JPH11288093A - Positive type photosensitive composition for infrared laser - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a positive type photosensitive compsn. for infrared laser for a direct photomechanical process excellent in handleability by adding a specified fluorine-contg. polymer. SOLUTION: The photosensitive compsn. contains a material that absorbs light and generates heat, a resin having phenolic hydroxyl groups and soluble in an aq. alkali soln. and a fluorine-contg. polymer contg. an addition polymerizable fluorine-contg. monomer having a fluoroaliphatic group contg. a fluorine atom substd. for a hydrogen atom on a carbon atom in a side chain, a monomer represented by the formula and an addition polymerizable monomer having an acidic group contg. an acidic hydrogen atom bonding to a nitrogen atom as copolymerizable components. In the formula, A<1> is H, halogen or alkyl, W is O or -NR<1> , R<1> is H, alkyl or aryl, R<2> is alkyl which may have a substituent or aryl, R<3> is alkyl or aryl and U is cyano, aryl, alkoxy, aryloxy or the like.

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 an offset printing master, and more particularly to a positive type photosensitive composition for an infrared laser for so-called direct plate making which can be directly made from digital signals of a computer or the like.

[0002]

2. Description of the Related Art In recent years, lasers have been remarkably developed.
2. Description of the Related Art Semiconductor lasers are easily available in small size with high output. These lasers are very useful as an exposure light source when making a plate directly from digital data of a computer or the like.

[0003] Positive lithographic printing plate materials for infrared lasers are:
An essential component is an alkaline aqueous solution-soluble binder resin and an IR dye or the like that absorbs light and generates heat. The IR dye or the like dissolves in the non-exposed area (image area) by interaction with the binder resin. In the exposed area (non-image area), the interaction between the IR dye etc. and the binder resin is weakened by the heat generated in the exposed area (non-image area), dissolving in the alkaline developer to form a lithographic printing plate. I do. However, such a positive lithographic printing plate material for an infrared laser has an unstable state before development. Even if the surface state slightly changes due to touching the surface during handling, etc., it is not exposed to light during development. There is a problem that the part (image part) is dissolved. Such a problem stems from an essential difference in the plate making mechanism between the positive lithographic printing plate material for infrared laser and the positive lithographic printing plate material made by UV exposure. That is, in a positive lithographic printing plate material made by UV exposure, a binder resin soluble in an aqueous alkali solution and an onium salt or a quinonediazide compound are essential components. In the image area), not only does it act as a dissolution inhibitor due to the interaction with the binder resin, but also in the exposed area (non-image area), it is decomposed by light to generate acid and acts as a dissolution promoter. Things. On the other hand, the IR dye or the like in the positive type lithographic printing plate material for an infrared laser only functions as a dissolution inhibitor in a non-exposed part (image part) and does not promote dissolution in an exposed part (non-image part). . Therefore, in order to obtain a difference in solubility between the non-exposed portion and the exposed portion in the infrared laser positive lithographic printing plate material, a binder resin having high solubility in an alkali developing solution must be used in advance. As a result, the state before development becomes unstable.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a positive photosensitive composition for an infrared laser for direct plate making, which has a stable state before development and is excellent in handleability.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that by adding a specific fluorine-containing polymer to a positive photosensitive composition for infrared laser, a positive plate obtained therefrom is obtained. It has been found that the state of the printing plate material before development is stabilized, and the present invention has been completed. That is, the present invention is a positive photosensitive composition for an infrared laser containing the following (a) to (c). (A) a substance that absorbs light to generate heat; (b) a resin soluble in an aqueous alkaline solution having a phenolic hydroxyl group; (c) at least the following (1) to
A fluorine-containing polymer containing (3) as a copolymer component,
(1) an addition-polymerizable fluorine-containing monomer having a fluoroaliphatic group in which a hydrogen atom on a carbon atom is replaced by a fluorine atom in a side chain; (2) the following structures [1] to [4]
A monomer represented by

[0006]

