiator used for the photosensitive-thermosensitive layer, the same radical polymerization initiator as described for the radical polymerization initiator used for the layer containing a polymer compound that changes color by the action of heat or light should be used. Can do.
These radical polymerization initiators are added in a proportion of 0.1 to 50% by mass, preferably 0.5 to 30% by mass, particularly preferably 1 to 20% by mass, based on the total solid content constituting the layer to be added. can do. Within this range, the printing durability is further improved. These radical polymerization initiators may be used alone or in combination of two or more. Further, these radical polymerization initiators may be added to the same layer as other components, or another layer may be provided and added thereto.

<Radically polymerizable compound>
The radically polymerizable compound (hereinafter also simply referred to as a polymerizable compound) that can be used in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and has at least one ethylenically unsaturated bond. It is selected from compounds having, preferably two or more.
Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. In this specification, the “radical polymerizable compound” includes not only a monomer but also a prepolymer, that is, a dimer, a trimer and an oligomer, a mixture thereof, a copolymer thereof, and the like. means. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid EO There are modified triacrylates and the like.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, JP-A-59-5241, and JP-A-2-226149. Those having the aromatic skeleton described above and those having an amino group described in JP-A-1-165613 are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

  In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (a) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

_{CH 2 = C (R 4)} COOCH 2 CH (R 5) OH (a)
(However, R ₄ and R ₅ represent H or CH _3. )

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, JP-B-56-17654, Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable. Further, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, It is possible to obtain a photopolymerizable composition having a very high photosensitive speed.

  Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-A-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337 and JP-B-1-40336, vinylphosphonic acid compounds described in JP-A-2-25493, and the like can also be mentioned. . In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

About these addition polymerizable compounds, the details of usage, such as the structure, single use or combination, addition amount, etc. can be arbitrarily set according to the performance design of the final lithographic printing plate precursor. For example, it is selected from the following viewpoints.
From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the image area, that is, the cured film, those having three or more functionalities are preferable. Further, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrenic compound, vinyl ether type). A method of adjusting both sensitivity and strength by using a compound) is also effective.
In addition, the selection and use method of the addition polymerization compound is also an important factor for the compatibility and dispersibility with other components in the photosensitive-thermosensitive layer (for example, binder polymer, initiator, colorant, etc.) For example, the compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected for the purpose of improving the adhesion of the substrate and the protective layer described later.

  The polymerizable compound is preferably used in the range of 5 to 90% by mass, more preferably 15 to 80% by mass, based on the total solid content of the layer to be added. These may be used alone or in combination of two or more. In addition, the use method of the addition polymerizable compound can be arbitrarily selected from the viewpoint of polymerization inhibition with respect to oxygen, resolution, fogging property, refractive index change, surface adhesiveness, etc. Depending on the case, a layer configuration and coating method such as undercoating and overcoating can be performed.

  The photosensitive / thermosensitive layer containing (D) and (E) used in the lithographic printing plate precursor according to the invention preferably contains the following compounds in addition to the above compounds.

<Infrared absorber>
As the infrared absorber used in the photosensitive-thermosensitive layer, the same infrared absorber as that described as the infrared absorber used in the layer containing a polymer compound that changes color by the action of heat or light can be used.
As the addition amount, when a negative lithographic printing plate precursor is prepared, the absorbance at the oscillation wavelength of the laser used for exposure of the surface having the photosensitive-thermosensitive layer of the lithographic printing plate precursor is 0.3 by reflection measurement. It is preferable to add so that it may exist in the range of -1.5, and it is more preferable to add so that it may exist in the range of 0.4-1.1. By being added so as to be in this range, a uniform polymerization reaction in the depth direction of the photosensitive-thermosensitive layer proceeds, good film strength of the image area and adhesion to the support can be obtained, and good Plate inspection can be achieved. The absorbance of the surface of the lithographic printing plate precursor having the photosensitive-thermosensitive layer is determined by the amount of infrared absorber added to the layer containing a polymer compound that changes color by the action of heat or light, the thickness of the layer, and the photosensitive-thermosensitive layer. It can adjust with the quantity of the infrared absorber added to, and the thickness (after-mentioned) of this layer. Absorbance can be measured by a conventional method. As a measuring method, for example, on a reflective support such as aluminum, a photosensitive-thermosensitive layer having a thickness appropriately determined as a lithographic printing plate in a coating amount after drying is formed, and the reflection density is optically measured. Examples thereof include a method of measuring with a densitometer, a method of measuring with a spectrophotometer by a reflection method using an integrating sphere, and the like.

<Binder polymer>
The photosensitive-thermosensitive layer can contain a binder polymer. As the binder polymer that can be used in the present invention, conventionally known binder polymers can be used without limitation, and a linear organic polymer having a film property is preferable. Examples of such binder polymers include acrylic resins, polyvinyl acetal resins, polyurethane resins, polyurea resins, polyimide resins, polyamide resins, epoxy resins, methacrylic resins, polystyrene resins, novolac phenolic resins, polyester resins, and synthetic rubbers. And natural rubber.

  The binder polymer preferably has crosslinkability in order to improve the film strength of the image area. In order to impart crosslinkability to the binder polymer, a crosslinkable functional group such as an ethylenically unsaturated bond may be introduced into the main chain or side chain of the polymer. The crosslinkable functional group may be introduced by copolymerization.

Examples of the polymer having an ethylenically unsaturated bond in the main chain of the molecule include poly-1,4-butadiene and poly-1,4-isoprene.
Examples of polymers having an ethylenically unsaturated bond in the side chain of the molecule are polymers of esters or amides of acrylic acid or methacrylic acid, where the ester or amide residue (-COOR or CONHR R) is ethylene. Examples thereof include polymers having a polymerizable unsaturated bond.

Examples of the residue (the R) having an ethylenically unsaturated _{bond, - (CH 2) n CR} 1 = CR 2 R 3, - (CH 2 O) n CH 2 CR 1 = CR 2 R 3, - _{(CH 2 CH 2 O) n} CH 2 CR 1 = CR 2 R 3, - (CH 2) n NH-CO-O-CH 2 CR 1 = CR 2 R 3, - (CH 2) n -O-CO —CR ¹ ═CR ² R ³ and (CH ₂ CH ₂ O) ₂ —X (wherein R ^{1 to} R ³ are each a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms, an aryl group, and alkoxy. R ¹ and R ² or R ³ may be bonded to each other to form a ring, n represents an integer of 1 to 10. X represents a dicyclopentadienyl residue. Represents a group).

Specific examples of the ester _{residue, -CH 2 CH = CH 2,} ( described in JP Kokoku _{7-21633.) - CH 2 CH 2} O-CH 2 CH = CH 2, -CH 2 C _{(CH 3) = CH 2,} -CH 2 CH = CH-C 6 H 5, -CH 2 CH 2 OCOCH = CH-C 6 H 5, -CH 2 CH 2 -NHCOO-CH 2 CH = CH 2 and CH ₂ CH ₂ O—X (wherein X represents a dicyclopentadienyl residue).
Specific examples of the amide residue include —CH ₂ CH═CH ₂ , —CH ₂ CH ₂ —Y (wherein Y represents a cyclohexene residue), —CH ₂ CH ₂ —OCO—CH═CH _2. Is mentioned.

  The binder polymer having crosslinkability, for example, has a free radical (polymerization initiation radical or a growth radical in the polymerization process of the polymerizable compound) added to the crosslinkable functional group, and the polymerization chain of the polymerizable compound is formed directly between the polymers. Through addition polymerization, a cross-link is formed between the polymer molecules and cured. Alternatively, atoms in the polymer (eg, hydrogen atoms on carbon atoms adjacent to the functional bridging group) are abstracted by free radicals to form polymer radicals that are bonded together, thereby causing cross-linking between polymer molecules. Forms and cures.

  The content of the crosslinkable group in the binder polymer (content of unsaturated double bond capable of radical polymerization by iodine titration) is preferably 0.1 to 10.0 mmol, more preferably 1.0, per 1 g of the binder polymer. -7.0 mmol, most preferably 2.0-5.5 mmol. Within this range, good sensitivity and good storage stability can be obtained.

For example, in the case of on-press development, the binder polymer preferably has high solubility or dispersibility in ink and / or fountain solution.
In order to improve solubility or dispersibility in ink, the binder polymer is preferably oleophilic, and in order to improve solubility or dispersibility in dampening water, the binder polymer is hydrophilic. Is preferred. For this reason, in the present invention, it is also effective to use a lipophilic binder polymer and a hydrophilic binder polymer in combination.

  Examples of hydrophilic binder polymers include hydroxy groups, carboxyl groups, carboxylate groups, hydroxyethyl groups, polyoxyethyl groups, hydroxypropyl groups, polyoxypropyl groups, amino groups, aminoethyl groups, aminopropyl groups, and ammonium. Preferred are those having a hydrophilic group such as a group, an amide group, a carboxymethyl group, a sulfonic acid group, and a phosphoric acid group.

  Specific examples include gum arabic, casein, gelatin, starch derivatives, carboxymethylcellulose and its sodium salt, cellulose acetate, sodium alginate, vinyl acetate-maleic acid copolymers, styrene-maleic acid copolymers, polyacrylic acids and their salts, Polymethacrylic acids and their salts, hydroxyethyl methacrylate homopolymers and copolymers, hydroxyethyl acrylate homopolymers and copolymers, hydroxypropyl methacrylate homopolymers and copolymers, hydroxypropyl acrylate homopolymers and copolymers, hydroxybutyl methacrylate homopolymers Polymers and copolymers, homopolymers and copolymers of hydroxybutyl acrylate, polyethylene glycol , Hydroxypropylene polymers, polyvinyl alcohols, hydrolyzed polyvinyl acetate, polyvinyl formal, polyvinyl butyral, polyvinyl pyrrolidone, acrylamide homopolymers and copolymers having a hydrolysis degree of 60 mol% or more, preferably 80 mol% or more Methacrylamide homopolymers and polymers, N-methylolacrylamide homopolymers and copolymers, polyvinylpyrrolidone, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, etc. Is mentioned.

  The binder polymer preferably has a weight average molecular weight of 5000 or more, more preferably 10,000 to 300,000, and a number average molecular weight of 1,000 or more, preferably 2000 to 250,000. More preferred. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1.1 to 10.

  The binder polymer may be any of a random polymer, a block polymer, and a graft polymer, but a random polymer is more preferable. Moreover, a binder polymer may be used independently or may be used in mixture of 2 or more types.

The binder polymer can be synthesized by a conventionally known method. Solvents used in the synthesis include, for example, tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, diethylene glycol dimethyl ether, 1-methoxy. Examples include 2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, and water. These may be used alone or in combination of two or more.
As the radical polymerization initiator used for synthesizing the binder polymer, known compounds such as an azo initiator and a peroxide initiator can be used.

The content of the binder polymer is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and 30 to 70% by mass with respect to the total solid content of the photosensitive-thermosensitive layer. Is more preferable. Within this range, good image area strength and image formability can be obtained.
Moreover, it is preferable to use a polymeric compound and a binder polymer in the quantity used as 1 / 9-7 / 3 by mass ratio.

<Surfactant>
As the surfactant used in the photosensitive-thermosensitive layer, the same surfactants as those described as the surfactant used in the layer containing a polymer compound that changes color by the action of heat or light can be used.
The content of the surfactant is preferably 0.001 to 10% by mass and more preferably 0.01 to 7% by mass with respect to the total solid content of the photosensitive-thermosensitive layer.

<Colorant>
In the present invention, various compounds other than these may be added as necessary. For example, a dye having a large absorption in the visible light region can be used as an image colorant. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (orientated chemistry) Kogyo Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI42535), Ethyl Violet, Rhodamine B (CI145170B), Malachite Green (CI42000), Methylene Blue (CI522015), etc., and JP-A-62-2 And dyes described in No. 293247. Also, pigments such as phthalocyanine pigments, azo pigments, carbon black, titanium oxide, etc. can be suitably used.

