JPH11218903A - Negative image recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a negative image recording material suitable for an excellent negative lithographic printing plate which can be directly processed into a printing plate by using an IR laser or the like, namely, which enables so-called direct plate making, and which has no void in an image in the image forming process after exposure to laser light. SOLUTION: This negative image forming material contains (A) a compd. which decomposes by light or heat to produce an acid, (B) a crosslinking agent which crosslinks with an acid. (C) at least one kind of alkali-soluble resin, (D) an IR absorbent, and (E) a polymer compd. having as copolymer components of (1) a component having at least fluorine atoms. (2) a component having acidic hydrogen atoms, and (3) a component showing lipophilicity.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image recording material which can be used as a lithographic printing plate material, and more particularly to a lithographic printing plate capable of directly making a lithographic printing plate from a digital signal of a computer or the like by using an infrared laser. The present invention relates to a negative type image recording material for materials.

[0002]

2. Description of the Related Art Lasers have been remarkably developed in recent years. In particular, solid-state lasers and semiconductor lasers which emit infrared rays having wavelengths of 760 nm to 1200 nm can be easily obtained with high output and small size. These lasers are very useful as a recording light source when making a plate directly from digital data of a computer or the like. However, many photosensitive recording materials that are practically useful have a photosensitive wavelength of 760 n.
m or less, the image cannot be recorded with these infrared lasers. Therefore, a material that can be recorded by an infrared laser is desired.

As an image recording material recordable by such an infrared laser, a recording material comprising an onium salt, a resole resin, a novolak resin, and an infrared absorber described in JP-A-7-20629 . is there. JP-A-7-271029, haloalkyl substituted s- triazine, resole resins, novolac resins, and more made recording material infrared absorber are described. However, there is a problem in that, when handling a lithographic printing plate material using such an image recording material, smudges such as fingerprints attached thereto cause image omission in image formation after laser exposure.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and achieve the following objects. That is, by recording using a solid-state laser and a semiconductor laser that emit infrared light, plate making can be performed directly from digital data of a computer or the like, and in image formation after laser exposure, excellent negative lithographic printing without image omission. An object of the present invention is to provide a negative type image recording material suitable for a plate material.

[0005]

Means for solving the above problems are as follows. That is, (A)
(E) a negative type image recording material, (A) a compound capable of decomposing by light or heat to generate an acid, (B) a crosslinking agent capable of crosslinking by an acid, and (C) an alkali-soluble material. At least one kind of resin, (D) an infrared absorber,
(E) a polymer compound containing at least the following components (1) to (3) as a copolymer component (hereinafter sometimes referred to as a “fluorine-containing copolymer”), and component (1) a hydrogen atom on a carbon atom Is an addition-polymerizable monomer having a fluoroaliphatic group substituted by a fluorine atom, component (2) at least one selected from monomers represented by the following structural formulas [1] to [4], component (3) The following structural formulas [5] to
At least one selected from monomers represented by [8]
seed.

[0006]

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In the above structural formulas [1] to [4], A represents a hydrogen atom, a halogen atom or an alkyl group. W represents an oxygen atom or —NR ₃ —. R ₃ represents a hydrogen atom, an alkyl group or an aryl group. R ₁ represents an alkylene group which may have a substituent or an arylene group which may have a substituent. R ₂ represents a hydrogen atom, an alkyl group or an aryl group. R ₄ represents an alkyl group or an aryl group. Y and Z represent an arylene group which may have a substituent, and Y and Z may be the same or different. X is a linking group, and represents a divalent organic group consisting of atoms selected from carbon, nitrogen, oxygen, sulfur, halogen and hydrogen atoms. m represents an integer of 0 to 1, and n represents an integer of 1 to 3.

[0008]

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In the above structural formulas [5] to [8], W represents an oxygen atom or -NR _3- . R ₃ represents a hydrogen atom, an alkyl group or an aryl group. R ₅ represents an alkyl group which may have a substituent or an aryl group which may have a substituent. R ₆ represents an alkyl group or an aryl group. U is a cyano group, an aryl group, an alkoxy group,
An aryloxy group, an acyloxymethyl group, or a heterocycle containing a nitrogen atom, or —CH ₂ OCOR ₆ (R ₆
Is as defined above. ). A has the same meaning as that represented by the structural formulas [1] to [4].

In the negative type image recording material of the present invention,
The energy given by the solid-state laser and the semiconductor laser emitting infrared light is converted into thermal energy by the infrared absorber (D), and the heat (A) decomposes by light or heat to decompose the compound that generates an acid. (B) a cross-linking agent cross-linked by the acid and (C)
Image recording, that is, plate making of a recording material is performed by accelerating a crosslinking reaction with at least one kind of an alkali-soluble resin. When (E) a fluorine-containing copolymer is present in this reaction system, In image formation of a lithographic printing plate material obtained from a negative image recording material, image omission is eliminated. Although the mechanism is unknown, it is speculated that (E) the fluorinated copolymer lowers the surface energy of the lithographic printing plate material and at the same time suppresses the ingress of moisture in the lithographic printing plate material. Is done.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, components and the like in a negative type image recording material of the present invention will be described in detail.
The (E) fluorine-containing copolymer which is an important component of the present invention will be described.

[(E) Fluorine-Containing Copolymer] In the present invention, the fluorine-containing copolymer is composed of a component (1) having a fluorine atom, a component (2) having an acidic hydrogen atom, and a component (3) having lipophilicity. Is a polymer compound containing at least a) as a copolymer component.

The component (1) is an addition-polymerizable monomer having a fluoroaliphatic group in which a hydrogen atom on a carbon atom is replaced by a fluorine atom.

In the monomer represented by the component (1), a fluoroaliphatic group in which a hydrogen atom on a carbon atom is substituted by a fluorine atom is usually a monovalent or divalent linear or branched chain. Or a cyclic saturated aliphatic group. The fluoroaliphatic group preferably has 3 to 20 carbon atoms from the viewpoint of sufficiently achieving the object of the present invention.
-12 is more preferable, and the fluorine atom bonded to the carbon atom is preferably 40% by weight or more, and 50% by weight
More preferably. Suitable fluoroaliphatic _{group, C n F 2n + 1 -} ( in n, usually an integer of 1 or more, 3 or more preferably an integer.) Are substantially completely or fully fluorinated as Perfluoroaliphatic group (hereinafter sometimes referred to as “Rf”).

In the monomer represented by the component (1), examples of the addition-polymerizable monomer portion include a vinyl monomer having a radically polymerizable unsaturated group. Among them, acrylate, methacrylate, acrylamide, methacrylamide Styrene-based, vinyl-based and the like.

In the monomer represented by the component (1), specific examples of acrylates and methacrylates obtained by addition polymerization of the fluoroaliphatic group include, for example, Rf-
R'-OOC-C (R " ) = CH 2 ( wherein R ', for example, a single bond, .R representing an alkylene group, a sulfonamide alkylene group, or a carbonamido alkylene group"
Represents a hydrogen atom, a methyl group, a halogen atom, or a perfluoroaliphatic group. )).

Specific examples of the monomer represented by the component (1) include, for example, US Pat. Nos. 2,803,615, 2,642,416, 2,826,564 and 310.
No. 2103, No. 3282905, No. 330427
No. 8, each of JP-A-6-256289 and JP-A-62-1987.
-1116, JP-A-62-48772, JP-A-63-7
7574, those described in JP-A-62-36657, and the journal of the Chemical Society of Japan 1985 (No. 10) 1884.
〜1888. In addition to the monomers to which these fluoroaliphatic groups are bonded, R
reports Res. Lab. Asahi G1ass
Co. , Ltd. 34, 1984, pp. 27-34. The monomer obtained by addition polymerization of the fluoroaliphatic group may be a mixture of monomers having different lengths such as a perfluoroalkyl group as shown in the following structural formula.

[0018]

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In the present invention, the content of the component (1) is preferably from 3 to 70% by weight, more preferably from 7 to 40% by weight, based on the total weight of the fluorinated copolymer. When the content is less than 3% by weight, fingerprint resistance may be poor. When the content is more than 70% by weight, the developability of the image recording material may be reduced, and the non-image portion may have poor development. Both are not preferred. The component (1) may be used alone or in combination of two or more.

The component (2) has the following structural formula [1] to
It is a monomer represented by [4].

[0021]

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In the above structural formulas [1] to [4], A represents a hydrogen atom, a halogen atom or an alkyl group. W represents an oxygen atom or —NR ₃ —. R ₃ represents a hydrogen atom, an alkyl group or an aryl group. R ₁ represents an alkylene group which may have a substituent or an arylene group which may have a substituent. R ₂ represents a hydrogen atom, an alkyl group or an aryl group. R ₄ represents an alkyl group or an aryl group. Y and Z represent an arylene group which may have a substituent, and Y and Z may be the same or different. X is a linking group, and represents a divalent organic group consisting of atoms selected from carbon, nitrogen, oxygen, sulfur, halogen and hydrogen atoms. m represents an integer of 0 to 1, and n represents an integer of 1 to 3.

In the structural formulas [1] to [4], A represents hydrogen
An atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms is preferable.
Good. W is -NR_Three-Is preferred. R_ThreeIs a hydrogen source
, An alkyl group having 1 to 20 carbon atoms, or 6 to 20 carbon atoms
Are preferred. R ₁Has a substituent
Having an alkylene group having 1 to 12 carbon atoms or a substituent.
An arylene group having 6 to 20 carbon atoms which may be
No. R_TwoIs a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,
Alternatively, an aryl group having 6 to 20 carbon atoms is preferable. R_FourIs
An alkyl group having 1 to 20 carbon atoms or an ant having 6 to 20 carbon atoms
Preferred are hydroxyl groups. Y and Z are ants having 6 to 20 carbon atoms.
An -lene group is preferred.