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Wherein A ¹ represents a hydrogen atom, a halogen atom or an alkyl group, W represents oxygen or —NR ¹ —, and R ¹ represents a hydrogen atom, an alkyl group or an aryl group;
R ² represents an alkyl group which may have a substituent or an aryl group which may have a substituent; R ³ represents an alkyl group or an aryl group; U is a cyano group, an aryl group, or an alkoxy group; , An aryloxy group, an acyloxymethyl group, a heterocycle containing a nitrogen atom, or —CH ₂ OCO
R ³ (R ³ is as defined above)] (3) An addition-polymerizable monomer having an acidic hydrogen atom and having an acidic group in which the acidic hydrogen atom is bonded to a nitrogen atom. Further, a phenolic hydroxyl group is used as a binder resin. An alkaline aqueous solution-soluble resin having the following formulas (4) to (6):
When a copolymer containing at least one of them as a copolymer component in an amount of 10 mol% or more is used in combination, the effect of adding the fluorine-containing polymer is remarkable. (4) A monomer having a sulfonamide group in which at least one hydrogen atom is bonded to a nitrogen atom in one molecule. (5) A monomer having an active imino group represented by the following formula in one molecule.

[0008]

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(6) Acrylamide, methacrylamide, acrylate, methacrylate, or hydroxystyrene each having a phenolic hydroxyl group

In the present invention, the reason why the addition of the above-mentioned fluorine-containing polymer stabilizes the state of the positive-working lithographic printing plate material obtained before development before development is not clear, but compared with the case where it is not added. Since the static friction coefficient of the surface of the obtained positive type lithographic printing plate material is reduced, the fluorine-containing polymer is coated with the photosensitive composition of the present invention on a support and dried. It is presumed that the film emerges on the surface of the lithographic printing plate material to form a film, which functions as a protective film.

According to the present invention, there is provided a positive photosensitive composition for an infrared laser for direct plate making, which is stable in a state before development and excellent in handleability by adding the fluorine-containing polymer.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. [Fluorine-containing polymer] The (c) fluorine-containing polymer used in the present invention contains at least the following (1) to (3) as a copolymer component. The component (1), a fluoroaliphatic group in which a hydrogen atom on a carbon atom is substituted with a fluorine atom, is usually a saturated and generally monovalent or divalent aliphatic group. This includes linear, branched and cyclic.
The fluoroaliphatic group must have from 3 to 20, preferably from 6 to 12, carbon atoms in order to achieve a satisfactory effect for the purposes of the present invention, and have a weight of 40% based on the total amount of fluorine-containing monomer. %, Preferably at least 50% by weight of fluorine bonded to carbon atoms. Suitable fluoroaliphatic groups are C _n F _{2n + 1-} (n is one or more, preferably 3
A perfluoroaliphatic group (hereinafter also abbreviated as Rf group) substantially completely or sufficiently fluorinated as in the above integer.

The addition-polymerizable monomer in the addition-polymerizable monomer having a fluoroaliphatic group in which a hydrogen atom on a carbon atom is replaced by a fluorine atom, which is represented by the component (1), may be a radically polymerizable unsaturated group. Vinyl and its derivatives are used. Preferred among the addition-polymerizable parts are acrylate, methacrylate, acrylamide, methacrylamide, styrene, vinyl and derivatives thereof. Specific examples of acrylates and methacrylates to which a fluoroaliphatic group is bonded include, for example, Rf-
R'-OOC-C (R " ) = CH 2 ( wherein R ', for example, a single bond, alkylene, sulfonamido alkylene or carbonamido alkylene,, R" is a hydrogen atom, a methyl group, a halogen atom, Or a perfluoroaliphatic group).

Specific examples of these are disclosed in US Pat. Nos. 2,803,615, 2,642,416, and 282.
No. 6564, No. 3102103, No. 328290
No. 5, No. 3,304,278, JP-A-6-2562.
No. 89, JP-A-62-1116, JP-A-62-487
No. 72, JP-A-63-77574, JP-A-62-36
657 and the Chemical Society of Japan 1985 (No.
10) Those described on pages 1884-1888. In addition to these fluoroaliphatic group-bonding monomers, Reports Res.Lab.Asahi Glass Co. Ltd.,
34, 1984, pp. 27-34, can be used to advantage. Further, as the fluoroaliphatic group-bonding monomer, a mixture having different lengths of perfluoroalkyl groups represented by the following structural formula can also be used.

[0015]

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The amount of these fluoroaliphatic group-containing monomers used in the fluorine-containing polymer used in the present invention is 3 to 70% by weight, preferably 7 to 40% by weight based on the weight of the polymer. Range.

The monomer used as the component (2) is
The following structures [1] to [4] are shown.