  These colorants are preferably added since it is easy to distinguish an image area from a non-image area after image formation. The addition amount is preferably 0.01 to 10% by mass with respect to the total solid content of the photosensitive-thermosensitive layer.

<Polymerization inhibitor>
A small amount of a thermal polymerization inhibitor is preferably added to the photosensitive-thermosensitive layer in order to prevent, for example, unnecessary thermal polymerization of the radical polymerizable compound during the production or storage of the photosensitive-thermosensitive layer.
Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t- (Butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt are preferred.
The addition amount of the thermal polymerization inhibitor is preferably about 0.01 to about 5% by mass with respect to the total solid content of the photosensitive-thermosensitive layer.

<Higher fatty acid derivatives, etc.>
In order to prevent polymerization inhibition due to oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide is added to the photosensitive-thermosensitive layer, and it is applied to the surface of the photosensitive-thermosensitive layer in the drying process after coating. It may be unevenly distributed. The amount of the higher fatty acid derivative added is preferably about 0.1 to about 10% by mass with respect to the total solid content of the photosensitive-thermosensitive layer.

<Plasticizer>
The photosensitive-thermosensitive layer may contain a plasticizer, for example, to improve on-press developability.
Examples of the plasticizer include phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, octyl capryl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, diallyl phthalate; Glycol esters such as glycol phthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, triethylene glycol dicaprylate; Phosphate esters such as tricresyl phosphate and triphenyl phosphate Diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sebacate, dioct Ruazereto, aliphatic dibasic acid esters such as dibutyl maleate; polyglycidyl methacrylate, triethyl citrate, glycerin triacetyl ester, butyl laurate in.
The content of the plasticizer is preferably about 30% by mass or less with respect to the total solid content of the photosensitive-thermosensitive layer.

<Inorganic fine particles>
The photosensitive-thermosensitive layer may contain inorganic fine particles for improving the strength of the cured film in the image area and improving the on-press developability of the non-image area.
As the inorganic fine particles, for example, silica, alumina, magnesium oxide, titanium oxide, magnesium carbonate, calcium alginate, or a mixture thereof is preferably exemplified. Even if they are not photothermally convertible, they can be used for strengthening the film, enhancing interfacial adhesion by surface roughening, and the like.
The inorganic fine particles preferably have an average particle size of 5 nm to 10 μm, and more preferably 0.5 to 3 μm. Within the above range, it is possible to stably disperse in the photosensitive-thermosensitive layer, sufficiently maintain the film strength of the photosensitive-thermosensitive layer, and form a non-image portion having excellent hydrophilicity that hardly causes stains during printing. it can.
The inorganic fine particles as described above can be easily obtained as a commercial product such as a colloidal silica dispersion.
The content of the inorganic fine particles is preferably 20% by mass or less, and more preferably 10% by mass or less, based on the total solid content of the photosensitive-thermosensitive layer.

<Low molecular hydrophilic compound>
The photosensitive-thermosensitive layer may contain a hydrophilic low molecular weight compound, for example, for improving on-press developability. Examples of the hydrophilic low-molecular compound include water-soluble organic compounds such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol and the like, and ether or ester derivatives thereof, glycerin, Polyhydroxys such as pentaerythritol, organic amines such as triethanolamine and diethanolamine monoethanolamine and salts thereof, organic sulfonic acids such as toluenesulfonic acid and benzenesulfonic acid and salts thereof, organic phosphonic acids such as phenylphosphonic acid and the like Examples thereof include organic carboxylic acids such as salts thereof, tartaric acid, oxalic acid, citric acid, malic acid, lactic acid, gluconic acid, and amino acids, and salts thereof.

<Formation of radical polymerization type photosensitive-thermosensitive layer>
In the present invention, several modes can be used as a method for incorporating the above-mentioned photosensitive-thermosensitive layer components into the photosensitive-thermosensitive layer. One is, for example, an embodiment in which the constituent components are dissolved and applied in an appropriate solvent as described in JP-A-2002-287334, and the other is, for example, JP-A-2001-277740, As described in Japanese Patent Application Laid-Open No. 2001-277742, it is an embodiment (microcapsule type photosensitive-thermosensitive layer) in which the constituent components of the photosensitive-thermosensitive layer are encapsulated in microcapsules and contained in the photosensitive-thermosensitive layer. Further, in the microcapsule type photosensitive-thermosensitive layer, the constituent component may be contained outside the microcapsule. In the microcapsule type photosensitive-thermosensitive layer, it is a more preferable embodiment that a hydrophobic constituent component is encapsulated in the microcapsule and a hydrophilic constituent component is contained outside the microcapsule.
Of the constituent components of the photosensitive-thermosensitive layer, it is a more preferred embodiment to encapsulate the infrared absorber.

  As a method for microencapsulating the above-mentioned constituents of the photosensitive-thermosensitive layer, known methods can be applied. For example, as a method for producing microcapsules, a method using coacervation found in U.S. Pat. Nos. 2,800,547 and 2,800,498, U.S. Pat. No. 3,287,154, JP-B-38-19574, 42-446 by the interfacial polymerization method, US Pat. No. 3,418,250, US Pat. No. 3,660,304 by polymer precipitation method, US Pat. No. 3,796,669, isocyanate polyol A method using a wall material, a method using an isocyanate wall material found in US Pat. No. 3,914,511, and a urea-formaldehyde system found in US Pat. Nos. 4,001,140, 4,087,376 and 4,089,802. Or urea formaldehyde-resorcinol A method using a wall forming material, a method using a wall material such as melamine-formaldehyde resin, hydroxycellulose, etc. found in US Pat. No. 4,025,445, and Japanese Patent Publication Nos. 36-9163 and 51-9079. In situ method by monomer polymerization, spray drying method found in British Patent No. 930422, US Pat. No. 3,111,407, electrolytic dispersion cooling method seen in British Patent Nos. 952807 and 967074, etc. However, it is not limited to these.

  A preferable microcapsule wall used in the present invention has a three-dimensional cross-linking and has a property of swelling with a solvent. From such a viewpoint, the wall material of the microcapsule is preferably polyurea, polyurethane, polyester, polycarbonate, polyamide, and a mixture thereof, and particularly preferably polyurea and polyurethane. Further, a compound having a crosslinkable functional group such as an ethylenically unsaturated bond capable of introducing the binder polymer may be introduced into the microcapsule wall.

  The average particle size of the microcapsules is preferably 0.01 to 3.0 μm. 0.05-2.0 micrometers is further more preferable, and 0.10-1.0 micrometer is especially preferable. Within this range, good resolution and stability over time can be obtained.

Moreover, in this invention, each component of the photosensitive-thermosensitive layer mentioned above, Especially preferably, an infrared absorber may be included in the resin fine particles.
Such an embodiment is achieved by preparing a resin fine particle dispersion obtained by dissolving each component in a solvent and then mixing with a polymer solution (preferably a polymer aqueous solution) and a homogenizer. it can.
Examples of the solvent that can be used in this case include ethyl acetate, methyl ethyl ketone (MEK), diisopropyl ether, dichloromethane, chloroform, toluene, dichloroethane, and mixed solvents thereof.
Examples of the polymer include polyvinyl alcohol (PVA), polyacrylic acid, sodium polyacrylate, polyacrylamide, polymethacrylic acid, polysodium methacrylate, polymethacrylamide, polystyrene sulfonic acid, sodium polystyrene sulfonate, acrylic acid. -Methyl acrylate copolymer, methacrylic acid-methyl methacrylate copolymer, styrene-sodium styrene sulfonate copolymer and the like.
Moreover, you may use the above-mentioned binder polymer as said polymer | macromolecule.

  The photosensitive-thermosensitive layer is coated by preparing a coating solution by dispersing or dissolving the necessary components in a solvent. Solvents used here include ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, dimethoxy Examples include ethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, γ-butyrolactone, toluene, water and the like. However, the present invention is not limited to this. These solvents are used alone or in combination. The solid content concentration of the coating solution is preferably 1 to 50% by mass. The photosensitive-thermosensitive layer can be formed by preparing a plurality of coating solutions in which the same or different components are dispersed or dissolved in the same or different solvents, and repeatedly applying and drying a plurality of times.

The coating, exposure of the support after drying - thermosensitive layer coating amount (solid content) may be varied according to the intended purpose, generally 0.3 to 3.0 g / m ² is preferred. Within this range, good sensitivity and good film characteristics of the image recording layer can be obtained.
Various methods can be used as a coating method. Examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating.

(B) Image forming element of hydrophobized precursor system <Hydrophobized precursor>
In the present invention, the hydrophobized precursor is a fine particle capable of converting a hydrophilic photosensitive-thermosensitive layer to hydrophobic when heat is applied. The fine particles are preferably at least one fine particle selected from thermoplastic polymer fine particles and heat-reactive polymer fine particles. Moreover, the microcapsule which included the compound which has a thermoreactive group may be sufficient.

  Examples of the thermoplastic polymer fine particles used in the photosensitive-thermosensitive layer include Research Disclosure No. 33303 of January 1992, JP-A-9-123387, JP-A-9-131850, JP-A-9-171249, The thermoplastic polymer fine particles described in JP-A No.-171250 and European Patent No. 931647 may be mentioned as preferable examples. Specific examples of the polymer constituting the polymer fine particle include homopolymers of monomers such as ethylene, styrene, vinyl chloride, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinylidene chloride, acrylonitrile, vinyl carbazole, or the like. Mention may be made of copolymers or mixtures thereof. Among them, more preferred are polystyrene and polymethyl methacrylate.

  The average particle size of the thermoplastic polymer fine particles used in the present invention is preferably 0.01 to 2.0 μm. As a method for synthesizing such thermoplastic polymer fine particles, in addition to emulsion polymerization and suspension polymerization, these compounds are dissolved in a water-insoluble organic solvent, and this is mixed and emulsified with an aqueous solution containing a dispersant. Further, there is a method (solution dispersion method) in which heat is further applied to solidify into fine particles while the organic solvent is being blown away.

  Examples of the heat-reactive polymer fine particles used in the present invention include thermosetting polymer fine particles and polymer fine particles having a heat-reactive group.

  Examples of the thermosetting polymer include a resin having a phenol skeleton, a urea resin (for example, a urea derivative such as urea or methoxymethylated urea resinized with an aldehyde such as formaldehyde), a melamine resin (for example, melamine or Examples thereof include those obtained by converting the derivatives into resins with aldehydes such as formaldehyde, alkyd resins, unsaturated polyester resins, polyurethane resins, and epoxy resins. Among these, resins having a phenol skeleton, melamine resins, urea resins and epoxy resins are particularly preferable.

  Suitable resins having a phenol skeleton include, for example, phenol resins obtained by resinizing phenol, cresol, etc. with aldehydes such as formaldehyde, hydroxystyrene resins, N- (p-hydroxyphenyl) methacrylamide, and p-hydroxyphenyl methacrylate. Examples thereof include a polymer or copolymer of methacrylamide or acrylamide or methacrylate or acrylate having a phenol skeleton.

  The average particle diameter of the thermosetting polymer fine particles used in the present invention is preferably 0.01 to 2.0 μm. Such thermosetting polymer fine particles can be easily obtained by a solution dispersion method, but may be formed into fine particles when the thermosetting polymer is synthesized. However, it is not restricted to these methods.

  The thermally reactive group of the polymer fine particle having a thermally reactive group used in the present invention may be any functional group that performs a reaction as long as a chemical bond is formed, but is an ethylenically unsaturated group that performs a radical polymerization reaction. Group (for example, acryloyl group, methacryloyl group, vinyl group, allyl group, etc.), cationically polymerizable group (for example, vinyl group, vinyloxy group, etc.), isocyanate group that performs addition reaction or its block, epoxy group, vinyloxy group And a functional group having an active hydrogen atom as a reaction partner (for example, an amino group, a hydroxyl group, a carboxyl group, etc.), a carboxyl group for performing a condensation reaction, a hydroxyl group or an amino group as a reaction partner, a ring-opening addition reaction The acid anhydride to be used and the amino group or hydroxyl group as the reaction partner may be mentioned as suitable ones. Kill.