In the structural formulas [1] and [2], A is more preferably a hydrogen atom or a methyl group.
R ₂ is more preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms such as methyl, ethyl and isopropyl, or an aryl group having 6 to 18 carbon atoms such as phenyl and naphthyl.
R ₁ and Y each have 6 to 6 carbon atoms such as phenylene and naphthylene;
Twelve arylene groups are more preferred.

In the structural formulas [1] to [4], the alkylene group and the arylene group representing R ₁ Y or Z may have a substituent. As the substituent, fluorine, chlorine,
Other than a halogen atom such as bromine, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, a cyano group, an amide group such as an acetamido group, and an alkoxydicarbonyl group such as an ethoxydicarbonyl group, Examples thereof include an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 18 carbon atoms.

Hereinafter, the structural formulas (1) to (2) of the component (2) will be described.
Preferred specific examples of the monomer represented by [4] are shown below.
The present invention is not limited to these specific examples.

[0027]

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[0028]

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In the present invention, the content of the component (2) is preferably from 5 to 70% by weight, more preferably from 10 to 50% by weight, based on the weight of the fluorinated copolymer. When the content is less than 5% by weight,
The developability of the image recording material may be reduced and the non-image area may be poorly developed, and if it exceeds 70% by weight, the fingerprint resistance may be poor, which is not preferable. Also,
Further, the component (2) may be used alone or in combination of two or more.

The component (3) is represented by the structural formula [5] to
It is a monomer represented by [8].

[0031]

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In the structural formulas [5] to [8], W represents an oxygen atom or -NR _3- . R ₃ represents a hydrogen atom, an alkyl group or an aryl group. R ₅ represents an alkyl group which may have a substituent or an aryl group which may have a substituent. R ₆ represents an alkyl group or an aryl group. U is a cyano group, an aryl group, an alkoxy group,
An aryloxy group, an acyloxymethyl group, or a heterocycle containing a nitrogen atom, or —CH ₂ OCOR ₆ (R ₆
Is as defined above. ). A has the same meaning as that represented by the structural formulas [1] to [4].

In the above structural formulas [5] to [8], W is preferably an oxygen atom or -NR _3- . R ₃ is a hydrogen atom,
An alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms is preferable. R ₅ is preferably an alkyl group having 1 to 8 carbon atoms which may have a substituent, or an aryl group having 6 to 12 carbon atoms which may have a substituent. R ₆ is
An alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms is preferable. U is a cyano group, having 6 to 12 carbon atoms.
Or a heterocyclic ring containing a nitrogen atom and having 12 or less carbon atoms is preferable.

In the structural formulas [5] to [8], the alkyl group represented by R ₅ may have a substituent. Examples of the substituent include a halogen atom such as fluorine, chlorine and bromine, a hydroxyl group,
Examples include an alkoxy group such as methoxy and ethoxy, an aryloxy group such as phenoxy, an amide group such as cyano group and acetamit, and an alkoxycarbonyl group such as acetoxycarbonyl group. The structural formula [5] to
In [8], the aryl group represented by R ₅ may have a substituent, and examples of the substituent include a methyl group in addition to the substituents of the alkyl group represented by R _5. .

Preferred specific examples of the monomers represented by the structural formulas [5] to [8] of the component (3) are shown below, but the present invention is not limited to these specific examples. Absent.

The structural formulas (5) to (5) of the component (3)
Preferred specific examples of the monomer represented by [8] include:
For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, 2-chloroethyl (meth) ) Acrylate, cyclohexyl (meth) acrylate, 2
-Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycidyl (meth) Acrylate, diethylaminoethyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofuryl (meth) acrylate, phenyl (meth) acrylate, hydroxyphenyl (meth) acrylate, cresyl (meth) acrylate, naphthyl (meth)
(Meth) acrylates such as acrylate, benzyl (meth) acrylate, and methoxybenzyl (meth) acrylate;

(Meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-octyl (meth) acrylamide, N- Cyclohexyl (meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-benzyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-nitrophenyl (meth) acrylamide, N- (Meta) such as tolyl (meth) acrylamide, N-hydroxyphenyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dicyclohexyl (meth) acrylamide Acrylamide;

N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-pentylmaleimide, Nn-hexylmaleimide, N-laurylmaleimide, N-stearylmaleimide, N-cyclohexylmaleimide, N-substituted maleimides such as N-phenylmaleimide, N-chlorophenylmaleimide, N-tolylmaleimide, N-hydroxymaleimide, N-benzylmaleimide;

Allyl compounds such as allyl acetate, allyl caproate, allyl stearate and allyloxyethanol; ethyl vinyl ether, propyl vinyl ether,
Vinyl ethers such as butyl vinyl ether, octyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, phenyl vinyl ether, tolyl vinyl ether, and diethylaminoethyl vinyl ether;

Vinyl esters such as vinyl acetate, vinyl butyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxyacetate, vinyl phenyl acetate, vinyl acetoacetate, vinyl benzoate and vinyl chlorobenzoate;

Styrenes such as styrene, α-methylstyrene, methylstyrene, dimethylstyrene, chloromethylstyrene, ethoxymethylstyrene, hydroxystyrene, chlorostyrene and bromostyrene;

N-vinylpyrrolidone, N-vinylpyridine, acrylonitrile and the like can be mentioned.

In the present invention, particularly preferred among these components (3) are the monomers represented by the structural formulas [5] and [7].

As the component (3), in addition to the monomers represented by the structural formulas [5] to [8], other addition-polymerized unsaturated compounds can be optionally used. Examples of the polymerizable unsaturated compound include Pol
ymer Handbook 2nd ed. , J. et al. Br
andrup, Wiley Interscience
(1975) ChaPter 2 Page 1-483
What is described is mentioned.

In the present invention, the content of the component (3) is preferably from 5 to 80% by weight, more preferably from 10 to 70% by weight, based on the weight of the fluorinated copolymer. When the content is less than 5% by weight,
Fingerprint resistance may be inferior, and even if it exceeds 70% by weight, fingerprint resistance may be inferior, and neither is preferred. The component (3) may be used alone or in combination of two or more.

In the present invention, the fluorinated copolymer can be produced by a known and commonly used method. For example, a (meth) acrylate having a fluoroaliphatic group, a (meth) acrylate having an aliphatic group or an aromatic group, and an acidic group-containing vinyl monomer having an acidic hydrogen atom bonded to a nitrogen atom may be optionally added to other components. The polymerizable unsaturated compound can be produced by adding a known radical polymerization initiator in an organic solvent and subjecting it to thermal polymerization.

Hereinafter, specific examples of the fluorine-containing copolymer will be described, but the present invention is not limited to these specific examples. The suffix indicates the composition molar ratio.

[0048]

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[0049]

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[0050]

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In the present invention, the molecular weight of the fluorine-containing polymer ranges from 3000 to 2 as a weight average molecular weight.
About 000 to 100,000
0 is preferred.

In the present invention, the content of the fluorocopolymer is based on the total solid content of the image recording material.
It is preferably from 0.5 to 10% by weight, more preferably from 1 to 6% by weight. When the content is less than 0.5% by weight,
Fingerprint resistance may be inferior, and if it exceeds 10% by weight, the curability of the image recording material may decrease, and the film strength of the image portion may decrease, which is not preferable.

The components other than the component (E) of the negative image recording material of the present invention will be described below. [(A) Compound that decomposes by light or heat to generate an acid]
In the present invention, a compound that decomposes by light or heat to generate an acid (hereinafter, may be referred to as an “acid generator”).
Means a compound that generates an acid by irradiation with light having a wavelength of 200 to 500 nm or heating at 100 ° C. or higher. As the acid generator suitably used in the present invention, a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photodecolorant for dyes, a photochromic agent, or a microresist is used. Known compounds such as a known acid generator, which generates an acid by thermal decomposition, and a mixture thereof are exemplified.

For example, S.I. I. Schlesinge
r, Photogr. Sci. Eng. , 18,387
(1974); S. Bal et al, Poly
mer, 21,423 (1980), U.S. Pat. Nos. 4,069,055 and 4,062.
9,056 and Re27,992, and ammonium salts described in JP-A-4-365049.
D. C. Necker etal, Macromole
cules, 17, 2468 (1984), C.I. S. W
en et al, Teh, Proc. Conf. Ra
d, CuringASIA, p478 Tokyo, O
ct (1988), U.S. Pat. No. 4,069,055,
The phosphonium salts described in each specification of JP-A-4,069,056; V. Crivello et al, Mac
romolecules, 10 (6), 1307 (19
77), Chem. & Eng. News, Nov .; 2
8, p31 (1988), EP 104,143.
Nos. 339,049 and 410,201.
Nos., JP-A-2-150848, JP-A-2-150848
Iodonium salts described in each publication of J.
V. Crivello et al, Polymer
J. 17, 73 (1985); V. Crivell
o et al. J. Org. Chem. , 43,30
55 (1978); R. Watt et al,
J. Polymer Sci. , Polymer Ch
em. Ed. , 22, 1789 (1984); V.
Crivello et al, Polymer

Bull. , 14, 279 (1985),
J. V. Crivello et al, Macrom
olecules, 14 (5), 1141 (198
1). V. Crivello et al, J. Mol. P
polymer Sci. , Polymer Chem.
Ed. , 17, 2877 (1979), EP 37
Nos. 0,693, 390,214, 233,567
Nos. 297,443 and 297,442; U.S. Pat. Nos. 4,933,377; 161,811;
No. 10,201, No. 339,049, No. 4,760,
No. 013, No. 4,734,444, No. 2,833,8
No. 27, German Patent Nos. 2,904,626 and 3,60
4,580, 3,604,581, the sulfonium salt described in each specification,