[0018]

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In the formula, A ¹ represents a hydrogen atom, a halogen atom or an alkyl group, W is oxygen or —NR ¹ —,
R ¹ represents a hydrogen atom, an alkyl group, or an aryl group. R ²
Represents an alkyl group which may have a substituent or an aryl group which may have a substituent, R ³ represents an alkyl group or an aryl group, and U represents a cyano group, an aryl group, an alkoxy group, or an aryl group. An oxy group, an acyloxymethyl group, a heterocycle containing a nitrogen atom, or —CH ₂ OCOR ³ (R
³ is the same as defined above). As a preferable range of the monomer represented by the structure [1] to [4], A ¹ is a hydrogen atom,
A halogen atom or an alkyl group having 1 to 4 carbon atoms,
Is oxygen or —NR ¹ —, and R ¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. R ² has 1 to 8 carbon atoms which may have a substituent.
R ³ is an alkyl group having 1 to 20 carbon atoms, an aryl group which may have a substituent,
Represents an aryl group of 0. U is a cyano group, an aryl group, an alkoxy group, an aryloxy group, an acyloxymethyl group, a heterocycle containing a nitrogen atom, or —CH ₂ OCO
R ³ (R ³ is as defined above).

When R ² is an alkyl group which may have a substituent, examples of the substituent include a halogen atom such as fluorine, chloro and bromo; a hydroxyl group; an alkoxy group such as methoxy and ethoxy; and an aryloxy group such as phenoxy. Group,
Examples include an amide group such as a cyano group and acetamide, and an alkoxycarbonyl group such as an ethoxycarbonyl group. When R ² is an aryl group which may have a substituent, examples of the substituent include a methyl group in addition to the above.

Preferred specific compounds of the component (2) are shown below. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
Octyl (meth) acrylate, 2-chloroethyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-
Hydroxylpropyl (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) acrylate, benzyl (meth) acrylate, methoxybenzyl (meth) ) (Meth) acrylic esters such as acrylates; (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-tolyl (meth) acrylamide, N-hydroxyphenyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, (Meth) acrylamides such as N-dicyclohexyl (meth) acrylamide; N
-Methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-pentylmaleimide, Nn-hexylmaleimide, N-laurylmaleimide, N-stearylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide , N-chlorophenylmaleimide, N-tolylmaleimide, N-
N such as hydroxymaleimide and N-benzylmaleimide
-Substituted maleimides; allyl acetate, allyl caproate,
Allyl compounds such as allyl stearate and allyloxyethanol; ethyl vinyl ether, propyl vinyl ether, 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, Vinyl ethers such as phenyl vinyl ether, tolyl vinyl ether and diethylaminoethyl vinyl ether: vinyl acetate, vinyl butyrate, vinyl caproate,
Vinyl chloroacetate, vinyl methoxyacetate,
Vinylphenyl acetate, vinyl acetoacetate,
Vinyl esters such as vinyl benzoate and vinyl chlorobenzoate; styrenes such as styrene, α-methylstyrene, methylstyrene, dimethylstyrene, chloromethylstyrene, ethoxymethylstyrene, hydroxystyrene, chlorostyrene, and bromostyrene; Vinylpyrrolidone, N-vinylpyridine, acrylonitrile and the like. Particularly preferred of these components (2) are
It is a monomer represented by the structure [1] or [3].

Having an acidic hydrogen atom which is a component (3);
As the acidic group in which the acidic hydrogen atom is bonded to the nitrogen atom,
Any of the acidic groups known in the literature can be used. Known literature on acidic groups includes JADean ed., Lange's Handbo
ok of Chemistry 3rd.ed.1985 McGraw-Hill Book Co.
Can be mentioned. Specific examples of the partial structure of an acidic group in which an acidic hydrogen atom is bonded to a nitrogen atom among these acidic groups include those represented by the following [A] to [G]. -SO ₂ NH ₂ (A) -SO ₂ NH- (B) -CONHSO ₂ - (C) -CONHCO- [D] -SO ₂ NHSO ₂ - (E) -CONHSO ₂ NH- [F] -NHCONHSO ₂ - [G] In addition to these structures, a nitrogen-containing heterocyclic structure having a coupler structure described in JP-A-7-248628 is also included. Examples of these nitrogen-containing heterocyclic structures include those represented by the following [H] and [I].