  The introduction of these functional groups into the polymer fine particles may be performed at the time of polymerization, or may be performed using a polymer reaction after the polymerization.

  When introduced at the time of polymerization, it is preferable to carry out emulsion polymerization or suspension polymerization of the monomer having the above functional group. Specific examples of the monomer having the above functional group include allyl methacrylate, allyl acrylate, vinyl methacrylate, vinyl acrylate, 2- (vinyloxy) ethyl methacrylate, p-vinyloxystyrene, p- {2- (vinyloxy) ethyl} styrene, Block isocyanate with glycidyl methacrylate, glycidyl acrylate, 2-isocyanatoethyl methacrylate or alcohol thereof, block isocyanate with 2-isocyanate ethyl acrylate or alcohol thereof, 2-aminoethyl methacrylate, 2-aminoethyl acrylate, 2- Hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, acrylic acid, methacrylic acid, maleic anhydride, bifunctional acrylate, 2 officers Methacrylate, and the like, but not limited thereto.

  In the present invention, a copolymer of these monomers and a monomer that is copolymerizable with these monomers and does not have a thermally reactive group can also be used. Examples of the copolymer monomer having no heat-reactive group include styrene, alkyl acrylate, alkyl methacrylate, acrylonitrile, vinyl acetate, and the like. It is not limited to.

  Examples of the polymer reaction used when the introduction of the thermally reactive group is carried out after the polymerization include the polymer reaction described in International Publication No. 96/34316 pamphlet.

  Among the polymer fine particles having a heat-reactive group, those in which the polymer fine particles are coalesced by heat are preferable, and those having a hydrophilic surface and being dispersed in water are particularly preferable. The contact angle (water droplets) of the film prepared by applying only polymer fine particles and drying at a temperature lower than the solidification temperature is higher than the contact angle (water droplets) of the film prepared by drying at a temperature higher than the solidification temperature. It is preferable to lower. In order to make the surface of the polymer fine particles hydrophilic in this way, a hydrophilic polymer or oligomer such as polyvinyl alcohol or polyethylene glycol or a hydrophilic low molecular weight compound may be adsorbed on the surface of the polymer fine particles. However, the surface hydrophilization method is not limited to this.

  The solidification temperature of the polymer fine particles having these thermoreactive groups is preferably 70 ° C. or higher, but more preferably 100 ° C. or higher in view of the stability over time. The average particle size of the polymer fine particles is preferably 0.01 to 2.0 μm, more preferably 0.05 to 2.0 μm, and most preferably 0.1 to 1.0 μm. Within this range, good resolution and stability over time can be obtained.

  As the heat-reactive group in the microcapsule encapsulating the compound having a heat-reactive group used in the present invention, the same heat-reactive group as that used for the polymer fine particles having the heat-reactive group is preferable. Can be mentioned. Below, the compound which has a thermoreactive group is demonstrated.

  As the compound having a radical polymerizable unsaturated group, the same compounds as those shown as the radical polymerization type microcapsules are preferably used.

  Examples of the compound having a vinyloxy group suitable for the present invention include compounds described in JP-A-2002-29162. Specific examples include tetramethylene glycol divinyl ether, trimethylolpropane trivinyl ether, tetraethylene glycol divinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, 1,4-bis {2- (vinyloxy) ethyloxy} Benzene, 1,2-bis {2- (vinyloxy) ethyloxy} benzene, 1,3-bis {2- (vinyloxy) ethyloxy} benzene, 1,3,5-tris {2- (vinyloxy) ethyloxy} benzene, 4 , 4′-bis {2- (vinyloxy) ethyloxy} biphenyl, 4,4′-bis {2- (vinyloxy) ethyloxy} diphenyl ether, 4,4′-bis {2- (vinyloxy) ester Ruoxy} diphenylmethane, 1,4-bis {2- (vinyloxy) ethyloxy} naphthalene, 2,5-bis {2- (vinyloxy) ethyloxy} furan, 2,5-bis {2- (vinyloxy) ethyloxy} thiophene, , 5-bis {2- (vinyloxy) ethyloxy} imidazole, 2,2-bis [4- {2- (vinyloxy) ethyloxy} phenyl] propane {bis (vinyloxyethyl) ether of bisphenol A}, 2,2- Examples include, but are not limited to, bis {4- (vinyloxymethyloxy) phenyl} propane, 2,2-bis {4- (vinyloxy) phenyl} propane, and the like.

  As the compound having an epoxy group suitable for the present invention, a compound having two or more epoxy groups is preferable, and a glycidyl ether compound obtained by reaction of a polyhydric alcohol or a polyhydric phenol with epichlorohydrin or a prepolymer thereof. Furthermore, a polymer or copolymer of glycidyl acrylate or glycidyl methacrylate can be used.

  Specific examples include propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl ether of hydrogenated bisphenol A, hydroquinone diglycidyl. Ether, resorcinol diglycidyl ether, diglycidyl ether or epichlorohydrin polyadduct of bisphenol A, diglycidyl ether or epichlorohydrin polyadduct of bisphenol F, diglycidyl ether or epichlorohydride of halogenated bisphenol A Phosphorus polyadduct, diglycidyl ether of biphenyl type bisphenol or epichlorohydrin polyadduct, novolak tree Etc. glycidyl ethers, furthermore, methyl methacrylate / glycidyl methacrylate copolymer, methacrylic acid ethyl / glycidyl methacrylate copolymer, and the like.

  Commercially available products of the above compounds include, for example, Epicoat 1001 (molecular weight: about 900, epoxy equivalent: 450 to 500), Epicoat 1002 (molecular weight: about 1600, epoxy equivalent: 600 to 700), Epicoat 1004 (about) manufactured by Japan Epoxy Resin Co., Ltd. 1060, epoxy equivalent 875-975), Epicoat 1007 (molecular weight about 2900, epoxy equivalent 2000), Epicoat 1009 (molecular weight about 3750, epoxy equivalent 3000), Epicoat 1010 (molecular weight about 5500, epoxy equivalent 4000), Epicoat 1100L (epoxy equivalent) 4000), Epicoat YX31575 (epoxy equivalent 1200), Sumitomo Chemical Co., Ltd. Sumiepoxy ESCN-195XHN, ESCN-195XL, ESCN-195XF, and the like.

  Suitable isocyanate compounds for the present invention include tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, xylylene diisocyanate, naphthalene diisocyanate, cyclohexanephenylene diisocyanate, isophorone diisocyanate, Examples include hexamethylene diisocyanate, cyclohexyl diisocyanate, and compounds obtained by blocking these with alcohol or amine.

  Suitable amine compounds for the present invention include ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, propylenediamine, polyethyleneimine and the like.

  Examples of the compound having a hydroxyl group suitable for the present invention include a compound having a terminal methylol group, a polyhydric alcohol such as pentaerythritol, and bisphenol / polyphenols.

Examples of the compound having a carboxyl group suitable for the present invention include aromatic polyvalent carboxylic acids such as pyromellitic acid, trimellitic acid and phthalic acid, and aliphatic polyvalent carboxylic acids such as adipic acid. Suitable acid anhydrides for the present invention include pyromellitic acid anhydride and benzophenone tetracarboxylic acid anhydride.

  Microencapsulation of the above-mentioned compound having a thermoreactive group can be carried out by the known method described above in the explanation of the radical polymerization system.

<Other photosensitive-thermosensitive layer components>
The photosensitive-thermosensitive layer can contain a hydrophilic resin for improving the on-press developability and the film strength of the photosensitive-thermosensitive layer itself. As hydrophilic resin, what has hydrophilic groups, such as a hydroxyl group, an amino group, a carboxyl group, a phosphoric acid group, a sulfonic acid group, an amide group, is preferable, for example.
The hydrophilic resin preferably has a group that reacts with the heat-reactive group because it reacts with the heat-reactive group of the hydrophobizing precursor and crosslinks to increase the image strength. . For example, when the hydrophobizing precursor has a vinyloxy group or an epoxy group, the hydrophilic resin preferably has a hydroxyl group, a carboxyl group, a phosphoric acid group, a sulfonic acid group, or the like. Among these, a hydrophilic resin having a hydroxyl group or a carboxyl group is preferable.

  Specific examples of hydrophilic resins include gum arabic, casein, gelatin, starch derivatives, soya gum, hydroxypropylcellulose, methylcellulose, carboxymethylcellulose and its sodium salt, cellulose acetate, sodium alginate, vinyl acetate-maleic acid copolymers, styrene-malein Acid copolymers, polyacrylic acids and their salts, polymethacrylic acids and their salts, homopolymers and copolymers of hydroxyethyl methacrylate, homopolymers and copolymers of hydroxyethyl acrylate, homopolymers and copolymers of hydroxypropyl methacrylate, hydroxypropyl acrylate Homopolymers and copolymers, hydroxybutyl methacrylate homopolymers and copolymers, Homopolymers and copolymers of butyl acrylate, polyethylene glycols, hydroxypropylene polymers, polyvinyl alcohols, hydrolyzed polyvinyl acetate having a degree of hydrolysis of at least 60 mol%, preferably at least 80 mol%, polyvinyl formal, polyvinylpyrrolidone, acrylamide Homopolymers and copolymers, methacrylamide homopolymers and copolymers, N-methylolacrylamide homopolymers and copolymers, 2-acrylamido-2-methyl-1-propanesulfonic acid homopolymers and copolymers, 2-methacryloyloxyethylphosphonic acid And homopolymers and copolymers thereof.

  The amount of the hydrophilic resin added to the photosensitive-thermosensitive layer is preferably 20% by mass or less, and more preferably 10% by mass or less.

  Further, the hydrophilic resin may be used after being cross-linked to such an extent that an unexposed portion can be developed on-press on a printing press. Cross-linking agents include glyoxal, aldehydes such as melamine formaldehyde resin, urea formaldehyde resin, methylol compounds such as N-methylol urea, N-methylol melamine, and methylolated polyamide resin, divinyl sulfone and bis (β-hydroxyethylsulfonic acid) Active vinyl compounds such as, epoxy compounds such as epichlorohydrin and polyethylene glycol diglycidyl ether, polyamides, polyamines, epichlorohydrin adducts, polyamide epichlorohydrin resins, ester compounds such as monochloroacetic acid esters and thioglycolic acid esters, Polycarboxylic acids such as polyacrylic acid and methyl vinyl ether / maleic acid copolymer, inorganic such as boric acid, titanyl sulfate, Cu, Al, Sn, V, Cr salts Crosslinking agents, such as modified polyamide polyimide resin. In addition, a crosslinking catalyst such as ammonium chloride, a silane coupling agent, a titanate coupling agent can be used in combination.

  The photosensitive-thermosensitive layer may contain a reaction accelerator that initiates or accelerates the reaction of the thermally reactive group. As such a reaction accelerator, the above radical polymerization initiator can be mentioned as a suitable one.

  Two or more kinds of the reaction accelerators can be used in combination. Further, the reaction accelerator may be added to the photosensitive-thermosensitive layer directly to the photosensitive-thermosensitive layer coating solution or may be added in the form of polymer fine particles. The content of the reaction accelerator in the photosensitive-thermosensitive layer is preferably from 0.01 to 20 mass%, more preferably from 0.1 to 10 mass%, based on the total solids of the photosensitive-thermosensitive layer. Within this range, good reaction initiation or acceleration effect can be obtained without impairing on-press developability.

  In order to further improve the printing durability, a polyfunctional monomer can be added to the photosensitive-thermosensitive layer matrix in the above-mentioned hydrophobized precursor-based photosensitive-thermosensitive layer. As this polyfunctional monomer, those exemplified as the polymerizable compound can be used. Among them, preferable monomers include trimethylolpropane triacrylate, pentaerythritol triacrylate, and the like.

  In addition, the hydrophobic-precursor-based photosensitive-thermosensitive layer includes a surfactant, a colorant, a polymerization inhibitor, and a higher fatty acid derivative described in <Other photosensitive-thermosensitive layer components> of the polymerization-based photosensitive-thermosensitive layer. Additives such as plasticizers, inorganic fine particles, and low molecular weight hydrophilic compounds can be included as necessary.