J. V. Crivello et al,
Macromolecules, 10 (6), 1307
(1977); V. Crivello et a
1, J .; Polymer Sci. , Polymer
Chem. Ed. , 17, 1047 (1979); S. Wen et al, Te
h, Proc. Conf. Rad. Curing AS
Onium salts such as arsonium salts described in IA, p478 Tokyo, Oct (1988), US Pat.
No. 5,815,815, JP-B-46-4605, JP-A-48-36281, JP-A-55-32070, JP-A-55-32070.
0-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62-212401, JP-A-63-70243, and JP-A-63-298339. Organic halogen compounds, K. Meier et al, J. Mol. Rad. Cur
ing, 13 (4), 26 (1986); P. Gi
ll et al, Inorg. Chem. , 19,3
007 (1980); Astruc, Acc. Ch
em. Res. , 19 (12), 377 (1896),
Organometallic / organic halides described in JP-A-2-161445; Hayase et al, J. Mol. P
polymer Sci. , 25, 753 (1987),
E. FIG. Reichmanis et al. Poly
mer Sci. , Polymer Chem. E
d. , 23, 1 (1985); Q. Zhu et
al, J Photochem. , 36, 85, 39,
317 (1987); Amit et al, Te
trahedron Lett. , (24) 2205
(1973),

D. H. R. Barton et al,
J. Chem. Soc. 3571 (1965);
M. Collins et al, J. Mol. Chem. So
c. , Perkin I, 1695 (1975);
Rudinstein et al, Tetrahed
ron Lett. , (17), 1445 (197
5). W. Walker et al, J.A. Am.
Chem. Soc. , 110, 7170 (1988),
S. C. Busman et al, J. M .; Imagin
gTechnol. , 11 (4), 191 (198
5), H. M. Houlihan et al, Mac
romolecules, 21, 2001 (198
8), p. M. Collins et al, J. Mol. Ch
em. Soc. Chem. Commun. , 532
(1972); Hayase et al, Mac
romolecules, 18, 1799 (198
5), E. Reichmanis et al. E
electrochem. Soc. , SolidStat
e Sci. Technol. , 130 (6);
M. Houlihan et al, Macromol
ecules, 21, 2001 (1988), European Patent Nos. 0290,750, 046,083 and 15
6,535, 271 and 851, 0,388,3
No. 43, U.S. Pat. Nos. 3,901,710 and 4,18
1,531, JP-A-60-198538
Described in each gazette of JP-A-53-133022.
A photoacid generator having a nitrobenzyl-type protecting group; Tu
nooka et al, Polymer Prepr
ints Japan, 38 (8); Berner
et al, J.A. Rad. Curing, 13
(4); J. Mijs et al, Coatin
gTechnol. , 55 (697), 45 (198
3), Akzo, H .; Adachi et al, Po
lymer Preprints, Japan, 37
(3), European Patent Nos. 0199,672 and 84515
Nos. 199,672, 044,115, 01
No. 01,122, U.S. Pat. Nos. 4,618,564, 4,371,605 and 4,431,774, JP-A-64-18143, JP-A-2-2457.
No. 56, Japanese Patent Application No. 3-140109, and compounds which generate sulfonic acid upon photolysis, such as iminosulfonates, described in JP-A-61-166544.
And the disulfone compound described in JP-A No. 2000-163,078.

Compounds in which these acid-generating groups or compounds are introduced into the main chain or side chain of the polymer, for example, M.P. E. FIG. Woodhouse et al, J. Mol. A
m. Chem. Soc. , 104, 5586 (198
2), S.M. P. Pappaset al, J .; Imag
ing Sci. , 30 (5), 218 (1986),
S. Kondo et al. Makromol. C
hem. , RapidCommun. , 9, 625 (1
988); Yamada et al, Makro
mol. Chem. , 152, 153, 163 (197
2). V. Crivello et al. J. P
polymer Sci. , Polymer Chem.
Ed. , 17, 3845 (1979); U.S. Pat.
849,137, German Patent No. 3,914,407, JP-A-63-26653, JP-A-55-1.
No. 64824, JP-A-62-69263 and JP-A-63-69263
Compounds described in JP-A-146037, JP-A-63-163452, JP-A-62-153853, and JP-A-63-146029 can be used.

Further, V.I. N. R. Pilai, Syn
thesis, (1), 1 (1980); Abad
et al, Tetrahedron Lett. ,
(47) 4555 (1971); H. R. Bart
on et al, J.A. Chem, Soc,. (C),
329 (1970); U.S. Pat. No. 3,779,778.
And the compounds capable of generating an acid by light described in the specifications of European Patent No. 126,712 and the like can also be used.
Among these, examples of the acid generator particularly preferably used in the present invention include compounds represented by the following general formulas (I) to (V).

[0060]

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In the general formulas (I) to (V), R¹, R^Two, R
^FourAnd R^FiveMay be the same or different, and the substituent
Represents a hydrocarbon group having 20 or less carbon atoms which may be present
You. R ^ThreeIs a halogen atom, an optionally substituted carbon
Hydrocarbon groups with 10 or fewer primes or alcohols with 10 or fewer carbons
It represents a lucoxy group. Ar¹, Ar^TwoAre the same but different
Having 20 carbon atoms which may have a substituent
The following aryl groups are shown. R⁶May have a substituent
It represents a divalent hydrocarbon group having a good number of carbon atoms of 20 or less. n is
Shows an integer of 0 to 4.

In the general formulas (I) to (V), R ¹ , R
² , R ⁴ and R ⁵ each independently represent a hydrocarbon group which may have a substituent and has 20 or less carbon atoms, and preferably a hydrocarbon group having 1 to 14 carbon atoms. Specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, t-butyl, hexyl, cyclohexyl, octyl, and octyl. Alkyl groups such as -ethylhexyl group, undecyl group and dodecyl group, allyl group, vinyl group, 1-methylvinyl group, alkenyl group such as 2-phenylvinyl group,
Aralkyl groups such as benzyl group, phenyl group, tolyl group,
And aryl groups such as a xylyl group, a cumenyl group, a mesityl group, a dodecylphenyl group, a phenylphenyl group, a naphthyl group, and an anthracenyl group. These hydrocarbon groups may have a substituent such as a halogen atom, an alkoxy group, a nitro group, a cyano group, and a carboxy group.
Specific examples of the hydrocarbon group having a substituent include a trifluoromethyl group, a chloroethyl group, a 2-methoxyethyl group, a fluorophenyl group, a chlorophenyl group, a bromophenyl group, an iodophenyl group, a methoxyphenyl group, a phenoxyphenyl group, Examples include a methoxyphenylvinyl group, a nitrophenyl group, a cyanophenyl group, a carboxyphenyl group, and a 9,10-dimethoxyanthracenyl group.

In the general formulas (I) to (V), R ³ is a halogen atom, an optionally substituted hydrocarbon group having 10 or less carbon atoms (for example, an alkyl group, an alkenyl group,
An aralkyl group, an aryl group) or an alkoxy group having 10 or less carbon atoms. Specifically, fluorine, chlorine, bromine,
Halogen atom of iodine, methyl group, ethyl group, n-propyl group, i-propyl group, allyl group, n-butyl group, s
ec-butyl group, t-butyl group, hexyl group, cyclohexyl group, benzyl group, phenyl group, hydrocarbon group such as tolyl group, 2-methoxyethyl group, fluorophenyl group,
Chlorophenyl group, bromophenyl group, iodophenyl group, hydrocarbon group having a substituent such as methoxyphenyl group,
Examples include an alkoxy group such as a methoxy group and an ethoxy group. When n is 2 or more, two adjacent R ³ may be bonded to each other to form a ring.

In the general formulas (I) to (V), Ar ¹ ,
Ar ² may be the same or different and represents an aryl group having 20 or less carbon atoms, which may have a substituent, preferably an aryl group having 6 to 14 carbon atoms. Specifically, a phenyl group, a tolyl group, a xylyl group, a cumenyl group,
Mesityl group, dodecylphenyl group, phenylphenyl group, naphthyl group, fluorophenyl group, chlorophenyl group, bromophenyl group, iodophenyl group, chloronaphthyl group, methoxyphenyl group, phenoxyphenyl group,
Examples include an ethoxynaphthyl group, a nitrophenyl group, a cyanophenyl group, a carboxyphenyl group, a nitronaphthyl group, an anthracenyl group and the like.

In the general formulas (I) to (V), R ⁶ is an optionally substituted divalent hydrocarbon group having 20 or less carbon atoms (for example, an alkylene group, an alkenylene group, an aralkylene group, Arylene group). Specifically, an ethynylene group, a 1,2-cyclohexenylene group, a 1,2-phenylene group, a 4-chloro-1,2-phenylene group,
Nitro-1,2-phenylene group, 4-methyl-1,2-
Phenylene group, 4-methoxy-1,2-phenylene group,
4-carboxy-1,2-phenylene group, 1,8-naphthalenylene group and the like. n shows the integer of 0-4. Here, when n is 0, it indicates that there is no R ₃ , that is, it is a hydrogen atom.

Among the compounds represented by formulas (I) to (V), preferred ones are shown below. These compounds can be synthesized, for example, by the methods described in JP-A Nos. 2-100054 and 2-100055.

[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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As the compound (A) which is decomposed by light or heat to generate an acid, an onium salt having a counter ion of a halide or sulfonic acid, preferably represented by the following general formulas (VI) to (VIII) Preferred are those having any one of the structural formulas of iodonium salt, sulfonium salt, and diazonium salt.