[0023]

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The addition-polymerizable moiety in the addition-polymerizable monomer having an acidic hydrogen atom represented by the component (3) and having the acidic hydrogen atom bonded to a nitrogen atom includes a radically polymerizable unsaturated group. Vinyl and its derivatives are used. Preferred among the addition-polymerizable parts are acrylate, methacrylate, acrylamide, methacrylamide, styrene, vinyl and derivatives thereof. Preferred examples of the acidic group-containing monomer having an acidic hydrogen atom and the acidic hydrogen atom bonded to a nitrogen atom include monomers having a structural unit represented by the following general formula [5], [6] or [7] Can be mentioned.

[0025]

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In the formula, A ² represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms. B represents an arylene group. X is -CO-, or -SO ₂ - represents a. X is -SO ₂ - when, Y represents a hydrogen atom, an alkyl group, an aryl group, -CO-R ⁴ or -SO ₂ -R ^4,. Also when X is -CO-, Y is -CO-R ⁴ or -SO ₂ -
Represents R ⁴ . Z is ^{-NH -, - NR 4 -,} - represents a O-.
E represents an arylene group or an alkylene group. R ⁵ represents a hydrogen atom, an alkyl group, or an aryl group. m and s
Represents 0 or 1, but m and s are not both 0. R ⁴ represents an alkyl group or an aryl group. Also,
B and Y, or E and R ⁵ may be linked to form a ring composed of a nonmetal atom.

[0027]

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F and G each represent a phenylene group or an alkylene group. T is -O-CO-, -CO-, or -SO
Represents _2- . p, p ', q and q' represent 0 or 1, but q and q 'do not become 0 at the same time. In the general formulas [5] and [6], A ² is preferably a hydrogen atom or a methyl group. Preferred alkyl groups represented by Y, R ⁴ or R ⁵ include alkyl groups having 1 to 20 carbon atoms such as methyl, ethyl and isopropyl, and preferred aryl groups represented by Y, R ⁴ or R ⁵ 6 carbon atoms such as phenyl and naphthyl
There are １８18 aryl groups. Preferred arylene groups represented by B or E include phenylene and naphthylene, and preferred alkylene groups represented by E have a carbon number of 1 to 2 such as methylene and ethylene.
There are 0 alkylene groups.

The alkyl group and the aryl group represented by Y, R ⁴ or R ⁵ and the arylene group and the alkylene group represented by B or E may have a substituent, such as fluorine, Halogen atoms such as chloro and bromo; alkoxy groups such as methoxy and ethoxy; aryloxy groups such as phenoxy; cyano groups; amide groups such as acetamide; alkoxycarbonyl groups such as ethoxycarbonyl; And an aryl group having 6 to 18 carbon atoms. In the general formula [7], preferred examples of F and G include the same as those used for B or E. In the general formulas [5] to [7], the monomers [5] and [6] are more preferable.
The amount of these acidic group-containing monomers used in the fluorine-containing polymer used in the present invention is from 5 to 80% by weight, preferably from 10 to 7% by weight, based on the weight of the polymer.
The range is 0% by weight. Next, specific examples of the structure of the acidic group-containing monomer having an acidic hydrogen atom bonded to a nitrogen atom used in the present invention are shown below.

[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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The fluorine-containing polymer of the present invention 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 a vinyl monomer having an acidic hydrogen atom bonded to a nitrogen atom are commonly used in an organic solvent. Can be produced by adding a radical polymerization initiator of the formula (1) and thermally polymerizing the same. Alternatively, if necessary, another addition-polymerizable unsaturated compound can be added to produce the compound in the same manner as described above.

Other optional addition-polymerized unsaturated compounds include Polymer Handbook 2nd ed.,
J. Brandrup, Wiley Interscience (1975) Chapter 2 Pa
ge 1 to 483 can be used. Examples of these are, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-chloroethyl (meth)
(Meth) acrylates such as acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-methylol ( (Meth) acrylamides such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N- (p-hydroxyphenyl) -meth-acrylamide, allyl acetate, allyl caproate, Allyl compounds such as allyloxyethanol; ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether,
-Vinyl ethers such as chloroethyl vinyl ether, hydroxyethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, phenyl vinyl ether, tolyl vinyl ether and diethylaminoethyl vinyl ether; vinyl acetate, vinyl butyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate Vinyl esters such as, vinylphenyl acetate, vinyl acetoacetate, vinyl benzoate, vinyl chlorobenzoate; styrene,
α-methylstyrene, methylstyrene, dimethylstyrene, chloromethylstyrene, ethoxymethylstyrene,
Styrenes such as hydroxystyrene, chlorostyrene, and bromostyrene; vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone; olefins such as isobutylene, butadiene, and isoprene; and others, butyl crotonate and itacone Acid dimethyl, diethyl itaconate, dimethyl maleate, diethyl fumarate, N-vinylpyrrolidone, N
-Vinyl pyridine, acrylonitrile and the like.