<Formation of photosensitive / thermosensitive layer of hydrophobized precursor system>
In the same way as in the case of the radical polymerization type photosensitive-thermosensitive layer, the hydrophobic precursor system photosensitive-thermosensitive layer is prepared by applying a coating solution obtained by dispersing or dissolving the necessary components in a solvent and coating the support on a support. , Formed by drying.

Coating the photosensitive on the support obtained after drying - thermosensitive layer coating amount (solid content) may be varied according to the intended purpose, generally 0.5 to 5.0 g / m ² is preferred.

When the photosensitive / thermosensitive layer of the hydrophobized precursor system is used, a lithographic printing plate precursor capable of on-press development can be produced.
On the other hand, the lithographic printing plate precursor of the present invention is not processed (no development) by making the photosensitive-thermosensitive layer of the hydrophobized precursor system a “hydrophilic layer having a crosslinked structure” having sufficient printing durability even when unexposed. ) Applicable to lithographic printing plate precursors of molds.

  The hydrophilic layer having such a crosslinked structure preferably includes at least one of a hydrophilic resin formed with a crosslinked structure and an inorganic hydrophilic binder resin formed by sol-gel conversion. It is. Of these, the hydrophilic resin will be described first. By adding this hydrophilic resin, the affinity with the hydrophilic component in the emulsion ink is improved, and the film strength of the photosensitive-thermosensitive layer itself is also improved. As the hydrophilic resin, those having a hydrophilic group such as hydroxyl, carboxyl, hydroxyethyl, hydroxypropyl, amino, aminoethyl, aminopropyl, carboxymethyl and the like are preferable.

Specific examples of hydrophilic resins include gum arabic, casein, gelatin, starch derivatives, carboxymethylcellulose and its sodium salt, cellulose acetate, sodium alginate, vinyl acetate-maleic acid copolymers, styrene-maleic acid copolymers, polyacrylic acids and Salts thereof, polymethacrylic acids and salts thereof, homopolymers and copolymers of hydroxyethyl methacrylate, homopolymers and copolymers of hydroxyethyl acrylate, homopolymers and copolymers of hydroxypropyl methacrylate, homopolymers and copolymers of hydroxypropyl acrylate, hydroxybutyl Methacrylate homopolymers and copolymers, hydroxybutyl acrylate homopolymers and copolymers, polyethylene Glycols, hydroxypropylene polymers, polyvinyl alcohols, and hydrolyzed polyvinyl acetate, polyvinyl formal, polyvinyl butyral, polyvinyl pyrrolidone, acrylamide homopolymers and copolymers having a degree of hydrolysis of at least 60 mol%, preferably at least 80 mol% Methacrylamide homopolymers and polymers, N-methylolacrylamide homopolymers and copolymers, and the like.

  When the hydrophilic resin is used in the photosensitive-thermosensitive layer according to the present invention, the hydrophilic resin may be used after being crosslinked. As the crosslinking agent used for forming the crosslinked structure, those described above are used.

  Moreover, what contains the inorganic hydrophilic binder resin formed by sol-gel conversion as a preferable aspect of an unprocessed (non-development) type photosensitive-thermosensitive layer can be mentioned. A preferred sol-gel conversion binder resin is that a bonding group coming out of a polyvalent element forms a network structure, that is, a three-dimensional crosslinked structure via an oxygen atom, and at the same time, the polyvalent metal is an unbonded hydroxyl group. And a polymer having a resinous 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 has a network shape as dehydration condensation proceeds. The resin structure becomes strong. Examples of the polyvalent binding element of the compound having a hydroxyl group or an alkoxy group that performs sol-gel conversion include aluminum, silicon, titanium, and zirconium, and any of these can be used in the present invention. Among them, a sol-gel conversion system using silicon is more preferable, and a system including a silane compound having at least one silanol group capable of sol-gel conversion is particularly preferable. Hereinafter, a sol-gel conversion system using silicon will be described. However, a sol-gel conversion system using aluminum, titanium, and zirconium can be implemented by replacing silicon described below with each element.

  The sol-gel conversion binder resin is preferably a resin having a siloxane bond and a silanol group, and a coating solution that is a sol system containing at least one compound having a silanol group is used for the photosensitive-thermosensitive layer. In the coating and drying process, the condensation of silanol groups proceeds to gel, and the siloxane skeleton structure is formed.

  In addition, the photosensitive-thermosensitive layer containing the sol-gel conversion binder resin is used for the purpose of improving physical properties such as film strength and film flexibility and improving coating properties, and the hydrophilic resin and the crosslinking agent. It can also be used in combination.

  The siloxane resin forming the gel structure is represented by the following general formula (V), and the silane compound having at least one silanol group is represented by the following general formula (VI). In addition, the material system added to the photosensitive-thermosensitive layer does not necessarily need to be the silane compound of the general formula (VI) alone. Generally, the substance system is a partially condensed oligomer of the silane compound or the silane compound of the general formula (VI). There may be a mixture of oligomers.

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

Formula (VI) (R ⁰ ) _n Si (Y) _4-n

Here, R ⁰ represents a hydroxyl group, a hydrocarbon group or a heterocyclic group. Y represents 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 each represents a hydrocarbon group or a hydrogen atom. n represents 0, 1, 2 or 3.

The hydrocarbon group or heterocyclic group for R ⁰ is, for example, a linear or branched alkyl group having 1 to 12 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group). Group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, etc .; these groups are substituted with halogen atom (chlorine atom, 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) Group, hexenyl group, octenyl group, 2-hydroxyethyl group, 3-chloropropyl group, 2-cyanoethyl group, N, N-dimethylaminoethyl group, 2-bromoethyl Til group, 2- (2-methoxyethyl) oxyethyl group, 2-methoxycarbonylethyl group, 3-carboxyethyl group, 3-carboxypropyl group, benzyl group, etc.), -OCOR '' group (R '' represents Represents the same contents as R ′), —COOR ″ group, —COR ″ group, —N (R ′ ″) (R ″ ′) group (R ′ ″ represents a hydrogen atom or R ′ represents the same content as R ′ and may be the same or different from each other), —NHCONHR ″ group, —NHCOOR ″ group, —Si (R ″) ₃ group, —CONHR ″ group and the like. In the alkyl group, a plurality of substituents may be substituted in a linear or branched alkenyl group having 2 to 12 carbon atoms (for example, a vinyl group, a propenyl group, a butenyl group, a pentenyl group, Hexenyl group, octenyl group, decenyl group, dodecenyl group, etc .; Examples of the group to be substituted include those having the same content as the group substituted with the alkyl group, and an aralkyl group having 7 to 14 carbon atoms which may be substituted (for example, benzyl group, phenethyl group, 3-phenylpropyl). Group, naphthylmethyl group, 2-naphthylethyl group and the like; examples of the group substituted by these include those having the same contents as the group substituted by the alkyl group, and a plurality of groups may be substituted), carbon An alicyclic group of 5 to 10 which may be substituted (for example, cyclopentyl group, cyclohexyl group, 2-cyclohexylethyl group, norbornyl group, adamantyl group, etc.); And a group having the same content as the group to be substituted, or a plurality of which may be substituted, and an aryl group having 6 to 12 carbon atoms which may be substituted (for example, phenyl group, In the til group, examples of the substituent include those having the same content as the group substituted with the alkyl group, and a plurality of substituents may be substituted), or at least selected from a nitrogen atom, an oxygen atom, and a sulfur atom Heterocyclic group containing one kind of atom which may be condensed (for example, pyran ring, furan ring, thiophene ring, morpholine ring, pyrrole ring, thiazole ring, oxazole ring, pyridine ring, piperidine ring, pyrrolidone ring, benzo A thiazole ring, a benzoxazole ring, a quinoline ring, a tetrahydrofuran ring and the like may contain a substituent. Examples of the substituent include those having the same content as the group substituted with the alkyl group, and a plurality of substituents may be substituted.

Examples of the substituent of the —OR ¹ group, —OCOR ² group, or —N (R ³ ) (R ⁴ ) group of Y in the general formula (VI) include the following substituents. In the —OR ¹ group, R ¹ is an optionally substituted aliphatic group having 1 to 10 carbon atoms [eg, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, pentyl group, octyl group, Nonyl group, decyl group, propenyl group, butenyl group, heptenyl group, hexenyl group, octenyl group, decenyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 2-methoxyethyl group, 2- (2-methoxyethyl) Oxyethyl group, 2- (N, N-dimethylamino) ethyl group, 2-methoxypropyl group, 2-cyanoethyl group, 3-methyloxypropyl group, 2-chloroethyl group, cyclohexyl group, cyclopentyl group, cyclooctyl group, chloro Cyclohexyl, methoxycyclohexyl, benzyl, phenethyl, dimethoxybenzyl, methyl A rubenzyl group, a bromobenzyl group, and the like.

In the —OCOR ² group, R ² is an aliphatic group having the same content as R ¹ or an aromatic group having 6 to 12 carbon atoms which may be substituted (the aromatic group is the same as that exemplified for the aryl group of R above. Are included). In the —N (R ³ ) (R ⁴ ) group, R ³ and R ⁴ may be the same as or different from each other, and each is a hydrogen atom or an aliphatic group having 1 to 10 carbon atoms which may be substituted (for example, And those having the same contents as R ¹ of the —OR ¹ group. 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 (VI) include the following, but are not limited thereto.

  Tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra n-propylsilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane , N-propyltrichlorosilane, n-propyltrimethoxysilane, n-hexyltrimethoxysilane, n-decyltrimethoxysilane, phenyltrichlorosilane, phenyltrimethoxysilane, dimethoxyditriethoxysilane, dimethyldichlorosilane, dimethyldimethoxysilane , Diphenyldimethoxysilane, phenylmethyldimethoxysilane, triethoxyhydrosilane, trimethoxyhydrosilane, vinyltrichlorosilane, Nyltrimethoxysilane, trifluoropropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropylpropyl Methoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β- (3,4- (Epoxycyclohexyl) ethyltrimethoxysilane and the like.

In the photosensitive-thermosensitive layer, together with the silane compound of the general formula (VI), Ti, Zn, Sn, Zr, Al, and other metal compounds that can be formed by bonding to a resin during sol-gel conversion are used in combination. Can do. Examples of the metal compound used include Ti (OR ″) ₄ , TiCl ₄ , Zn (OR ″) ₂ , Zn (CH ₃ COCHCOCH ₃ ) ₂ , Sn (OR ″) ₄ , Sn (CH ₃ COCHCOCH ₃ ) ₄ , Sn (OCOR ″) ₄ , SnCl ₄ , Zr (OR ″) ₄ , Zr (CH ₃ COCHCOCH ₃ ) ₄ , (NH ₄ ) ₂ ZrO (CO ₃ ) ₂ , Al (OR ″) ₃ , Al (CH ₃ COCHCOCH ₃ ) _{3 and the} like. Here, R ″ represents a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group or the like.

Furthermore, in order to accelerate the hydrolysis and polycondensation reaction of the compound represented by the general formula (VI) 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 is used as it is or in a state in which it is dissolved in a solvent such as water or alcohol (hereinafter referred to as an acidic catalyst and a basic catalyst, respectively). The concentration at that time is not particularly limited, but when the concentration is high, the hydrolysis and polycondensation rates tend to increase.
However, when a basic catalyst having a high concentration is used, a precipitate may be generated in the sol solution. Therefore, the concentration of the basic catalyst is preferably 1 N (concentration in aqueous solution) or less.

  Specific examples of the acidic catalyst include hydrohalic acid such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, carbonic acid, carboxylic acid such as formic acid and acetic acid, and sulfonic acid such as benzenesulfonic acid. Is mentioned. Specific examples of the basic catalyst include, but are not limited to, an ammoniacal base such as aqueous ammonia and amines such as ethylamine and aniline.