[0079]

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In the general formulas (VI) to (VIII), X^-Is halo
Genide ion, ClO_Four ^-, PF ₆ ^-, SbF₆ ^-,
BF_Four ^-Or R⁷-SO_Three ^-Where R
⁷Is a hydrocarbon having 20 or less carbon atoms which may have a substituent
Represents an elementary group. Ar^Three, Ar^FourEach has a substituent
Represents an aryl group having 20 or less carbon atoms which may be present.
R ⁸, R⁹, R^TenRepresents an optionally substituted carbon number of 1
And 8 or less hydrocarbon groups.

[0081] In the general formula (VI) ~ (VIII), X - as a, R ⁷ -SO ₃ ^- is particularly preferably used, wherein the carbon atoms which may have a substituent as R ⁷ 20
The following hydrocarbon groups are shown. Specific examples of the hydrocarbon group represented by R ⁷ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an allyl group, an n-butyl group, and sec.
Alkyl groups such as -butyl group, t-butyl group, hexyl group, cyclohexyl group, octyl group, 2-ethylhexyl group, dodecyl group, vinyl group, 1-methylvinyl group, 2-
Aryl groups such as alkenyl groups such as phenylvinyl group, aralkyl groups such as benzyl group and phenethyl group, phenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, dodecylphenyl group, phenylphenyl group, naphthyl group and anthracenyl group Is mentioned. These hydrocarbon groups have a substituent such as a halogen atom, a hydroxy group, an alkoxy group, an allyloxy group, a nitro group, a cyano group, a carbonyl group, a carboxyl group, an alkoxycarbonyl group, an anilino group, and an acetamido group. Is also good.
Specific examples of the hydrocarbon group having a substituent include a trifluoromethyl group, a 2-methoxyethyl group, a 10-campanyl group, a fluorophenyl group, a chlorophenyl group, a bromophenyl group, an iodophenyl group, a methoxyphenyl group, and a hydroxy group. Examples include a phenyl group, a phenoxyphenyl group, a nitrophenyl group, a cyanophenyl group, a carboxyphenyl group, a methoxynaphthyl group, a dimethoxyanthracenyl group, a diethoxyanthracenyl group, and an anthraquinonyl group.

In the general formulas (VI) to (VIII),
r ³ and Ar ⁴ each represent an aryl group having 20 or less carbon atoms which may have a substituent, and specifically, a phenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a dodecylphenyl group , Phenylphenyl group, naphthyl group, anthracenyl group, fluorophenyl group, chlorophenyl group, bromophenyl group, iodophenyl group, methoxyphenyl group, hydroxyphenyl group, phenoxyphenyl group, nitrophenyl group, cyanophenyl group, carboxyphenyl group, Examples thereof include an anilinophenyl group, an anilinocarbonylphenyl group, a morpholinophenyl group, a phenylazophenyl group, a methoxynaphthyl group, a hydroxynaphthyl group, a nitronaphthyl group, and an anthraquinonyl group.

In the general formulas (VI) to (VIII), R ⁸ ,
R ⁹ and R ¹⁰ each independently represent a hydrocarbon group having 18 or less carbon atoms which may have a substituent, and specifically, a methyl group, an ethyl group, an n-propyl group, an i-propyl group ,
Hydrocarbon groups such as allyl group, n-butyl group, sec-butyl group, t-butyl group, hexyl group, cyclohexyl group, benzyl group, phenyl group, tolyl group, t-butylphenyl group, naphthyl group, anthracenyl group, etc. , 2-methoxyethyl, fluorophenyl, chlorophenyl, bromophenyl, iodophenyl, methoxyphenyl, hydroxyphenyl, phenylthiophenyl,
Examples thereof include a hydrocarbon group having a substituent such as a hydroxynaphthyl group, a methoxynaphthyl group, a benzoylmethyl group, a naphthoylmethyl group, and the like. Further, R ⁸ and R ⁹ may be bonded to each other to form a ring.

Examples of the cation portion of the onium salt represented by the general formulas (VI) to (VIII) include an iodonium ion, a sulfonium ion and a diazonium ion. Specific structures of the cation portion of these onium salts are shown below, but the invention is not limited thereto.

[0085]

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[0086]

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[0087]

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[0088]

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[0089]

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On the other hand, among the counter anions of these onium salts, particularly preferred examples of the sulfonate ion include: 1) methanesulfonate, 2) ethanesulfonate, 3) 1-propanesulfonate, 4) 2-propanesulfonate. 5) n-butanesulfonate, 6) allylsulfonate, 7) 10-camphorsulfonate, 8) trifluoromethanesulfonate, 9) pentafluoroethanesulfonate, 10) benzenesulfonate, 11) p-toluenesulfonate, 12) 3-methoxy Benzenesulfonate, 13) 4-methoxybenzenesulfonate, 14) 4-hydroxybenzenesulfonate, 15) 4-chlorobenzenesulfonate, 16) 3-nitrobenzenesulfonate, 17) 4-d Lobenzenesulfonate, 18) 4-acetylbenzenesulfonate, 19) pentafluorobenzenesulfonate, 20) 4-dodecylbenzenesulfonate, 21) mesitylenesulfonate, 22) 2,4,6-triisopropylbenzenesulfonate, 23) 2-hydroxy -4-methoxybenzophenone-
5-sulfonate, 24) dimethyl-5-sulfonate isophthalate, 25) diphenylamine-4-sulfonate, 26) 1-naphthalene sulfonate, 27) 2-naphthalene sulfonate, 28) 2-naphthol-6-sulfonate, 29) 2- Naphthol-7-sulfonate, 30) anthraquinone-1-sulfonate, 31) anthraquinone-2-sulfonate, 32) 9,10-dimethoxyanthracene-2-sulfonate, 33) 9,10-diethoxyanthracene-2-sulfonate, 34 ) Quinoline-8-sulfonate, 35) 8-hydroxyquinoline-5-sulfonate, 36) 8-anilino-naphthalene-1-sulfonate.

Also, 41) m-benzene disulfonate, 42) benzaldehyde-2,4-disulfonate, 43) 1,5-naphthalenedisulfonate, 44) 2,6-naphthalenedisulfonate, 45) 2, 7- Naphthalenedisulfonate, 46) anthraquinone-1,5-disulfonate, 47) anthraquinone-1,8-disulfonate, 48) anthraquinone-2,6-disulfonate, 49) 9,10-dimethoxyanthracene-2,6- Disulfonates, 50) 9,10-diethoxyanthracene-2,6-disulfonate, and the like, and salts of two equivalents of an onium salt cation can also be used.

The onium salt sulfonate preferably used in the present invention can be prepared by converting the corresponding Cl ^- salt or the like into a mixed solvent of sulfonic acid or sodium or potassium sulfonate and water, or a mixed solvent of a hydrophilic solvent such as alcohol and water. It can be obtained by performing salt exchange together.
Synthesis of the onium compound can be performed by a known method,
For example, Maruzen and New Experimental Chemistry Course 14-I, Chapter 2.3 (p.448), and Volume 14-III, Chapter 8.16 (p.18)
38), Chapter 7-14 (p. 1564); W. Kn
apczyk et al., Journal of American Chemical Society (J. Am. Chem. Soc.) 91
Vol., 145 (1969); L. Maycok et al., Journal of Organic Chemistry (J. Or
g. Chem. 35, 2532 (1970);
V. Crivello et al., Polymer Chemistry Edition (Polym. Chem. Ed.), Vol. 18,
2677 (1980); U.S. Pat. No. 2,807,648.
Nos. 4,247,473 and JP-A-53-473.
Compounds can be synthesized by the methods described in JP-B Nos. 101331 and 5-53166. Preferred examples of the onium salt sulfonate favorably used as an acid generator in the present invention are shown below.

[0093]

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[0094]

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[0095]

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[0096]

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[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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[0104]

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In the present invention, these acid generators are used in an amount of 0.01 to 50% by weight, preferably 0.1 to 25% by weight, more preferably 0.5 to 2% by weight based on the total solid content of the image recording material.
0% by weight is added to the image recording material. When the addition amount is less than 0.01% by weight, no image is obtained, and when the addition amount is more than 50% by weight, non-image portions are stained at the time of printing. These compounds may be used alone or in combination of two or more.

[(B) Crosslinking Agent Cross-Linked by Acid] A cross-linking agent crosslinked by an acid (hereinafter referred to as “B”) which can be used in the present invention.
The “acid crosslinking agent” or simply “crosslinking agent” as appropriate) will be described. Examples of the crosslinking agent preferably used in the present invention include the following. (I) an aromatic compound substituted with an alkoxymethyl group or a hydroxymethyl group (ii) a compound having an N-hydroxymethyl group, an N-alkoxymethyl group or an N-acyloxymethyl group (iii) an epoxy compound These will be described in detail. I do. (I) Examples of the aromatic compound substituted with an alkoxymethyl group or a hydroxymethyl group include an aromatic compound and a heterocyclic compound poly-substituted with a hydroxymethyl group, an acetoxymethyl group, or an alkoxymethyl group. . However, it does not include resinous compounds obtained by polycondensing phenols and aldehydes known as resol resins under basic conditions. Although the resole resin is excellent in crosslinkability, it does not have sufficient thermal stability. In particular, when the resol resin is contained in a photosensitive material and stored at a high temperature for a long period of time, uniform development becomes difficult, which is not preferable.

Among aromatic compounds and heterocyclic compounds poly-substituted with a hydroxymethyl group or an alkoxymethyl group, compounds having a hydroxymethyl group or an alkoxymethyl group at a position adjacent to the hydroxy group are preferred. it can. In the case of an alkoxymethyl group, the alkoxymethyl group is preferably a compound having 18 or less carbon atoms. Particularly preferred examples include compounds represented by the following general formulas (1) to (4).