Further, in addition to these monomers,
Polyoxyalkylene (meth) acrylates described in JP-A-226143 and JP-A-3-172849 can be used. Hereinafter, specific examples of the structure of the fluorine-containing polymer according to the present invention will be described. The numbers in the formula indicate the molar ratio of each monomer component.

[0038]

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[0039]

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[0040]

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[0041]

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The molecular weight of the fluorine-containing polymer used in the present invention ranges from 3,000 to 200,000 as an average molecular weight.
And preferably from 6,000 to 100,0
Up to 00 can be used. The amount of the fluorine-containing polymer used in the present invention is in the range of 0.001 to 10% by weight, more preferably 0.01 to 5% by weight, based on the total composition except for the solvent.

[Aqueous Alkaline Aqueous Soluble Resin Having Phenolic Hydroxyl Group] Examples of the aqueous solution of phenolic hydroxyl group-containing alkaline aqueous solution (hereinafter referred to as “resin having a phenolic hydroxyl group”) used in the present invention include phenol formaldehyde resin. m-cresol formaldehyde resin, p-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin,
Phenol / cresol (m-, p-, or m- / p
Novolak resin such as mixed formaldehyde resin.

The resin having a phenolic hydroxyl group preferably has a weight average molecular weight of 500 to 20,000 and a number average molecular weight of 200 to 10,000. Further, as described in U.S. Pat. No. 4,123,279, a condensate of phenol having a C3-8 alkyl group as a substituent and formaldehyde, such as t-butylphenol formaldehyde resin and octylphenol formaldehyde resin. May be used in combination. The resin having such a phenolic hydroxyl group may be one type or two types.
A combination of more than two types may be used.

In the present invention, the resin having a phenolic hydroxyl group and a copolymer containing at least one of the above (4) to (6) as a copolymer component in an amount of 10 mol% or more (hereinafter referred to as a “specific copolymer”) It is preferable to use them together. The specific copolymer of the present invention is required to contain at least one of the above (4) to (6) as a copolymer component in an amount of 10 mol% or more, and more preferably 20 mol% or more. . If the amount is less than 10 mol%, the interaction with the resin having a phenolic hydroxyl group becomes insufficient, and the development latitude decreases. Further, other copolymer components other than the above (4) to (6) may be contained.

The monomer corresponding to (4) is a low molecular weight compound having, in one molecule, a sulfonamide group having at least one hydrogen atom bonded to a nitrogen atom and one or more polymerizable unsaturated bonds. Is a monomer consisting of
Among them, a low molecular compound having an acryloyl group, an allyl group, or a vinyloxy group and a substituted or monosubstituted aminosulfonyl group or a substituted sulfonylimino group is preferable. Examples of such compounds include compounds represented by the following general formulas (I) to (V).

[0047]

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In the formula, X ¹ and X ² are each —O— or —
NR ²² -is shown. It represents a ^{R 6, R 9, R 12} , R 14, R 18 each represents a hydrogen atom or -CH _3. R ⁷ , R ¹⁰ , R ¹³ ,
R ^16, R ²⁰ each represent an alkylene group having 1 to 12 carbon atoms which may have a substituent, a cycloalkylene group, an arylene group or an aralkylene group. R ⁸ , R ¹⁷ and R ²² each represent a hydrogen atom, each having 1 carbon atom which may have a substituent;
To 12 alkyl groups, cycloalkyl groups, aryl groups or aralkyl groups. R ¹¹ and R ²¹ each represent an optionally substituted alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group. R ¹⁵ and R ¹⁹ each represent a single bond or an optionally substituted alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, an arylene group or an aralkylene group.
Y ¹ and Y ² each represent a single bond or —CO—.

Specifically, m-aminosulfonylphenyl methacrylate, N- (p-aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonylphenyl) acrylamide and the like can be preferably used.

The monomer corresponding to (5) is a monomer composed of a low-molecular compound having an active imino group represented by the following formula and one or more polymerizable unsaturated bonds in one molecule. . As such a compound, specifically, N- (p-toluenesulfonyl) methacrylimide, N- (p-toluenesulfonyl) acrylimide and the like can be suitably used.