  The photosensitive-thermosensitive layer using the sol-gel method described above is particularly preferable as the configuration of the photosensitive-thermosensitive layer according to the present invention. For further details of the sol-gel method, see Sakuo Sakuo, “Science of Sol-Gel Method”, published by Agne Jofusha Co., Ltd. (1988), Satoshi Hirashima “Functional Thin Film Preparation by Latest Sol-Gel Method” Technology ", published by the General Technology Center (1992).

  The amount of the hydrophilic resin added in the photo-thermosensitive layer having a crosslinked structure is preferably 5 to 70% by mass, more preferably 5 to 50% by mass, based on the solid content of the photo-thermosensitive layer.

  In addition, the thickness of the photosensitive-thermosensitive layer is preferably 0.1 to 10 μm from the viewpoint of printing durability, and more preferably 0.5 to 5 μm.

[Hydrophilic support]
The hydrophilic support (hereinafter also simply referred to as “support”) used in the lithographic printing plate precursor according to the invention is not particularly limited as long as it is a dimensionally stable plate. For example, paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, aluminum, zinc, copper, etc.), plastic film (eg, cellulose diacetate, cellulose triacetate, cellulose propionate) Cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), and paper or plastic films on which the above-mentioned metals are laminated or deposited. A preferable support includes a polyester film and an aluminum plate. Among these, an aluminum plate that has good dimensional stability and is relatively inexpensive is preferable.

  The aluminum plate is a pure aluminum plate, an alloy plate containing aluminum as a main component and containing a trace amount of foreign elements, or a plastic laminated on a thin film of aluminum or an aluminum alloy. Examples of foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, and titanium. The content of foreign elements in the alloy is preferably 10% by mass or less. In the present invention, a pure aluminum plate is preferable, but completely pure aluminum is difficult to manufacture in terms of refining technology, and therefore may contain a slightly different element. The composition of the aluminum plate is not specified, and a publicly known material can be used as appropriate.

  The thickness of the support is preferably from 0.1 to 0.6 mm, more preferably from 0.15 to 0.4 mm, and even more preferably from 0.2 to 0.3 mm.

  Prior to using the aluminum plate, it is preferable to perform a surface treatment such as roughening treatment or hydrophilic film formation. By the surface treatment, it is easy to improve hydrophilicity and secure adhesion between the photosensitive-thermosensitive layer and the support. Prior to roughening the aluminum plate, a degreasing treatment with a surfactant, an organic solvent, an alkaline aqueous solution or the like for removing rolling oil on the surface is performed as desired.

<Roughening treatment>
The surface roughening treatment of the aluminum plate is performed by various methods. For example, mechanical surface roughening treatment, electrochemical surface roughening treatment (surface roughening treatment for dissolving the surface electrochemically), chemical treatment, etc. Surface roughening treatment (roughening treatment that chemically selectively dissolves the surface).
As a method for the mechanical surface roughening treatment, a known method such as a ball polishing method, a brush polishing method, a blast polishing method, or a buff polishing method can be used.
Examples of the electrochemical surface roughening treatment include 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. Another example is a method using a mixed acid as described in JP-A-54-63902.

<Formation of hydrophilic film>
A treatment for providing a hydrophilic film having a low thermal conductivity is applied to the aluminum plate that has been subjected to the roughening treatment and other treatments as necessary. The hydrophilic film has a thermal conductivity in the film thickness direction of 0.05 W / mK or more, preferably 0.08 W / mK or more, and 0.5 W / mK or less, preferably 0.3 W / m. mK or less, more preferably 0.2 W / mK or less. When the thermal conductivity in the film thickness direction is 0.05 to 0.5 W / mK, it is possible to suppress the heat generated in the photosensitive-thermosensitive layer from being diffused to the support by laser light exposure. As a result, when the lithographic printing plate precursor according to the present invention is used as an on-press development type or an unprocessed type, heat generated by laser exposure can be used effectively, so that the sensitivity is increased and sufficient image formation and printing are performed. It is possible to form an output image.

  Hereinafter, the thermal conductivity in the film thickness direction of the hydrophilic film defined in the present invention will be described. Various methods have been reported so far for measuring the thermal conductivity of thin films. In 1986, ONO et al. Reported the thermal conductivity in the planar direction of the thin film using a thermograph. Attempts have also been made to apply an AC heating method to the measurement of thermophysical properties of thin films. The origin of the AC heating method can be traced back to the report of 1863, but in recent years, various measurement methods have been proposed by combining a heating method using a laser and a Fourier transform. Devices using the laser angstrom method are actually commercially available. All of these methods determine the thermal conductivity in the plane direction (in-plane direction) of the thin film.

However, when considering the thermal conduction of thin films, thermal diffusion in the depth direction is rather an important factor.
As reported variously, it is said that the thermal conductivity of the thin film is not isotropic, and it is extremely important to directly measure the thermal conductivity in the film thickness direction particularly in the case of the present invention. From such a viewpoint, a method using a thermocomparator as an attempt to measure the thermophysical properties in the film thickness direction of a thin film is described by Lambropoulos et al. (J. Appl. Phys., 66 (9) (1 November 1989)) and Hengeer et al. Paper (APPLIED OPT
ICS, Vol. 32, no. 1 (1 January 1993)). Furthermore, in recent years, a method for measuring the thermal diffusivity of a polymer thin film by temperature wave thermal analysis using Fourier analysis has been reported by Hashimoto et al. (Net Sukutei, 27 (3) (2000)).

The thermal conductivity in the film thickness direction of the hydrophilic film defined in the present invention is measured by the method using the thermo-comparator. Hereinafter, the method will be described in detail. The basic principle of the method is described in detail in the above-mentioned Lambropoulos et al. Paper and Henger et al. Paper. In the present invention, the measurement was performed by the method described in the publication using a thermo-comparator shown in FIG. 3 of JP-A-2003-103951.

  The relationship between each temperature and the thermal conductivity of the film is expressed by the following formula (1).

However, the code | symbol in said Formula (1) is as follows.
T _t : tip temperature, T _b : heat sink temperature, T _r : reservoir temperature, K _tf : film thermal conductivity, K ₁ : reservoir thermal conductivity, K ₂ : chip thermal conductivity (400 W for oxygen-free copper) / MK), K ₄ : metal substrate thermal conductivity (when no film is provided), r ₁ : tip tip radius of curvature, A ₂ : contact area between reservoir and chip, A ₃ : contact area between chip and film , T: film thickness, t ₂ : contact thickness (≈0)

By measuring and plotting each temperature (T _t , T _b and T _r ) while changing the film thickness (t), the slope of the above equation (1) is obtained, and the film thermal conductivity (K _tf ) is obtained. Can do. That is, as is apparent from the above equation (1), this inclination is the reservoir thermal conductivity (K ₁ ), the tip radius of curvature (r ₁ ), the film thermal conductivity (K _tf ), and the contact between the chip and the film. Since it is a value determined by the area (A ₃ ) and K ₁ , r ₁ and A ₃ are known values, the value of K _tf can be obtained from the slope.

The present inventors determined the thermal conductivity of the hydrophilic film (anodized film Al ₂ O ₃ ) provided on the aluminum substrate using the above measurement method. The temperature was measured while changing the film thickness, and the thermal conductivity of Al ₂ O ₃ determined from the slope of the graph was 0.69 W / mK. This is in good agreement with the results of the above-mentioned Lambropoulos et al. This result also shows that the thermophysical value of the thin film is different from the bulk thermophysical value (the thermal conductivity of bulk Al ₂ O ₃ is 28 W / mK).

  When the above method is used to measure the thermal conductivity in the film thickness direction of the hydrophilic film of the lithographic printing plate precursor according to the present invention, the tip end is made minute and the lithographic printing plate is kept constant by keeping the pressing load constant. For the surface roughened for the purpose, it is preferable because a result without variation can be obtained. The value of thermal conductivity is preferably measured at a plurality of different points on the sample, for example, 5 points, and obtained as an average value.

  The film thickness of the hydrophilic film is preferably 0.1 μm or more, more preferably 0.3 μm or more, particularly 0.6 μm or more in terms of scratch resistance and printing durability. Preferably, from the viewpoint of manufacturing cost, in view of the fact that a great amount of energy is required to provide a thick film, it is preferably 5 μm or less, more preferably 3 μm or less, and 2 μm or less. Is particularly preferred.

The hydrophilic film preferably has a density of 1000 to 3200 kg / m ³ from the viewpoint of the effect on heat insulation, the film strength, and the difficulty of smearing in printing.

  As the density measurement method, for example, it is calculated by the following formula from the mass measurement by the Mason method (anodized film mass method by dissolution of chromic acid / phosphoric acid mixed solution) and the film thickness obtained by observing the cross section with SEM. can do.

Density (kg / m ³ ) = (Hydrophilic film mass / film thickness per unit area)

  The method for providing the hydrophilic film is not particularly limited, and an anodic oxidation method, a vapor deposition method, a CVD method, a sol-gel method, a sputtering method, an ion plating method, a diffusion method, and the like can be appropriately used. Moreover, the method of apply | coating the solution which mixed the hollow particle in hydrophilic resin or sol-gel liquid can also be used.

Among them, it is most preferable to use an anodizing process, that is, an anodizing process. The anodizing treatment can be performed by a method conventionally used in this field. Specifically, when direct current or alternating current is applied to an aluminum plate in an aqueous solution or non-aqueous solution of sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, etc., alone or in combination of two or more. An anodized film that is a hydrophilic film can be formed on the surface of the aluminum plate. The conditions for anodizing treatment vary depending on the electrolyte used, and thus cannot be determined unconditionally. In general, however, the electrolyte concentration is 1 to 80% by mass, the solution temperature is 5 to 70 ° C., and the current density is 0.5. ˜60 A / dm ² , voltage 1 to 200 V, electrolysis time 1 to 1000 seconds are appropriate. Among these anodizing treatments, a method for anodizing at a high current density in a sulfuric acid electrolyte solution described in British Patent No. 1,412,768, and US Pat. No. 3,511, A method of anodizing treatment using phosphoric acid as an electrolytic bath described in the specification of No. 661 is preferable. Further, multi-stage anodizing treatment such as anodizing treatment in sulfuric acid and further anodizing treatment in phosphoric acid can be performed.

In the present invention, the anodized film is preferably 0.1 g / m ² or more, more preferably 0.3 g / m ² or more in terms of scratch resistance and printing durability. / M ² or more is particularly preferable, and 3.2 g / m ² or more is more preferable. In view of the fact that enormous energy is required to provide a thick film, it is preferably 100 g / m ² or less, more preferably 40 g / m ² or less, and 20 g / m ² or less. It is particularly preferred.

  On the surface of the anodized film, fine recesses called micropores are uniformly distributed. The density of the micropores present in the anodized film can be adjusted by appropriately selecting the treatment conditions. By increasing the density of the micropores, the thermal conductivity in the film thickness direction of the anodized film can be 0.05 to 0.5 W / mK. Further, the diameter of the micropores can be adjusted by appropriately selecting the processing conditions. By increasing the diameter of the micropore, the thermal conductivity in the film thickness direction of the anodized film can be set to 0.05 to 0.5 W / mK. Further, the diameter of the micropores can be adjusted by appropriately selecting the processing conditions. By increasing the diameter of the micropore, the thermal conductivity in the film thickness direction of the anodized film can be set to 0.05 to 0.5 W / mK.

In the present invention, for the purpose of lowering the thermal conductivity, it is preferable to perform a pore wide treatment for expanding the pore diameter of the micropore after the anodizing treatment. In this pore wide treatment, an aluminum substrate on which an anodized film is formed is immersed in an acid aqueous solution or an aqueous alkali solution to dissolve the anodized film and expand the pore diameter of the micropore. In the pore wide treatment, the amount of dissolution of the anodized film is preferably 0.01 to 20 g / m ² , more preferably 0.1 to 5 g / m ² , and particularly preferably 0.2 to 4 g / m ^2. Done.