[0108]

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[0109]

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In the general formulas (1) to (4), L _{1 to} L ₈ each independently represent a hydroxymethyl group or an alkoxymethyl group substituted by an alkoxy group having 18 or less carbon atoms such as methoxymethyl, ethoxymethyl and the like. Represents a group. These are preferred because they have high crosslinking efficiency and can improve printing durability. The crosslinking compounds exemplified above may be used alone or in combination of two or more.

(Ii) Compounds having an N-hydroxymethyl group, an N-alkoxymethyl group or an N-acyloxymethyl group include those disclosed in European Patent Publication (hereinafter referred to as EP-A) No. 0,133,216, West German Patent No. 3,6
No. 34,671, No. 3,711,264, monomer and oligomer-melamine-formaldehyde condensate and urea-formaldehyde condensate, EP-A
And the alkoxy-substituted compounds disclosed in Japanese Patent No. 0,212,482. More preferred examples include, for example, melamine-formaldehyde derivatives having at least two free N-hydroxymethyl groups, N-alkoxymethyl groups or N-acyloxymethyl groups, among which N-alkoxymethyl derivatives are particularly preferred.

(Iii) Examples of the epoxy compound include monomer, dimer, oligomer, and polymer epoxy compounds containing one or more epoxy groups. For example, a reaction product of bisphenol A with epichlorohydrin, a reaction product of a low molecular weight phenol-formaldehyde resin with epichlorohydrin and the like can be mentioned. Other examples include epoxy resins described and used in U.S. Pat. No. 4,026,705 and British Patent 1,539,192.

The crosslinking agent (i) to (iii) which can be used in the present invention is 5 to 5% of the total solid content of the image recording material.
It is in the range of -80% by weight, preferably 10-75% by weight, particularly preferably 20-70% by weight. If the addition amount of the crosslinking agent is less than 5% by weight, the durability of the photosensitive layer of the obtained image recording material is deteriorated, and if it exceeds 80% by weight, it is not preferable from the viewpoint of storage stability.

(Iv) In the present invention, it is also preferable to use a phenol derivative represented by the following general formula (5) as a crosslinking agent.

[0115]

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In the above general formula (5), Ar ¹ represents an aromatic hydrocarbon ring which may have a substituent. From the viewpoint of availability of raw materials, the aromatic hydrocarbon ring is preferably a benzene ring, a naphthalene ring or an anthracene ring. Preferred examples of the substituent include a halogen atom, a hydrocarbon group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, an alkylthio group having 12 or less carbon atoms, a cyano group, a nitro group, and a trifluoromethyl group. Is mentioned. Because of high sensitivity, Ar ¹ includes an unsubstituted benzene ring and a naphthalene ring, or a halogen atom,
Hydrocarbon groups or less, alkoxy groups having 6 or less carbon atoms,
A benzene ring and a naphthalene ring each having, as a substituent, an alkylthio group or a nitro group having 6 or less carbon atoms are particularly preferable. In the general formula (5), R ¹ and R ² may be the same or different, and each represents a hydrogen atom or a carbon atom
And not more than hydrocarbon groups. It is particularly preferable that R ¹ and R ² are a hydrogen atom or a methyl group because of easy synthesis. R ³ is a hydrogen atom or a carbon atom
And not more than hydrocarbon groups. Because of the high sensitivity,
R ³ is particularly preferably a hydrocarbon group having 7 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group, a cyclohexyl group, and a benzyl group. m shows the integer of 2-4. n shows the integer of 1-3.

Specific examples of the phenol derivative represented by formula (5) preferably used in the present invention are shown below (crosslinking agents [KZ-1] to [KZ-8]). It is not limited to.

[0118]

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[0119]

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These phenol derivatives can be synthesized by a conventionally known method. For example, [KZ-1] reacts phenol, formaldehyde, and a secondary amine such as dimethylamine and morpholine to form tri (dialkylaminomethyl) phenol, and then reacts with acetic anhydride.
Further, by reacting with ethanol in the presence of a weak alkali such as potassium carbonate, the compound can be synthesized by a route represented by the following reaction formula [1]. Reaction formula [1]

[0121]

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Further, it can be synthesized by another method.
For example, [KZ-1] is obtained by reacting phenol with formaldehyde or paraformaldehyde in the presence of an alkali such as KOH to give 2,4,6-trihydroxymethylphenol, and then reacting with ethanol in the presence of an acid such as sulfuric acid. Thus, the compound can also be synthesized by a route represented by the following reaction formula [2]. Reaction formula [2]

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These phenol derivatives may be used alone or in combination of two or more. Further, when synthesizing these phenol derivatives, the phenol derivatives may condense with each other to produce by-products such as dimers and trimers, but the phenol derivatives may be used while containing these impurities. In this case, the impurity is 3
It is preferably at most 0%, more preferably at most 20%.

In the present invention, the phenol derivative accounts for 5 to 70% by weight, preferably 10% by weight, based on the total solid content of the image recording material.
It is used in an amount of 〜50% by weight. Here, when the addition amount of the phenol derivative as a cross-linking agent is less than 5% by weight, the film strength of the image portion when the image is recorded is deteriorated.
Exceeding 0% by weight is not preferred in terms of stability during storage.

[(C) Alkali-soluble resin] Examples of the alkali-soluble resin used in the present invention include a novolak resin and a polymer having a hydroxyaryl group in a side chain. The novolak resin that can be used as the alkali-soluble resin in the present invention is a resin obtained by condensing phenols and aldehydes under acidic conditions. Preferred novolak resins include, for example, a novolak resin obtained from phenol and formaldehyde, a novolak resin obtained from m-cresol and formaldehyde,
Novolak resin obtained from p-cresol and formaldehyde, novolak resin obtained from o-cresol and formaldehyde, novolak resin obtained from octylphenol and formaldehyde, novolak resin obtained from m- / p-mixed cresol and formaldehyde, phenol / cresol ( m-, p-, o- or m
-/ P-, m- / o-, o- / p-) and a novolak resin obtained from formaldehyde. These novolak resins are
Those having a weight average molecular weight of 800 to 200,000 and a number average molecular weight of 400 to 60,000 are preferred.

Further, as the alkali-soluble resin in the present invention, a polymer having a hydroxyaryl group in a side chain can also be preferably mentioned. In this polymer, a hydroxyaryl group refers to an aryl group in which one or more -OH groups are bonded. Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, and a phenanthrenyl group. From the viewpoint of availability and physical properties, a phenyl group or a naphthyl group is preferable. Accordingly, the hydroxyaryl group is preferably a hydroxyphenyl group, a dihydroxyphenyl group, a trihydroxyphenyl group, a tetrahydroxyphenyl group, a hydroxynaphthyl group, a dihydroxynaphthyl group, or the like. These hydroxyaryl groups may further have a substituent such as a halogen atom, a hydrocarbon group having 20 or less carbon atoms, an alkoxy group having 20 or less carbon atoms, and an aryloxy group having 20 or less carbon atoms. Good. These hydroxyaryl groups are pendantly bonded to the polymer main chain as side chains of the polymer, but may have a linking group with the main chain.

The polymer having a hydroxyaryl group in the side chain suitably used in the present invention is a polymer containing any one of the structural units represented by the following general formulas (IX) to (XII). .

[0129]

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In the general formulas (IX) to (XII), R ¹¹ represents a hydrogen atom or a methyl group. R ¹² and R ¹³ may be the same or different and are a hydrogen atom, a halogen atom, a hydrocarbon group having 10 or less carbon atoms, an alkoxy group having 10 or less carbon atoms, or an aryloxy group having 10 or less carbon atoms. Is shown. R ¹² and R ¹³ may combine to form a condensed benzene ring or cyclohexane ring. R ¹⁴ represents a single bond or a divalent hydrocarbon group having 20 or less carbon atoms. R ¹⁵
Represents a single bond or a divalent hydrocarbon group having 20 or less carbon atoms. R ¹⁶ represents a single bond or a divalent hydrocarbon group having 10 or less carbon atoms. X1 is a single bond, an ether bond,
Shows a thioether bond, an ester bond or an amide bond. p shows the integer of 1-4. q and r are each 0
Indicates an integer of 3. )

Among the structural units represented by formulas (IX) to (XII), examples of specific structural units suitably used in the present invention are shown below.

[0132]

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[0133]

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[0134]

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[0135]

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[0136]

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These polymers can be synthesized by a conventionally known method. For example, a polymer having a structural unit represented by the general formula (IX) is obtained by subjecting a corresponding styrene derivative in which a hydroxy group is protected as an acetic ester or t-butyl ether to a polymer by radical polymerization or anion polymerization, and then deprotecting the polymer. It is obtained by doing. Polymers having a structural unit represented by formula (X) are described in JP-A-64-32256 and JP-A-64-32256.
The compound can be synthesized by a method described in each publication of JP-A-35436. Further, the polymer having the structural unit represented by the general formula (XI) is obtained by reacting an amine compound having a hydroxy group with maleic anhydride to obtain a corresponding monomer, and then forming the polymer by radical polymerization. . Further, the polymer having the structural unit represented by the general formula (XII) is derived from a styrene having a functional group useful in synthesis such as chloromethylstyrene or carboxystyrene as a raw material to a monomer corresponding to the general (XII). And further obtained by making it into a rimer by radical polymerization.

In the present invention, a homopolymer composed of only the structural units represented by the general formulas (IX) to (XII) may be used, or a copolymer containing other structural units may be used. Other structural units suitably used include, for example, acrylic esters, methacrylic esters, acrylamides, methacrylamides, vinyl esters, styrenes, acrylic acid, methacrylic acid, acrylonitrile, maleic anhydride, maleic anhydride Structural units introduced from known monomers such as acid imides are exemplified.