The monomer corresponding to (6) is a monomer composed of acrylamide, methacrylamide, acrylate, methacrylate or hydroxystyrene each having a phenolic hydroxyl group. As such a compound, specifically, N- (4
-Hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide, o-hydroxyphenyl acrylate, m-hydroxyphenyl acrylate, p-hydroxyphenyl acrylate, o-hydroxyphenyl methacrylate, m-hydroxyphenyl methacrylate, p-hydroxy Phenyl methacrylate, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene and the like can be suitably used.

As the other copolymer components, for example, the following monomers (7) to (18) can be used. (7) Acrylic esters having an aliphatic hydroxyl group, such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, and methacrylic esters. (8) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, glycidyl acrylate, N-dimethylaminoethyl Alkyl acrylates such as acrylates; (9) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, glycidyl methacrylate, N-dimethylaminoethyl Alkyl methacrylates such as methacrylate. (10) acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N
-Hexyl methacrylamide, N-cyclohexyl acrylamide, N-hydroxyethyl acrylamide, N
Acrylamide or methacrylamide such as -phenylacrylamide, N-nitrophenylacrylamide, N-ethyl-N-phenylacrylamide; (11) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.

(12) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate. (13) Styrenes such as styrene, α-methylstyrene, methylstyrene, and chloromethylstyrene. (14) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone and phenyl vinyl ketone. (15) Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene. (16) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile and the like. (17) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide. (18) acrylic acid, methacrylic acid, maleic anhydride,
Unsaturated carboxylic acids such as itaconic acid;

As the specific copolymer of the present invention, those having a weight average molecular weight of 2,000 or more and a number average molecular weight of 1,000 or more are preferably used. More preferably, the weight average molecular weight is 5,000 to 300,000, and the number average molecular weight is 200
0 to 250,000, and the degree of dispersion (weight average molecular weight / number average molecular weight) is 1.1 to 10.

These specific copolymers may be used alone or in combination of two or more.

The compounding weight ratio of the resin having a phenolic hydroxyl group to the specific copolymer is 50:50 to 5: 5.
95: 40:60 to 1
More preferably, it is in the range of 0:90. When the amount of the resin having a phenolic hydroxyl group is increased, the sea-island structure is reversed, and the solvent resistance and the like cannot be improved. Conversely, when the amount of the copolymer is larger than this, the surface layer of the resin having the phenolic hydroxyl group becomes too thin, and the improvement in development latitude becomes insufficient.

These alkali-soluble polymer compounds composed of a resin having a phenolic hydroxyl group and a specific copolymer may be used alone or in combination of two or more. , 30-99
% By weight, preferably 40 to 95% by weight, particularly preferably 50 to 90% by weight. If the amount of the alkali-soluble polymer compound is less than 30% by weight, the durability of the recording layer is deteriorated, and if it exceeds 99% by weight, it is not preferable in terms of both sensitivity and durability.

[Substance that Absorbs Light and Generates Heat] In the present invention, as the substance that absorbs light and generates heat, various pigments or dyes can be used. As pigments, commercially available pigments and Color Index (C.I.) 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 pigments include black pigment, yellow pigment, orange pigment, brown pigment, red pigment, purple pigment,
Blue pigment, green pigment, fluorescent pigment, metal powder pigment, etc.
Polymer-bound dyes. Specifically, insoluble azo pigments, azo lake pigments, condensation azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments,
Perylene and perinone pigments, thioindigo pigments,
Quinacridone pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, dye lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black and the like can be used.

These pigments may be used without being subjected to a surface treatment, or may be used after being subjected to a 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),
"Printing ink technology" (CMC Publishing, 1984) and "Latest Pigment Application Technology" (CMC Publishing, 1986)
It is described in.

The particle size of the pigment is preferably in the range of 0.01 μm to 10 μm, more preferably in the range of 0.05 μm to 1 μm, and particularly preferably in the range of 0.1 μm to 1 μm.
Is preferably within the range. Pigment particle size 0.01μ
When it is less than m, the dispersion is not preferred in terms of stability in a photosensitive layer coating solution, and when it exceeds 10 μm, it is not preferred in terms of uniformity of the photosensitive layer. As a method for dispersing the pigment, a known dispersion technique used in the production of ink or toner can be used. Dispersers include ultrasonic dispersers, sand mills, attritors, pearl mills, super mills,
Examples include a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill, and a pressure kneader. For details, see “Latest Pigment Application Technology”
(CMC Publishing, 1986).