When using an acid aqueous solution for pore wide treatment, it is preferable to use an aqueous solution of an inorganic acid such as sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, or a mixture thereof. The concentration of the acid aqueous solution is preferably 10 to 1000 g / L, and more preferably 20 to 500 g / L. The temperature of the acid aqueous solution is preferably 10 to 90 ° C, and more preferably 30 to 70 ° C. The immersion time in the acid aqueous solution is preferably 1 to 300 seconds, and more preferably 2 to 100 seconds. On the other hand, when an alkaline aqueous solution is used for pore wide treatment, it is preferable to use an aqueous solution of at least one alkali selected from the group consisting of sodium hydroxide, potassium hydroxide and lithium hydroxide. The pH of the alkaline aqueous solution is preferably 10 to 13, and more preferably 11.5 to 13.0. The temperature of the aqueous alkali solution is preferably 10 to 90 ° C, and more preferably 30 to 50 ° C. The immersion time in the alkaline aqueous solution is preferably 1 to 500 seconds, and more preferably 2 to 100 seconds. Since it is possible to suppress deterioration of the stain resistance performance during printing, the micropore diameter on the outermost surface is preferably 40 nm or less, more preferably 20 nm or less, and most preferably 10 nm or less. Therefore, both heat insulation and dirt performance are achieved. As a more preferable anodic oxide film shape, the surface micropore diameter is 0 to 40 nm and the internal micropore diameter is 20 to 300 nm. For example, it is known that if the type of the electrolytic solution is the same, the pore diameter of the pore generated by electrolysis is proportional to the electrolytic voltage during electrolysis. A method in which pores having an expanded bottom portion can be generated by gradually increasing the electrolysis voltage using this property can be used. Further, it is known that the pore diameter changes when the type of the electrolytic solution is changed, and the pore diameter increases in the order of sulfuric acid, oxalic acid, and phosphoric acid. Therefore, it is possible to use a method in which sulfuric acid is used as the electrolytic solution in the first stage and phosphoric acid is used in the second stage. Moreover, you may perform the below-mentioned sealing process to the support body obtained by the anodizing process and / or the pore wide process.

  Further, the hydrophilic film may be an inorganic film provided by a sputtering method, a CVD method or the like in addition to the above-described anodized film. Examples of the compound constituting the inorganic film include oxides, nitrides, silicides, borides, and carbides. Moreover, the inorganic film may be comprised only from the compound single-piece | unit, and may be comprised by the mixture of the compound. Specific examples of the compound constituting the inorganic film include aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, hafnium oxide, vanadium oxide, niobium oxide, tantalum oxide, molybdenum oxide, tungsten oxide, chromium oxide; aluminum nitride , Silicon nitride, titanium nitride, zirconium nitride, hafnium nitride, vanadium nitride, niobium nitride, tantalum nitride, molybdenum nitride, tungsten nitride, chromium nitride, silicon nitride, boron nitride; Titanium silicide, zirconium silicide, hafnium silicide, vanadium silicide, niobium silicide, tantalum silicide, molybdenum silicide, tungsten silicide, chromium silicide; titanium boride, zirconium boride, hafnium boride, vanadium boride , Niobium boride, boride Tantalum, molybdenum boride, tungsten boride, chromium boride; aluminum carbide, silicon carbide, titanium carbide, zirconium carbide, hafnium carbide, vanadium carbide, niobium carbide, tantalum carbide, molybdenum carbide, tungsten carbide, and a chromium carbide.

<Sealing treatment>
In the present invention, the hydrophilic support obtained by providing the hydrophilic film as described above may be subjected to a sealing treatment. Examples of the sealing treatment used in the present invention include sealing treatment of an anodized film with pressurized steam or hot water described in JP-A-4-176690 and JP-A-11-301135. In addition, silicate treatment, dichromate aqueous solution treatment, nitrite treatment, ammonium acetate treatment, electrodeposition sealing treatment, triethanolamine treatment, barium carbonate treatment, hydrothermal treatment containing a trace amount of phosphate It can also carry out using well-known methods, such as. For example, when the electrodeposition sealing process is performed, the sealing treatment film is formed from the bottom of the pore, and when the water vapor sealing process is performed, it is formed from the top of the pore. The formation of the pore-treated film is different. In addition, there are immersion treatment with a solution, spray treatment, coating treatment, vapor deposition treatment, sputtering, ion plating, thermal spraying, plating, etc., but there is no particular limitation. Among these, a sealing treatment using particles having an average particle diameter of 8 to 800 nm described in JP-A No. 2002-214764 is particularly preferable.

  The sealing treatment using the particles is performed with particles having an average particle diameter of 8 to 800 nm, preferably an average particle diameter of 10 to 500 nm, and more preferably an average particle diameter of 10 to 150 nm. Within this range, there is little risk of particles entering the inside of the micropores present in the hydrophilic film, and the effect of increasing the sensitivity is sufficiently obtained, and the adhesiveness with the photosensitive-thermosensitive layer is sufficient, and the resistance is improved. Excellent printability. The thickness of the particle layer is preferably 8 to 800 nm, and more preferably 10 to 500 nm.

  The particles used in the present invention preferably have a thermal conductivity of 60 W / mK or less, more preferably 40 W / mK or less, and particularly preferably 0.3 to 10 W / mK or less. When the thermal conductivity is 60 W / mK or less, the thermal diffusion to the aluminum substrate is sufficiently suppressed, and the effect of increasing the sensitivity is sufficiently obtained.

  Examples of the method for providing the particle layer include, but are not limited to, immersion treatment with a solution, spray treatment, coating treatment, electrolytic treatment, vapor deposition treatment, sputtering, ion plating, thermal spraying, and plating.

  For the electrolytic treatment, direct current or alternating current can be used. Examples of the alternating current waveform used in the electrolytic treatment include a sine wave, a rectangular wave, a triangular wave, and a trapezoidal wave. The frequency of the alternating current is preferably 30 to 200 Hz, and more preferably 40 to 120 Hz, from the viewpoint of the cost of manufacturing the power supply device. When a trapezoidal wave is used as the waveform of the alternating current, the time tp until the current reaches a peak from 0 is preferably 0.1 to 2 msec, and more preferably 0.3 to 1.5 msec. If the tp is less than 0.1 msec, the impedance of the power supply circuit is affected, and a large power supply voltage is required at the rising of the current waveform, which may increase the equipment cost of the power supply.

As the hydrophilic particles, Al ₂ O ₃ , TiO ₂ , SiO ₂ and ZrO ₂ are preferably used alone or in combination of two or more. The electrolytic solution is obtained, for example, by suspending the hydrophilic particles in water or the like so that the content becomes 0.01 to 20% by mass of the whole. In order to charge the electrolyte positively or negatively, the pH of the electrolytic solution can be adjusted, for example, by adding sulfuric acid. The electrolytic treatment is performed, for example, using a direct current, an aluminum plate as a cathode, the above electrolytic solution, and a voltage of 10 to 200 V for 1 to 600 seconds. According to this method, it is possible to easily close the mouth while leaving a void inside the micropore existing in the anodized film.

  Further, the sealing treatment was selected from the group consisting of at least one amino group, a carboxyl group and a salt group thereof, and a sulfo group and a salt group described in JP-A-60-149491. A layer comprising a compound having at least one group, selected from compounds having at least one amino group and at least one hydroxy group described in JP-A-60-232998, and salts thereof; A layer comprising a compound, a layer containing a phosphate described in JP-A-62-19494, and at least one monomer unit having a sulfo group described in JP-A-59-101651 The method of providing the layer etc. which consist of a high molecular compound which has in a molecule | numerator as a unit by coating is mentioned.

In addition, carboxymethyl cellulose; dextrin; gum arabic; phosphonic acids having an amino group such as 2-aminoethylphosphonic acid; phenylphosphonic acid, naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, which may have a substituent, Organic phosphonic acid such as methylene diphosphonic acid and ethylene diphosphonic acid; organic phosphoric acid ester such as phenyl phosphoric acid, naphthyl phosphoric acid, alkyl phosphoric acid and glycerophosphoric acid which may have a substituent; Organic phosphinic acids such as phenylphosphinic acid, naphthylphosphinic acid, alkylphosphinic acid and glycerophosphinic acid; amino acids such as glycine and β-alanine; hydrochlorides of amines having a hydroxy group such as hydrochloride of triethanolamine Provide a compound layer selected from The method may also be mentioned.

  In the sealing treatment, a silane coupling agent having an unsaturated group may be applied. Examples of the silane coupling agent include N-3- (acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, (3-acryloxypropyl) dimethylmethoxysilane, and (3-acryloxypropyl) methyldimethoxy. Silane, (3-acryloxypropyl) trimethoxysilane, 3- (N-allylamino) propyltrimethoxysilane, allyldimethoxysilane, allyltriethoxysilane, allyltrimethoxysilane, 3-butenyltriethoxysilane, 2- ( Chloromethyl) allyltrimethoxysilane, methacrylamidopropyltriethoxysilane, N- (3-methacryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, (methacryloxymethyl) dimethylethoxysilane, Tacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxypropyldimethylethoxysilane, methacryloxypropyldimethylmethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropylmethyltriethoxysilane , Methacryloxypropylmethyltrimethoxysilane, methacryloxypropyltris (methoxyethoxy) silane, methoxydimethylvinylsilane, 1-methoxy-3- (trimethylsiloxy) butadiene, styrylethyltrimethoxysilane, 3- (N-styrylmethyl-2) -Aminoethylamino) -propyltrimethoxysilane hydrochloride, vinyldimethylethoxysilane, vinyldiphenyl ester Xysilane, vinylmethyldiethoxysilane, vinylmethyldimethoxysilane, O- (vinyloxyethyl) -N- (triethoxysilylpropyl) urethane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri-t-butoxysilane, vinyltriisopropoxy Examples include silane, vinyltriphenoxysilane, vinyltris (2-methoxyethoxy) silane, and diallylaminopropylmethoxysilane. Of these, a silane coupling agent having a methacryloyl group or an acryloyl group having a fast reactivity of the unsaturated group is preferable.

  In addition, the sol-gel coating treatment described in JP-A-5-50779, the phosphonic acid coating treatment described in JP-A-5-246171, JP-A-6-234284, JP-A-6-6- No. 19173 and JP-A-6-230563, a method for treating a backcoat material by coating, treatment of phosphonic acids described in JP-A-6-262872, and JP-A-6-297875. The coating treatment described in the gazette, the anodizing method described in JP-A-10-109480, the immersion treatment method described in JP-A-2000-81704 and JP-A-2000-89466 Any method may be used.

After forming the hydrophilic film, the surface of the aluminum plate is subjected to a hydrophilic treatment as necessary.
The hydrophilization treatment is described in US Pat. Nos. 2,714,066, 3,181,461, 3,280,734, and 3,902,734. There are such alkali metal silicate methods. In this method, the support is immersed in an aqueous solution such as sodium silicate or electrolytically treated. In addition, the treatment with potassium zirconate fluoride described in JP-B 36-22063, U.S. Pat. Nos. 3,276,868, 4,153,461 and 4,689, And a method of treating with polyvinylphosphonic acid as described in each specification of No.272.

The support preferably has a center line average roughness of 0.10 to 1.2 μm. Within this range, good adhesion to the photosensitive-thermosensitive layer, good printing durability and good stain resistance can be obtained.
The color density of the support is preferably 0.15 to 0.65 as the reflection density value. Within this range, good image formability by preventing halation during image exposure and good plate inspection after development can be obtained.

[Back coat layer]
A back coat can be provided on the back surface of the support, if necessary, after surface treatment or after forming an undercoat layer on the support.
Examples of the back coat include hydrolysis and polycondensation of organic polymer compounds described in JP-A-5-45885, organometallic compounds or inorganic metal compounds described in JP-A-6-35174. A coating layer made of a metal oxide obtained in this manner is preferred. Among them, it is inexpensive to use a silicon alkoxy compound such as Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si (OC ₃ H ₇ ) ₄ , Si (OC ₄ H ₉ ) _4. It is preferable in terms of easy availability.