Specific examples of the acrylates that can be used include methyl acrylate, ethyl acrylate, (n- or i-) propyl acrylate, and (n
-, I-, sec- or t-) butyl acrylate, amyl acrylate, 2-ethylhexyl acrylate,
Dodecyl acrylate, chloroethyl acrylate, 2
-Hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 5-hydroxypentyl acrylate, cyclohexyl acrylate, allyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, methoxy benzyl acrylate, chlorobenzyl acrylate, 2- (P-hydroxyphenyl) ethyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, chlorophenyl acrylate, sulfamoylphenyl acrylate, and the like.

Specific examples of the methacrylates include methyl methacrylate, ethyl methacrylate,
(N- or i-) propyl methacrylate, (n-, i
-, Sec- or t-) butyl methacrylate, amyl methacrylate, 2-ethylhexyl methacrylate,
Dodecyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 5-hydroxypentyl methacrylate, cyclohexyl methacrylate, allyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate,
Examples include glycidyl methacrylate, methoxybenzyl methacrylate, chlorobenzyl methacrylate, 2- (p-hydroxyphenyl) ethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, chlorophenyl methacrylate, and sulfamoylphenyl methacrylate.

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

Specific examples of methacrylamides include methacrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, N-propyl methacrylamide, N-butyl methacrylamide, N-benzyl methacrylamide, N-hydroxyethyl methacryl Amide,
N-phenyl methacrylamide, N-tolyl methacrylamide, N- (p-hydroxyphenyl) methacrylamide, N- (sulfamoylphenyl) methacrylamide, N- (phenylsulfonyl) methacrylamide, N
-(Tolylsulfonyl) methacrylamide, N, N-dimethylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-hydroxyethyl-N-methylmethacrylamide and the like.

Specific examples of vinyl esters include vinyl acetate, vinyl butyrate, vinyl benzoate and the like. Specific examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, propylstyrene, cyclohexylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, methoxystyrene, and dimethoxystyrene. , Chlorostyrene, dichlorostyrene, bromostyrene, iodostyrene, fluorostyrene, carboxystyrene and the like.

Of these monomers, particularly preferably used are acrylic esters, methacrylic esters, acrylamides, methacrylamides, vinyl esters, styrenes and acrylic acids having 20 or less carbon atoms. Methacrylic acid and acrylonitrile.

The proportion of the structural units represented by the general formulas (IX) to (XII) contained in the copolymers using them is from 5 to 1
00% by weight, more preferably 1% by weight.
0 to 100% by weight. Further, the molecular weight of the polymer used in the present invention is preferably 4000 in terms of weight average molecular weight.
And more preferably in the range of 10,000 to 300,000, preferably in the number average molecular weight of 1,000 or more, and more preferably in the range of 2000 to 250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, more preferably in the range of 1.1 to 10. These polymers are random polymers, block polymers,
Although any of a graft polymer and the like may be used, a random polymer is preferable.

The alkali-soluble resin used in the present invention may be used alone or in combination of two or more. The alkali-soluble resin is used in an amount of 5 to 95% by weight, preferably 10 to 95% by weight, particularly preferably 20 to 90% by weight, based on the total solid content of the image recording material. If the added amount of the alkali-soluble resin is less than 5% by weight, the durability of the recording layer deteriorates, and if the added amount exceeds 95% by weight, no image is formed.

[(D) Infrared absorber] The infrared absorber used in the present invention has a wavelength of 760 nm to 1200.
It is a dye or pigment that effectively absorbs infrared rays of nm. Preferably, the dye or the pigment has an absorption maximum at a wavelength of 760 nm to 1200 nm. As the dye, commercially available dyes and known dyes described in literatures (for example, "Dye Handbook" edited by The Society of Synthetic Organic Chemistry, published in 1970) can be used. Specifically, dyes such as azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, and metal thiolate complexes Is mentioned. Preferred dyes include, for example, those described in
-125246, JP-A-59-84356, JP-A-59-84356
Cyanine dyes described in JP-A-202829 and JP-A-60-78787;
6, JP-A-58-181690, JP-A-58-1945
Methine dyes described in Japanese Unexamined Patent Publication No.
8-112793; JP-A-58-224793; JP-A-59-48187; JP-A-59-73996;
Naphthoquinone dyes described in JP-A-52-940 and JP-A-60-63744;
Squarylium dyes described in JP 792 and the like, cyanine dyes described in British Patent No. 434,875, and the like.

The near-infrared absorption sensitizer described in US Pat. No. 5,156,938 is also preferably used, and the substituted sensitizer described in US Pat. No. 3,881,924 is used. Arylbenzo (thio) pyrylium salts described in JP-A-57-142645 (U.S. Pat. No. 4,327,1).
No. 69), a trimethine thiapyrylium salt described in
JP-A-58-181051, JP-A-58-220143, JP-A-59-41363, JP-A-59-84248, and JP-A-59-84
249, 59-146063, 59-146061
Pyrylium compounds described in JP-A-59-2
Cyanine dyes described in U.S. Pat.
Pentamethine thiopyrylium salt described in JP-A-83,475, JP-B-5-13514 and JP-B-5-19702.
The pyrylium compounds disclosed in the above publications are also preferably used. Further, as another preferable example of the dye, the compound represented by the formula (I) in U.S. Pat. No. 4,756,993,
Near-infrared absorbing dyes described as (II) can be mentioned. Among these dyes, particularly preferred are cyanine dyes, squarylium dyes, pyrylium salts, and nickel thiolate complexes.

The pigment used in the present invention includes
Commercial Pigment and Color Index (CI) Handbook,
"Latest Pigment Handbook" (edited by Japan Pigment Technical Association, 1977), "Latest Pigment Application Technology" (CMC Publishing, 1986), "Printing Ink Technology" CMC Publishing, 1984)
Can be used. The types of pigments include black pigment, yellow pigment, orange pigment, brown pigment,
Red pigment, purple pigment, blue pigment, green pigment, fluorescent pigment,
Metal powder pigments and other polymer-bound dyes can be used.
Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelated azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments And quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black and the like. Preferred among these pigments is carbon black.

The pigment may be used without surface treatment, or may be used after surface treatment. Methods of surface treatment include a method of surface-coating a resin or wax, a method of attaching a surfactant, and a reactive substance (for example, a silane coupling agent, an epoxy compound, or a polyisocyanate).
Can be conceived on the surface of the pigment. The above surface treatment methods are described in "Properties and Applications of Metallic Soap" (Koshobo),
It is described in "Printing Ink Technology" (CMC Publishing, 1984) and "Latest Pigment Application Technology" (CMC Publishing, 1986).

The pigment has a particle size of 0.01 μm to
10 μm, preferably 0.05 μm to 1 μm
Is more preferable, and particularly preferably 0.1 μm to 1 μm. The particle size of the pigment is 0.01 μm
If it is less than 10 μm, it is not preferred in terms of the stability of the dispersion in the coating solution for the photosensitive layer. As a method of dispersing the pigment, a known dispersing technique using a dispersing machine, which is widely 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. Detail is,
It is described in "Latest Pigment Application Technology" (CMC Publishing, 1986).

The content of these dyes or pigments in the image recording material is based on the total solid content of the image recording material.
About 0.01 to 50% by weight, and 0.1 to 10% by weight
Preferably, in the case of a dye, 0.5 to 10% by weight is particularly preferable, and in the case of a pigment, 1.0 to 10% by weight is particularly preferable. The amount of the pigment or dye added is 0.01
When the amount is less than 50% by weight, the sensitivity is lowered. These dyes or pigments may be added to the same layer as other components,
Another layer may be provided and added thereto.

[Other Components] In the present invention, the above five components are essential, but 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 a colorant for an image. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green B
G, oil blue BOS, oil blue # 603, oil black BY, oil black BS, oil black T-505 (all manufactured by Orient Chemical Industries, Ltd.), Victoria Pure Blue, crystal violet (CI4
2555), methyl violet (CI42535),
Ethyl violet, rhodamine B (CI145170
B), malachite green (CI42000), methylene blue (CI52015), etc.
And dyes described in JP-293247. These dyes are preferably added because the image area and the non-image area can be easily distinguished after image formation. The amount of addition was 0.1 to the total solid content of the image recording material.
It is a ratio of 01 to 10 wt%.

In the negative type image recording material of the present invention, in order to increase the stability of processing under development conditions,
JP-A-62-251740 and JP-A-3-2085
Non-ionic surfactants described in JP-A No. 14-114, JP-A-59-121044 and JP-A-4-1314.
An amphoteric surfactant as described in each publication of JP-A No. 9 can be added. Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, monoglyceride stearic acid, and polyoxyethylene nonyl phenyl ether. Specific examples of the amphoteric surfactant include alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N, N- Betaine type (for example, trade name Amogen K, manufactured by Daiichi Kogyo Co., Ltd.) and the like. The proportion of the nonionic surfactant and amphoteric surfactant in the image recording material is 0.05 to 1
5% by weight is preferred, more preferably 0.1-5% by weight
It is.

Further, a plasticizer may be added to the negative-working image recording material of the present invention, if necessary, to impart flexibility to the coating film. For example, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, oligomers of acrylic acid or methacrylic acid And polymers. In addition to these, epoxy compounds, vinyl ethers and the like may be added.