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. Specific examples include azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes, methine dyes, and cyanine dyes. In the present invention, among these pigments or dyes, those that absorb infrared light or near-infrared light are particularly preferable because they are suitable for use in lasers that emit infrared light or near-infrared light.

As such a pigment absorbing infrared light or near infrared light, carbon black is preferably used. Dyes that absorb infrared light or near infrared light include, for example, JP-A-58-125246 and JP-A-59-125246.
-84356, JP-A-59-202829, JP-A-60-78787 and the like.
JP-A-58-173696, JP-A-58-18169
0, methine dyes described in JP-A-58-194595, JP-A-58-112793, and JP-A-58-112793.
Naphthoquinone dyes described in JP-A-224793, JP-A-59-48187, JP-A-59-73996, JP-A-60-52940, JP-A-60-63744 and the like; And the cyanine dyes described in British Patent No. 434,875.

As a dye, US Pat.
No. 938 is also preferably used, and substituted arylbenzo (thio) pyrylium salts described in U.S. Pat. No. 3,881,924;
No. 42645 (U.S. Pat. No. 4,327,169), a trimethinethiapyrylium salt described in JP-A-58-1810.
No. 51, No. 58-220143, No. 59-41363
Nos. 59-84248, 59-84249, 59-146063, and 59-146061 and pyrylium compounds described in JP-A-59-2161.
No. 46, a cyanine dye disclosed in U.S. Pat. No. 4,283,4.
No. 75, pentamethine thiopyrylium salt and the like, and pyrilium compounds disclosed in Japanese Examined Patent Publication Nos. 5-135514 and 5-19702, Epollight III-1
78, Epollight III-130, Epollight
t III-125 and the like are particularly preferably used.

Another particularly preferred example of the dye is a near-infrared absorbing dye described as formulas (I) and (II) in US Pat. No. 4,756,993. These pigments or dyes are used in an amount of 0.01 to 50% by weight, preferably 0.1 to 10% by weight, particularly preferably 0.5 to 10% by weight, in the case of dyes, Particularly preferred is 3.1.
It can be added to the printing plate material at a ratio of 10 to 10% by weight. If the amount of the pigment or dye is less than 0.01% by weight, the sensitivity is lowered. If the amount exceeds 50% by weight, the uniformity of the photosensitive layer is lost and the durability of the recording layer is deteriorated. These dyes or pigments may be added to the same layer as other components, or a separate layer may be provided and added thereto. If it is a separate layer, it is desirable to add it to a layer adjacent to the layer containing a substance which substantially reduces the solubility of the binder when it is thermally decomposable and does not decompose. The dye or pigment and the binder resin are preferably in the same layer, but may be in different layers.

[Other Components] Various additives can be further added to the positive photosensitive composition of the present invention, if necessary. For example, a thermally decomposable substance such as an onium salt, an o-quinonediazide compound, an aromatic sulfone compound, an aromatic sulfonic acid ester compound, and a substance that substantially lowers the solubility of an alkali water-soluble polymer compound when not decomposed is used in combination. This is preferable from the viewpoint of improving the dissolution inhibiting property of the image area in the developer. Examples of the onium salt include a diazonium salt, an ammonium salt, a phosphonium salt, an iodonium salt, a sulfonium salt, a selenonium salt, and an arsonium salt.

Suitable onium salts used in the present invention include, for example, SI Schlesinger,
Photogr. Sci. Eng., 18, 387 (1974), TS Bal et a
1, Polymer, 21, 423 (1980), JP-A-5-158230
No. 4,069,055 diazonium salt described in U.S. Pat.
No. 4,069,056, ammonium salt described in the specification of JP-A-3-140140, DC Necker et al, Macromolecul
es, 17, 2468 (1984), CS Wen et al, Teh, Proc. Co.
nf.Rad. Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat.Nos. 4,069,055 and 4,069,056, phosphonium salts described in JVCrivello et al, Macromorecules, 10
(6), 1307 (1977), Chem. & Eng. News, Nov. 28, p31.
(1988), EP 104,143, U.S. Patent 339,049
No. 410,201, JP-A-2-150848, JP-A-2-2-2965
Iodonium salt described in No. 14, JVCrivello et al, P
olymer J. 17, 73 (1985), JV Crivello et al. J.
Org.Chem., 43, 3055 (1978), WR Watt et al, J. P.
olymer Sci., Polymer Chem. Ed., 22, 1789 (1984),
JV Crivello et al, Polymer Bull., 14, 279 (198
5), JV Crivello et al, Macromorecules, 14 (5)
, 1141 (1981), JV Crivello et al, J. Polymer Sc
i., Polymer Chem.Ed., 17, 2877 (1979), European Patent Nos. 370,693, 233,567, 297,443, 297,44
No. 2, U.S. Pat.Nos. 4,933,377, 3,902,114, 41
0,201, 339,049, 4,760,013, 4,734,44
No. 4, No. 2,833,827, German Patent No. 2,904,626, No. 3,
Nos. 604,580 and 3,604,581, sulfonium salts,
JV Crivello et al, Macromorecules, 10 (6), 1307
(1977), JV Crivello et al, J. Polymer Sci., Pol
selenonium salt described in ymer Chem. Ed., 17, 1047 (1979), CS Wen et al, Teh, Proc. Conf. Rad. Curing
ASIA, p478 Tokyo, Oct (1988).