[Undercoat layer]
In the lithographic printing plate precursor according to the invention, an undercoat layer can be provided between the photosensitive-thermosensitive layer and the support, if necessary. Since the undercoat layer functions as a heat insulating layer, heat generated by laser exposure is not diffused to the support and can be used efficiently, so that there is an advantage that high sensitivity can be achieved. Further, in the unexposed area, the on-press developability is improved because peeling of the photosensitive-thermosensitive layer from the support is likely to occur.
As the undercoat layer, specifically, a silane coupling agent having an addition-polymerizable ethylenic double bond reactive group described in JP-A-10-282679, JP-A-2-304441. Preferred examples include phosphorus compounds having an ethylenic double bond reactive group described in the publication.
The coating amount (solid content) of the undercoat layer is preferably from 0.1-100 mg / m ^2, and more preferably 1 to 30 mg / m ^2.

〔exposure〕
The lithographic printing plate precursor according to the invention is preferably used after imagewise exposure with a laser.
As the laser used at this time, a solid laser and a semiconductor laser that emit infrared rays having a wavelength of 760 to 1200 nm are particularly preferable. The output of the infrared laser is preferably 100 mW or more. In order to shorten the exposure time, it is preferable to use a multi-laser device.
The exposure time per pixel is preferably within 20 μsec. Moreover, it is preferable that irradiation energy amount is 10-300 mJ / cm < ² >.

Another laser that can be suitably used is a laser that emits light having a wavelength of 250 nm to 400 nm. Specifically, as a gas laser, Ar ion laser (364 nm, 351 nm, 10 mW to 1 W), Kr ion laser (356 nm, 351 nm, 10 mW to 1 W), He—Cd laser (325 nm, 1 mW to 100 mW), and solid laser , YAG, YVO _4, etc. 1064 nm oscillation mode-locked solid-state laser 4th harmonic (266 nm, 20-100 mW), waveguide type wavelength conversion element and AlGaAs, InGaAs semiconductor combination (380 nm-400 nm, 5 mW-100 mW), guided wave Type wavelength conversion element combined with AlGaInP and AlGaAs semiconductor (300 nm to 350 nm, 5 mW to 100 mW), AlGaInN (350 nm to 470 nm, 5 mW to 100 mW), and N ₂ laser (33 7 nm, pulse 0.1 to 10 mJ), XeF (351 nm, pulse 10 to 250 mJ), triple wave (355 nm, 1 to ₄ W) of a 1064 nm oscillation mode-locked solid-state laser such as YAG, YVO ₄ and the like.
In particular, a suitable laser among these is an AlGaInN semiconductor laser (commercially available InGaN-based semiconductor laser 375 nm or 405 nm, 5 to 100 mW) and productivity in terms of cost and high illuminance short-time exposure capable of increasing the polymerization rate. This is a 355 nm laser with high output on the surface, and a 266 nm laser with the smallest spectral overlap of the white fluorescent lamp in terms of wavelength suitability and high sensitivity.

[Printing method]
The lithographic printing plate precursor according to the present invention may be printed by, for example, imagewise exposure with an infrared laser, heating the entire surface if necessary, and then supplying an oil-based ink and an aqueous component without any development processing steps. .
Specifically, the lithographic printing plate precursor is exposed with an infrared laser, and the entire surface of the plate is heated in an oven, and then mounted on a printing press without passing through a development processing step. And a method of printing without passing through a development processing step after exposing the entire surface of the plate on the printing machine.

For example, in one embodiment of a negative on-press development type lithographic printing plate precursor, an aqueous component and an oily composition are used without undergoing a development processing step such as a wet development processing step after exposing the lithographic printing plate precursor imagewise with an infrared laser. When ink is supplied and printing is performed, in the exposed portion of the photosensitive-thermosensitive layer, the photosensitive-thermosensitive layer cured by exposure forms an oil-based ink receiving portion having a lipophilic surface. On the other hand, in the unexposed area, the uncured photosensitive-thermosensitive layer is dissolved or dispersed and removed by the supplied aqueous component and / or oil-based ink, and a hydrophilic surface is exposed at that portion.
As a result, the aqueous component adheres to the exposed hydrophilic surface, and the oil-based ink is deposited on the light-sensitive layer in the exposed area, and printing is started. Here, an aqueous component or an oil-based ink may be first supplied to the plate surface, but the oil-based ink is firstly used in order to prevent the aqueous component from being contaminated by the light-sensitive layer in the unexposed area. Is preferably supplied. As the aqueous component and oil-based ink, a dampening water and printing ink for ordinary lithographic printing are used.
In addition, the exposed portion is excellent in visibility because the layer containing a polymer compound that changes color by heat or light changes color.
In this way, the lithographic printing plate precursor is developed on-press on an offset printing machine, for example, and can be used as it is for printing a large number of sheets.

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

[Example 1]
(Production of support)
Using an aluminum plate according to JIS-A-1050 having a thickness of 0.3 mm, the following steps (a) to (k) were carried out in this order.

(A) Mechanical surface roughening treatment While supplying a suspension of abrasive (silica sand) having a specific gravity of 1.12. Roughening was performed. The average particle size of the abrasive was 8 μm, and the maximum particle size was 50 μm. The material of the nylon brush was 6 · 10 nylon, the hair length was 50 mm, and the hair diameter was 0.3 mm. The nylon brush was planted so as to be dense by making a hole in a stainless steel tube having a diameter of 300 mm. Three rotating brushes were used. The distance between the two support rollers (Φ200 mm) at the bottom of the brush was 300 mm. The brush roller was pressed until the load of the drive motor for rotating the brush became 7 kW plus with respect to the load before the brush roller was pressed against the aluminum plate. The rotating direction of the brush was the same as the moving direction of the aluminum plate. The rotation speed of the brush was 200 rpm.

(B) Alkali etching treatment The obtained aluminum plate was sprayed with an aqueous NaOH solution (concentration 26 mass%, aluminum ion concentration 6.5 mass%) at a temperature of 70 ° C. to dissolve the aluminum plate 6 g / m ^2. did. Thereafter, washing with water was performed using well water.

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

(D) Electrochemical roughening treatment An electrochemical roughening treatment was carried out continuously using an alternating voltage of 60 Hz. The electrolytic solution at this time was a nitric acid 10.5 g / liter aqueous solution (aluminum ion 5 g / liter) at a temperature of 50 ° C. The AC power supply waveform has an electrochemical surface roughening treatment using a carbon electrode as a counter electrode using a trapezoidal rectangular wave alternating current with a time TP of 0.8 ms until the current value reaches a peak from zero, a duty ratio of 1: 1, and a trapezoidal rectangular wave alternating current. went. Ferrite was used for the auxiliary anode. The electrolytic cell used was a radial cell type. The current density was 30 A / dm ² at the peak current value, and the amount of electricity was 220 C / dm ² in terms of the total amount of electricity when the aluminum plate was the anode. 5% of the current flowing from the power source was shunted to the auxiliary anode. Thereafter, washing with water was performed using well water.

(E) Alkali etching treatment An aluminum plate is sprayed with a caustic soda concentration 26 mass% aqueous solution (containing 6.5 mass% of aluminum ions) at 32 ° C., and the aluminum plate is dissolved at 0.20 g / m ^2. The smut component mainly composed of aluminum hydroxide generated when electrochemical surface roughening was performed using the alternating current of, and the edge part of the generated pit was melted to smooth the edge part. . Thereafter, washing with water was performed using well water. The etching amount was 3.5 g / m ² .

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

(G) Electrochemical surface roughening treatment An electrochemical surface roughening treatment was performed continuously using an alternating voltage of 60 Hz. The electrolytic solution at this time was a hydrochloric acid 7.5 g / liter aqueous solution (containing 5 g / liter of aluminum ions) at a temperature of 35 ° C. The AC power supply waveform was a rectangular wave, and an electrochemical surface roughening treatment was performed using a carbon electrode as a counter electrode. Ferrite was used for the auxiliary anode. The electrolytic cell used was a radial cell type. The current density was 25 A / dm ² at the peak current value, and the amount of electricity was 50 C / dm ² in terms of the total amount of electricity when the aluminum plate was the anode. Thereafter, washing with water was performed using well water.

(H) Alkaline etching treatment An aluminum plate is sprayed with a caustic soda concentration 26 mass% aqueous solution (containing 6.5 mass% of aluminum ions) at 32 ° C., and the aluminum plate is dissolved at 0.10 g / m ^2. Remove the smut component mainly composed of aluminum hydroxide that was generated when electrochemical surface roughening treatment was performed using AC, and melt the edge part of the generated pit to smooth the edge part. did. Thereafter, washing with water was performed using well water.

(I) Desmut treatment A desmut treatment by spraying was performed with a 25% by mass aqueous solution of sulfuric acid having a temperature of 60 ° C. (containing 0.5% by mass of aluminum ions), and then water washing by spraying was performed using well water.

(J) Anodizing treatment As the electrolytic solution, sulfuric acid was used. The electrolyte solutions all had a sulfuric acid concentration of 170 g / liter (containing 0.5 mass% of aluminum ions), and the temperature was 43 ° C. Thereafter, washing with water was performed using well water. Both current densities were about 30 A / dm ² . The final oxide film amount was 2.7 g / m ² .

(K) Alkali metal silicate treatment An alkali metal silicate treatment (silicate treatment) was performed by immersing the obtained aluminum plate in a treatment layer of a 1 mass% aqueous solution of sodium silicate No. 3 at a temperature of 30 ° C. for 10 seconds. ) Then, the aluminum support body was produced by performing the water washing by the spray using well water. The amount of silicate adhering at that time was 3.6 mg / m ² .

(Formation of the lower layer)
On the obtained support, a methanol solution of a copolymer represented by the following polymer compound (1) (mass average molecular weight 35000) was applied with a wire bar, and dried at 80 ° C. for 60 seconds to form a lower layer. . The coating amount was 0.01 g / m ² .

(Formation of light-sensitive layer)
Subsequently, the photosensitive-thermosensitive layer coating solution (1) having the following composition was bar-coated, followed by oven drying at 70 ° C. for 60 seconds to form a photosensitive-thermosensitive layer having a dry coating amount of 1.0 g / m ^2. An original printing plate was obtained.

Photosensitive-thermosensitive layer coating solution (1)
-The following binder polymer (1) (mass average molecular weight 80000) 0.50 g
・ Polymerizable compound 1.00g
Isocyanuric acid EO-modified triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester M-315)
・ The following polymerization initiator (1) 0.20 g
・ The following infrared absorber (1) 0.05 g
・ The following fluorosurfactant (1) 0.05g
・ Methyl ethyl ketone 18.00g

(Formation of overcoat layer)
Subsequently, an overcoat layer coating solution (1) having the following composition was bar coated, followed by oven drying at 100 ° C. for 60 seconds to form an overcoat layer having a dry coating amount of 0.7 g / m ^2. The original version was obtained.

Overcoat layer coating solution (1)
-The following binder polymer (A) (mass average molecular weight 100,000) 1.00 g
・ The following acid generator (1) 0.05 g
・ The following infrared absorber (2) 0.03 g
・ Methanol 8.00 g
・ Water 8.00g

[Comparative Example 1]
On the support obtained in the same manner as in Example 1, a lower layer and a photosensitive-thermosensitive layer were formed in the same manner as in Example 1.
(Formation of overcoat layer)
Subsequently, an overcoat layer coating solution (2) having the following composition was applied to the bar, followed by oven drying at 100 ° C. for 60 seconds to form an overcoat layer having a dry coating amount of 0.7 g / m ^2. The original version was obtained.

Overcoat layer coating solution (2)
-The following binder polymer (B) (mass average molecular weight 100,000) 1.00 g
・ The acid generator (1) 0.05 g
・ 0.03 g of the above infrared absorber (2)
・ The following discoloring agent (1) 0.50 g
・ Methanol 8.00 g
・ Water 8.00g

[Example 2]
On the support obtained in the same manner as in Example 1, a lower layer and a photosensitive-thermosensitive layer were formed in the same manner as in Example 1.
(Formation of overcoat layer)
Subsequently, an overcoat layer coating solution (3) having the following composition was bar coated, followed by oven drying at 100 ° C. for 60 seconds to form an overcoat layer having a dry coating amount of 1.0 g / m ^2. The original version was obtained.