The negative type image recording material of the present invention can be usually produced by dissolving each of the above-mentioned components in a solvent and coating it on a suitable support. As the solvent used herein, 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 Ethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, γ-butyllactone, toluene, water and the like. However, the present invention is not limited to this. These solvents are used alone or as a mixture.
The concentration of the above components (total solids including additives) in the solvent,
Preferably it is 1 to 50% by weight. The amount of coating (solid content) on the support obtained after coating and drying varies depending on the application, but generally speaking, about a lithographic printing plate material, it is not more than 0.1%.
5~5.0g / m ² is preferred. As a method of applying, various methods can be used, for example, bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating,
Roll coating and the like can be mentioned. As the coating amount decreases, the apparent sensitivity increases, but the film characteristics of the negative type image recording material deteriorate.

In the negative image recording material of the present invention, a surfactant for improving coating properties, for example, a fluorine-based surfactant described in JP-A-62-170950 is added. can do. The preferable addition amount is 0.01 to 1% by weight, more preferably 0.05 to 0.5% by weight, based on the total solid content of the image recording material.

The support used in the present invention is a dimensionally stable plate-like material such as paper, plastic (eg, polyethylene, polypropylene, polystyrene, etc.) laminated paper, metal plate ( For example, aluminum, zinc, copper, etc.), plastic film (for example, 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 film on which a metal is laminated or vapor-deposited as described above. As the support used in the present invention, a polyester film or an aluminum plate is preferable, and among them, an aluminum plate which has good dimensional stability and is relatively inexpensive is particularly preferable. Suitable aluminum plates are a pure aluminum plate and an alloy plate containing aluminum as a main component and containing a trace amount of a different element, and may be a plastic film on which aluminum is laminated or vapor-deposited. The foreign elements contained in the aluminum alloy include:
Silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, titanium and the like. The content of the foreign element in the alloy is at most 10% by weight or less. Aluminum which is particularly preferred in the present invention is pure aluminum. However, completely pure aluminum is difficult to produce due to refining technology, and therefore may contain a slightly different element.
As described above, the composition of the aluminum plate applied to the present invention is not specified, and an aluminum plate of a conventionally known and used material can be appropriately used. The thickness of the aluminum plate used in the present invention is about 0.1
mm to 0.6 mm, preferably 0.15 mm to 0.1 mm.
4 mm, particularly preferably 0.2 mm to 0.3 mm.

Prior to roughening the aluminum plate, if necessary, a degreasing treatment with, for example, a surfactant, an organic solvent or an alkaline aqueous solution is performed to remove rolling oil on the surface. The surface roughening treatment of the aluminum plate
The method is performed by various methods, for example, a method of mechanically roughening the surface, a method of electrochemically dissolving and roughening the surface, and a method of chemically selectively dissolving the surface. As a mechanical method, a known method such as a ball polishing method, a brush polishing method, a blast polishing method, and a buff polishing method can be used. In addition, as an electrochemical surface roughening method, there is a method of performing an alternating or direct current in a hydrochloric acid or nitric acid electrolyte.
Further, as disclosed in JP-A-54-63902, a method in which both are combined can be used. The aluminum plate thus roughened is subjected to an alkali etching treatment and a neutralization treatment as required, and then subjected to an anodic oxidation treatment as required to increase the water retention and abrasion resistance of the surface. As the electrolyte used for the anodic oxidation treatment of the aluminum plate, various electrolytes that form a porous oxide film can be used. Generally, sulfuric acid, phosphoric acid,
Oxalic acid, chromic acid or a mixed acid thereof is used. The concentration of these electrolytes is appropriately determined depending on the type of the electrolyte.

The conditions of the anodizing treatment vary depending on the electrolyte used, and thus cannot be specified unconditionally. However, in general, the concentration of the electrolyte is 1 to 80% by weight, the solution temperature is 5 to 70 ° C., and the current density is 5 to 60 A. / Dm ² , a voltage of 1 to 100 V, and an electrolysis time of 10 seconds to 5 minutes are appropriate. When the amount of the anodic oxide film is less than 1.0 g / m ² , the printing durability is insufficient or the non-image portion of the lithographic printing plate is easily scratched,
So-called "scratch stains" in which ink adheres to scratches during printing are likely to occur. After the anodizing treatment, the aluminum surface is subjected to a hydrophilic treatment as necessary. U.S. Pat. Nos. 2,7,7
No. 14,066, No. 3,181,461, No. 3,2
There is an alkali metal silicate (for example, sodium silicate aqueous solution) method as disclosed in the specifications of Nos. 80,734 and 3,902,734. In this method, the support is immersed or electrolytically treated with an aqueous solution of sodium silicate. Further, potassium fluorozirconate disclosed in JP-B-36-22063 and U.S. Pat. Nos. 3,276,868 and 4,153,46 are disclosed.
For example, a method of treating with polyvinyl phosphonic acid as disclosed in the specifications of JP-A Nos. 1 and 4,689,272 is used.

In the negative image recording material of the present invention, an undercoat layer can be provided on the support, if necessary. As the undercoat layer component, various organic compounds are used, for example, carboxymethyl cellulose, dextrin, gum arabic, phosphonic acids having an amino group such as 2-aminoethylphosphonic acid, and phenyl which may have a substituent. Organic phosphonic acids such as phosphonic acid, naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid, optionally substituted phenylphosphoric acid, naphthylphosphoric acid, alkylphosphoric acid and glyceroline Organic phosphoric acids such as acids, organic phosphinic acids such as phenylphosphinic acid, naphthylphosphinic acid, alkylphosphinic acid and glycerophosphinic acid which may have a substituent, amino acids such as glycine and β-alanine, and triethanolamine Hydroxy such as hydrochloride -Alanine, and hydrochlorides of amines having a, may be used by mixing two or more. The coating amount of the organic undercoat layer is suitably from ² to 200 mg / m ² .

As described above, a planographic printing plate using the negative image recording material of the present invention can be prepared. This lithographic printing plate material has a wavelength of 760 nm to 120.
Image exposure is performed by a solid-state laser and a semiconductor laser that emit 0-nm infrared light. In the present invention, the developing treatment may be performed immediately after the laser irradiation, but it is preferable to perform the heating treatment between the laser irradiation step and the developing step. The heat treatment is preferably performed in a range of 80 ° C. to 150 ° C. for 10 seconds to 5 minutes. By this heat treatment, the laser energy required for recording at the time of laser irradiation can be reduced.

After performing a heat treatment as required, the negative type image recording material of the present invention is developed with an alkaline aqueous solution. As the developer and replenisher for the negative-working image recording material of the present invention, conventionally known aqueous alkaline solutions can be used. For example, sodium silicate, potassium, tribasic sodium, potassium, ammonium, dibasic sodium, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium bicarbonate, potassium, potassium Ammonium, sodium borate, potassium, ammonium, sodium hydroxide,
And inorganic alkali salts such as ammonium, potassium and lithium. Also, monomethylamine, dimethylamine, trimethylamine, monoethylamine,
Organic alkaline agents such as diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine and pyridine are also used. Can be These alkali agents may be used alone or in combination of two or more. Among these alkali agents, particularly preferred developers are aqueous silicate solutions such as sodium silicate and potassium silicate. The reason is that the developability can be adjusted by the ratio and concentration of silicon oxide SiO ₂ and alkali metal oxide M ₂ O which are components of silicate.
No. 4, the alkali metal silicate described in JP-B-57-7427 is effectively used.

In the case of further developing using an automatic developing machine, an aqueous solution having a higher alkali strength than the developing solution (replenisher)
It has been known that a large amount of lithographic printing plate material can be processed without replacing the developing solution in the developing tank for a long time by adding to the developing solution. This replenishment system is also preferably applied in the present invention. Various surfactants and organic solvents can be added to the developing solution and the replenishing solution as needed for the purpose of accelerating or suppressing the developing property, dispersing the developing residue and improving the ink affinity of the printing plate image area. Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants. Further, the developing solution and the replenisher may contain, if necessary, a reducing agent such as a sodium salt or a potassium salt of an inorganic acid such as hydroquinone, resorcinol, sulfurous acid, and bisulfite, and further include an organic carboxylic acid, an antifoaming agent, and a water softener. Can be added. The printing plate developed using the above developer and replenisher is post-treated with washing water, a rinsing solution containing a surfactant and the like, and a desensitizing solution containing gum arabic and a starch derivative. As the post-processing when the negative-type image recording material of the present invention is used as a printing plate, various combinations of these processings can be used.

In recent years, in the plate making and printing industry, automatic developing machines for printing plate materials have been widely used in order to rationalize and standardize plate making operations. This automatic developing machine generally consists of a developing section and a post-processing section, and consists of a device for transporting printing plate material, each processing solution tank and a spray device, and pumps the exposed printing plate horizontally while pumping it. Each processing liquid is sprayed from a spray nozzle to perform development processing. Recently, a method has been known in which a printing plate material is immersed and transported by a submerged guide roll or the like in a processing liquid tank filled with a processing liquid, and the processing is performed. In such an automatic processing, the processing can be performed while replenishing each processing liquid with a replenisher according to the processing amount, the operating time, and the like. Further, a so-called disposable processing method in which processing is performed with a substantially unused processing liquid can also be applied.

The lithographic printing plate obtained as described above can be subjected to a printing step after coating with a desensitized gum if desired. However, when a lithographic printing plate having a higher printing durability is desired to be obtained, Is subjected to a burning process. When burning a lithographic printing plate, before burning,
-2518, 55-28062, JP-A-62-318
It is preferable to carry out treatment with a surface-regulating liquid as described in JP-A Nos. 59 and 61-159655. As a method, a sponge or absorbent cotton impregnated with the surface conditioning liquid is applied on a lithographic printing plate, or a method in which the printing plate is immersed in a vat filled with the surface conditioning solution and applied, Application by an automatic coater or the like is applied. Further, it is more preferable to make the application amount uniform with a squeegee or a squeegee roller after the application. The application amount of the surface conditioning liquid is generally 0.03 to 0.8 g / m ² (dry weight).
Is appropriate.

The lithographic printing plate to which the surface conditioning liquid has been applied is dried if necessary, and then heated to a high temperature with a burning processor (eg, a burning processor sold by Fuji Photo Film Co., Ltd .: BP-1300). Is done. The heating temperature and time in this case depend on the type of the component forming the image, but may be 1 to 100 ° C. to 300 ° C.
A range of up to 20 minutes is preferred. The burned lithographic printing plate can be subjected to conventional treatments such as washing with water and gumming, if necessary.However, a surface conditioning liquid containing a water-soluble polymer compound or the like is used. In such a case, a so-called desensitizing treatment such as gumming can be omitted. The lithographic printing plate obtained by such a process is set on an offset printing machine or the like and used for printing a large number of sheets.

[0168]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, and examples of synthesizing a fluorine-containing copolymer will be shown along with examples. However, the present invention is not limited to these specific examples. is not.

<Fluorine-Containing Copolymer [P-
1], [P-2], [P-3], and [P-
Synthesis Example of 4]> 2- (purple orooctyl) ethyl acrylate, N- (4-sulfamoylphenyl) methacrylamide, and 2-ethylhexyl methacrylate in an N, N-dimethylacetamide solvent in 2,2 ′
Radical polymerization was carried out using -azobis (2,4-dimethylvaleronitrile) as a polymerization initiator to obtain the fluorine-containing copolymer [P-1]. The weight-average molecular weight measured by GPC was 28,000. In the same manner as described above, [P-
2] and the fluorinated copolymers of [P-3] and [P-4] were obtained. When the weight average molecular weight was measured by GPC, they were 18,000, 15,000, and 2.2, respectively.
10,000 fluorine-containing copolymers. .

<Polymer Compounds [R-1] and [R-2]
Synthesis Example> In the same manner as in the above-mentioned synthesis example of the fluorine-containing copolymer, a polymer of a copolymer of 30 mol% of N- (4-sulfamoylphenyl) methacrylamide and 70 mol% of 2-ethylhexyl methacrylate Compound [R-
1] was synthesized. When the weight average molecular weight was measured by GPC, it was a high molecular compound of 25,000. Furthermore, in the same manner, a polymer compound [R-2] of a copolymer of 30 mol% of 2- (purple octyl) ethyl acrylate and 70 mol% of 2-ethylhexyl methacrylate was synthesized. When the weight average molecular weight was measured by GPC, it was a 32,000 high molecular compound.

<Synthesis of Crosslinking Agent [KZ-9]> 1- [α-
Methyl-α- (4-hydroxyphenyl) ethyl] -4
-[Α, α-bis (4-hydroxyphenyl) ethyl]
Benzene was reacted with formalin in aqueous potassium hydroxide solution. The reaction solution was acidified with sulfuric acid, crystallized, and recrystallized from methanol to obtain a crosslinking agent [KZ-9] having the following structure. The purity was measured by reverse phase HPLC to be 92%.

[0172]

Embedded image

<Synthesis of Crosslinking Agent [KZ-10]> o-Cresol was reacted with paraformaldehyde in an aqueous potassium hydroxide solution. The reaction solution was acidified with sulfuric acid, crystallized, and further purified by column chromatography to obtain a cross-linking agent [KZ-10] having the following structure. The purity was measured by reverse phase HPLC to be 96%.

[0174]

Embedded image

<Preparation of Binder Polymer [BP-1]> Poly (p-hydroxystyrene) and Marca Linker MS-4P (trade name) manufactured by Maruzen Petrochemical Co., Ltd. were obtained, and [BP-1] and did.

(Examples 1-4) Al having a thickness of 0.30 mm
Trichlorethylene cleaning of minium plate (material 1050)
And degrease, then use a nylon brush and 400 mesh
Use a miston-water suspension to grain the surface,
Washed with water. This plate is made of 25% sodium hydroxide at 45 ° C.
After immersion in an aqueous solution for 9 seconds for etching and washing with water,
2% HNO _ThreeFor 20 seconds and washed with water. At this time
The amount of etching of the grained surface is about 3g / m^TwoSo
Was. Next, this plate is_TwoSO_FourCurrent density as electrolyte
Degree 15A / dm^Two3g / m^TwoDC anodized film
After drying, it was washed with water and dried. Next, add the following
An undercoat solution was applied and dried at 80 ° C. for 30 seconds. After drying
10 mg / m^TwoMet.

Undercoat solution β-alanine 0.1 g Phenylphosphonic acid 0.05 g Methanol 40 g Pure water 60 g

Next, the following solution [G] was prepared, and this solution was applied to the above-mentioned primed aluminum plate.
Dry at 0 ° C. for 1 minute to prepare a negative type lithographic printing plate [G-1]
To [G-4]. The coated amount after drying is 1.5 g / m ²
Met.

Solution [G] Fluorine-containing copolymer 0.05 g Acid generator [SH-1] 0.3 g Crosslinker 0.5 g Binder polymer [BP-1] 1.5 g Infrared absorber [IK- 1] 0.07 g AIZEN SPILON BLUE C-RH 0.035 g (manufactured by Hodogaya Chemical Co., Ltd.) Megafac F-177 0.01 g (manufactured by Dainippon Ink and Chemicals, Inc., fluorine surfactant) Methyl ethyl ketone 12 g Methyl alcohol 10 g 1-methoxy-2-propanol 8 g

Table 1 shows the fluorinated copolymers and crosslinking agents used in Solutions [G-1] to [G-4]. Also,
The structures of the acid generator [SH-1] and the infrared absorber [IK-1] are shown below.

[0181]

[Table 1]

[0182]

Embedded image

The obtained negative type lithographic printing plate material [G-1]
To the surface of [G-4] with bare hands,
Scanning exposure was performed using a semiconductor laser that emits infrared light of about 850 nm. After exposure, 3 hours at 110 ° C with panel heater
After heat treatment for 0 second, development was carried out with a developing solution DP-4 (1: 8 water dilution) manufactured by Fuji Photo Film Co., Ltd. After the image formation, it was visually determined whether or not the image touched by the bare hand was missing. However, the negative type lithographic printing plate [G-
In [1] to [G-4], clear image omission did not occur.

(Comparative Example 1) Solution [G] used in Example 1
, A solution was prepared in the same manner as in Example 1 except that the polymer compound [R-1] was used instead of the fluorinated copolymer. This solution was applied to the primed aluminum plate used in Example 1, and
After drying for minutes, a negative type lithographic printing plate material [Q-1] was obtained.
The weight after drying was 1.5 g / m ² . An image was formed on the obtained lithographic printing plate material [Q-1] in the same manner as in Example 1. After the image formation, it was visually determined whether or not the image of the portion touched by the bare hand was missing. In the negative type lithographic printing plate material [Q-1], clear image missing occurred.

(Comparative Example 2) Solution [G] used in Example 1
, A solution was prepared in the same manner as in Example 1 except that the polymer compound [R-2] was used instead of the fluorinated copolymer. This solution was applied to the primed aluminum plate used in Example 1, and
After drying for minutes, a negative type lithographic printing plate material [Q-2] was obtained.
The weight after drying was 1.5 g / m ² . An image was formed on the obtained lithographic printing plate material [Q-1] in the same manner as in Example 1. After the image formation, it was visually determined whether or not the image of the portion touched with the bare hand was missing, but clear image missing occurred in the negative type lithographic printing plate [Q-2].

[0186]

As described above, according to the present invention, it is possible to make a plate directly from digital data of a computer or the like by recording using a solid-state laser and a semiconductor laser emitting infrared rays. It is possible to provide a negative type image recording material suitable for a negative type lithographic printing plate material having no image omission.

Claims (1)

[Claims] 1. A negative type image recording material comprising the following (A) to (E). (A) a compound that decomposes by light or heat to generate an acid; (B) a crosslinking agent that crosslinks with an acid; (C) at least one alkali-soluble resin; (D) an infrared absorber; (E) at least the following components: (1) to (3) a polymer compound containing as a copolymerization component, component (1) addition polymerizable monomer having a fluoroaliphatic group in which a hydrogen atom on the carbon atoms are substituted with fluorine atoms, component (2 ) At least one selected from the monomers represented by the following structural formulas [1] to [4], and component (3) at least one selected from the monomers represented by the following structural formulas [5] to [8] . Embedded image In the structural formulas [1] to [4], A represents a hydrogen atom, a halogen atom or an alkyl group. W is an oxygen atom, or-
Represents NR ₃ —. R ₃ represents a hydrogen atom, an alkyl group or an aryl group. R ₁ represents an alkylene group which may have a substituent or an arylene group which may have a substituent. R ₂ represents a hydrogen atom, an alkyl group or an aryl group. R ₄ represents an alkyl group or an aryl group.
Y and Z represent an arylene group which may have a substituent, and Y and Z may be the same or different. X is a linking group, and represents a divalent organic group consisting of atoms selected from carbon, nitrogen, oxygen, sulfur, halogen and hydrogen atoms. m is an integer of 0 to 1; n is 1
Represents an integer of 1 to 3. Embedded image In the structural formulas [5] to [8], W is an oxygen atom or-
Represents NR ₃ —. R ₃ represents a hydrogen atom, an alkyl group or an aryl group. R ₅ represents an alkyl group which may have a substituent or an aryl group which may have a substituent. R ₆ represents an alkyl group or an aryl group. U
Represents a cyano group, an aryl group, an alkoxy group, an aryloxy group, an acyloxymethyl group, a heterocyclic ring containing a nitrogen atom, or —CH ₂ OCOR ₆ (R ₆ has the same meaning as described above). A represents the structural formula [1] to
It has the same meaning as that represented by [4].