Overcoat layer coating solution (3)
・ The following binder polymer (C) (mass average molecular weight 200,000) 1.00 g
・ The acid generator (1) 0.05 g
・ 0.03 g of the above infrared absorber (2)
・ Methanol 8.00 g
・ Water 8.00g

[Comparative Example 2]
On the support obtained in the same manner as in Example 1, a lower layer and a photosensitive-thermosensitive layer were formed in the same manner as in Example 1.
(Formation of overcoat layer)
Subsequently, an overcoat layer coating solution (4) having the following composition was bar coated, followed by oven drying at 100 ° C. for 60 seconds to form an overcoat layer having a dry coating amount of 0.7 g / m ² to form a lithographic printing plate. The original version was obtained.

Overcoat layer coating solution (4)
-Binder polymer (D) (mass average molecular weight 100,000) 1.00 g
・ The acid generator (1) 0.05 g
・ 0.03 g of the above infrared absorber (2)
-0.44g of the following discoloring agent (2)
・ Methanol 8.00 g
・ Water 8.00g

[Example 3]
On the support obtained in the same manner as in Example 1, a lower layer and a photosensitive-thermosensitive layer were formed in the same manner as in Example 1.
(Formation of overcoat layer)
Subsequently, an overcoat layer coating solution (5) having the following composition was applied to the bar and then oven-dried at 100 ° C. for 60 seconds to form an overcoat layer having a dry coating amount of 1.2 g / m ^2. The original version was obtained.

Overcoat layer coating solution (5)
-The following binder polymer (E) (mass average molecular weight 200,000) 1.00 g
・ The following radical generator (1) 0.05 g
・ 0.03 g of the above infrared absorber (2)
・ Methanol 8.00 g
・ Water 8.00g

[Example 4]
On the support obtained in the same manner as in Example 1, a lower layer and a photosensitive-thermosensitive layer were formed in the same manner as in Example 1.
(Formation of overcoat layer)
Subsequently, an overcoat layer coating solution (6) having the following composition was applied to the bar and then oven dried at 100 ° C. for 60 seconds to form an overcoat layer having a dry coating amount of 1.1 g / m ^2. The original version was obtained.

Overcoat layer coating solution (6)
-The following binder polymer (F) (mass average molecular weight 150,000) 1.00 g
-0.05 g of the following base generator (1)
・ 0.03 g of the above infrared absorber (2)
・ Methanol 8.00 g
・ Water 8.00g

[Example 5]
On the support obtained in the same manner as in Example 1, a lower layer and a photosensitive-thermosensitive layer were formed in the same manner as in Example 1.
(Formation of overcoat layer)
Subsequently, an overcoat layer coating solution (7) having the following composition was applied to the bar, followed by oven drying at 100 ° C. for 60 seconds to form an overcoat layer having a dry coating amount of 0.8 g / m ^2. The original version was obtained.

Overcoat layer coating solution (7)
・ The following binder polymer (G) (mass average molecular weight 80,000) 1.00 g
・ The following infrared absorber (3) 0.03 g
・ Methanol 8.00 g
・ Water 8.00g

[Example 6]
(Formation of the lower layer)
On the support obtained in the same manner as in Example 1, a methanol solution of the copolymer (mass average molecular weight 35000) represented by the polymer compound (1) was applied with a wire bar, and the mixture was heated at 80 ° C. for 60 seconds. Dried to form a lower layer. The coating amount was 0.02 g / m ² .

(Synthesis of microcapsules)
As an oil phase component, trimethylolpropane and xylene diisocyanate adduct (manufactured by Mitsui Takeda Chemical Co., Ltd., Takenate D-110N) 10 g, pentaerythritol triacrylate (manufactured by Nippon Kayaku Co., Ltd., SR444) 3.15 g, The following infrared absorber (4) 0.35 g and Pionein A-41C (manufactured by Takemoto Yushi Co., Ltd.) 0.1 g were dissolved in 17 g of ethyl acetate. As an aqueous phase component, 40 g of a 4% by mass aqueous solution of PVA-205 was prepared. The oil phase component and the aqueous phase component were mixed and emulsified for 10 minutes at 12000 rpm using a homogenizer. The obtained emulsion was added to 25 g of distilled water, stirred at room temperature for 30 minutes, and then stirred at 40 ° C. for 3 hours. The microcapsule solution thus obtained was diluted with distilled water so that the solid content concentration became 20% by mass. All of the average particle diameters were 0.3 μm.

(Formation of light-sensitive layer)
Subsequently, the photosensitive-thermosensitive layer coating solution (2) having the following composition was bar-coated, followed by oven drying at 70 ° C. for 60 seconds to form a photosensitive-thermosensitive layer having a dry coating amount of 1.0 g / m ^2. An original printing plate was obtained.
Photosensitive-thermosensitive layer coating solution (2)
-Binder polymer (1) (mass average molecular weight 80000) 0.50 g
・ Polymerizable compound 1.00g
Isocyanuric acid EO-modified triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester M-315)
・ The above polymerization initiator (1) 0.20 g
・ The above infrared absorbing agent (1) 0.05 g
・ The above microcapsule solution 2.00g
・ 0.05g of the above fluorosurfactant (1)
・ Methyl ethyl ketone 18.00g

(Formation of overcoat layer)
Subsequently, an overcoat layer coating solution (8) having the following composition was bar coated, followed by oven drying at 100 ° C. for 60 seconds to form an overcoat layer having a dry coating amount of 0.7 g / m ^2. The original version was obtained.
Overcoat layer coating solution (8)
-Binder polymer (A) (mass average molecular weight 100,000) 1.00 g
・ The acid generator (1) 0.05 g
・ 0.03 g of the above infrared absorber (2)
・ Methanol 8.00 g
・ Water 8.00g

2. Exposure and Printing Each lithographic printing plate precursor obtained in the above examples and comparative examples was exposed with a water-cooled 40 W infrared semiconductor laser-mounted Creo Trendsetter 3244VX under conditions of an output of 9 W, an outer drum rotating speed of 210 rpm, and a resolution of 2400 dpi. . The obtained exposed original plate was attached to a cylinder of a printing machine SOR-M manufactured by Heidelberg without developing. Dampening water (EU-3 (etch solution manufactured by Fuji Photo Film Co., Ltd.) / Water / isopropyl alcohol = 1/89/10 (volume ratio)) and TRANS-G (N) black ink (Dainippon Ink & Chemicals, Inc.) After supplying dampening water and ink, printing was performed at a printing speed of 6000 sheets per hour.
When the on-press development of the unexposed part of the image recording layer was completed on the printing press and the number of printing papers required until the ink was not transferred to the printing paper was measured as on-press developability, Even when the planographic printing plate precursor was used, a printed matter having no stain on the non-image area was obtained within 100 sheets.

3. Evaluation (1) Exposed Part Visibility As described above, after laser exposure, the distinction between the exposed part and the unexposed part was visually evaluated as good and defective.
(2) Printing durability As described above, as the number of printed sheets was increased, the image recording layer was gradually worn out and the ink acceptability was lowered, so that the ink density in the printing paper was lowered. Printing durability was evaluated by the number of printed sheets when the ink density (reflection density) was reduced by 0.1 from the start of printing.
Table 1 shows the evaluation results of (1) and (2).

[Example 7]
On the support prepared in the same manner as in Example 1, the following undercoat liquid (1) was applied so that the dry coating amount was 10 mg / m ² to prepare a support used in the following experiments.

Undercoat liquid (1)
・ Undercoat compound (1) below 0.017g
・ Methanol 9.00 g
・ Water 1.00g

On the support provided with the undercoat layer, a photosensitive-thermosensitive layer coating solution (3) having the following composition was bar-coated, followed by oven drying at 100 ° C. for 60 seconds, and a dry coating amount of 1.0 g / m ² . A photosensitive-thermosensitive layer was formed, and a protective layer coating solution (1) having the following composition was applied thereon using a bar so that the coating amount during drying was 1.0 g / m ^2, and then 120 ° C. And dried for 1 minute to obtain a lithographic printing plate precursor.

Photosensitive-thermosensitive layer coating solution (3)
・ The following polymerization initiator (2) 0.2 g
・ The following binder polymer (1) 12.0 g
-Polymerizable compound, Aronix M-315 (manufactured by Toa Gosei Co., Ltd.) 6.0 g
-The following compound C-1 1.5g
・ Thermal polymerization inhibitor 0.1g
N-nitrosophenylhydroxylamine aluminum salt 0.1 g of the following fluorosurfactant (2)
・ Methyl ethyl ketone 70.0g

Protective layer coating solution (1)
・ 88g of water
・ 10 g of the binder polymer (E)
・ Polyethylene glycol (molecular weight 2000) 2g
・ Polymerization initiator 0.1g
・ 1g of the following surfactant

The obtained lithographic printing plate precursor was subjected to imagewise exposure under the condition of energy density of 0.5 mJ / cm ² using a 375 nm semiconductor laser with an output of 10 mW. The exposed plate had good image visibility. Subsequently, the obtained printing plate was printed in the same manner as in Example 1 without any treatment. As a result, 30000 good prints were obtained.

[Example 8]
On the support provided with the undercoat layer prepared in Example 7, a photosensitive-thermosensitive layer coating solution (4) having the following composition was bar-coated, followed by oven drying at 100 ° C. for 60 seconds. A 4 g / m ² image recording layer was formed, and a protective layer coating solution (1) having the above composition was coated thereon using a bar so that the coating amount when dried was 1.0 g / m ² . Thereafter, it was dried at 120 ° C. for 1 minute to obtain a lithographic printing plate precursor.

Photosensitive-thermosensitive layer coating solution (4)
・ 2.0 g of the above binder polymer (1)
・ Polymerizable compound 1.5g
Isocyanuric acid EO-modified triacrylate (manufactured by Toa Gosei Co., Ltd., Aronix M-315)
-Compound represented by the following (1) 0.15 g
-Compound represented by (2) below 0.20 g
・ 0.4 g of the compound represented by the following (3)
・ Thermal polymerization inhibitor 0.1g
N-nitrosophenylhydroxylamine aluminum salt 0.02 g of the above fluorosurfactant (1)
・ Tetraethylamine hydrochloride 0.06g
・ 17.5 g of 1-methoxy-2-propanol
・ Methyl ethyl ketone 19.0g

The obtained lithographic printing plate precursor was subjected to imagewise exposure under the condition of energy density of 0.5 mJ / cm ² using a 405 nm semiconductor laser having an output of 10 mW. The exposed plate had good image visibility. Subsequently, the obtained printing plate was used for printing in the same manner as in Example 1 without any treatment. As a result, 30000 good prints were obtained.

Claims (6)

  A lithographic printing plate precursor having a photosensitive-thermosensitive layer capable of recording an image by laser exposure on a support, the layer containing a polymer compound that changes color by the action of heat or light on the photosensitive-thermosensitive layer A lithographic printing plate precursor characterized by comprising   2. The lithographic printing plate according to claim 1, wherein the polymer compound that changes color by the action of heat or light is a polymer compound having a unit that imparts a heat or photochromic function to the polymer compound (a1). Original edition.   The lithographic printing plate precursor as claimed in claim 1 or 2, wherein the photosensitive-thermosensitive layer contains (D) a radical polymerizable compound and (E) a radical polymerization initiator.   The lithographic printing plate precursor as claimed in any one of claims 1 to 3, wherein the polymer compound that changes color by the action of heat or light is a water-soluble polymer compound.   The lithographic printing plate precursor is a lithographic printing plate precursor that can be printed by mounting it in a printing machine without passing through a development process after image recording by laser exposure, or by recording an image after mounting the printing machine. The lithographic printing plate precursor as claimed in claim 1, wherein the lithographic printing plate precursor is a lithographic printing plate precursor.   The lithographic printing plate precursor according to any one of claims 1 to 4 is mounted on a printing machine without passing through a development processing step after image recording by laser exposure, or by printing an image after mounting the printing machine. Planographic printing method.