In the present invention, diazonium salts are particularly preferred. Particularly preferred diazonium salts include those described in JP-A-5-158230. Suitable quinonediazides include o-quinonediazide compounds. The o-quinonediazide compound used in the present invention is a compound having at least one o-quinonediazide group, which increases alkali solubility by thermal decomposition, and can be a compound having various structures. In other words, o-quinonediazide helps the solubility of the light-sensitive material system by both the effect of losing the ability to suppress the dissolution of the binder due to thermal decomposition and the fact that o-quinonediazide itself changes to an alkali-soluble substance. O used in the present invention
Examples of the quinonediazide compound include: "Wright-Sensitive Systems" by Coser (John Wil
ey & Sons. Inc.) pp. 339-352 can be used. Particularly, sulfonic esters or sulfonic amides of o-quinonediazide reacted with various aromatic polyhydroxy compounds or aromatic amino compounds can be used. It is suitable. Also, benzoquinone (1,2) -diazide sulfonic acid chloride or naphthoquinone- (1,2) -diazide-5-sulfonic acid chloride and pyrogallol-acetone resin as described in JP-B-43-28403. Esters of the benzoquinones described in U.S. Patents 3,046,120 and 3,188,210
Esters of (1,2) -diazidesulfonic acid chloride or naphthoquinone- (1,2) -diazide-5-sulfonic acid chloride with a phenol-formaldehyde resin are also suitably used.

Further, esters of naphthoquinone- (1,2) -diazide-4-sulfonic acid chloride with phenol formaldehyde resin or cresol-formaldehyde resin, naphthoquinone- (1,2) -diazide-
Esters of 4-sulfonic acid chloride with pyrogallol-acetone resin are likewise preferably used. Other useful o-quinonediazide compounds are reported and known in numerous patents. For example, JP-A-47-5303, JP-A-48-63802, JP-A-48-63803, JP-A-48-96
No. 575, JP-A-49-38701, JP-A-48-13354, JP-B-41-11222, JP-B-45-9610, JP-B-49-17481
U.S. Pat.Nos. 2,797,213, 3,454,400, 3,544,323, 3,573,917, and 3,674,495
No. 3,785,825; British Patent No. 1,227,602;
Nos. 1,251,345, 1,267,005, 1,329,888,
No. 1,330,932, and German Patent No. 854,890, etc. can be mentioned.

The addition amount of the o-quinonediazide compound is preferably 1 to 50% by weight, more preferably 5 to 30% by weight, particularly preferably 10 to 3% by weight, based on the total solids of the printing plate material.
The range is 0% by weight. These compounds can be used alone, but may be used as a mixture of several kinds.

As the counter ion of the onium salt, tetrafluoroboric acid, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, 5-nitro-o-toluenesulfonic acid,
-Sulfosalicylic acid, 2,5-dimethylbenzenesulfonic acid, 2,4,6-trimethylbenzenesulfonic acid, 2
-Nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-fluorocaprylnaphthalenesulfonic acid, dodecylbenzenesulfonic acid, 1-naphthol-5-sulfonic acid, 2-methoxy-4-hydroxy-5- Benzoyl-benzenesulfonic acid, paratoluenesulfonic acid and the like can be mentioned. Among them, alkyl aromatic sulfonic acids such as hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid and 2,5-dimethylbenzenesulfonic acid are particularly preferable.

The amount of additives other than the o-quinonediazide compound is preferably 1 to 50% by weight, more preferably 5 to 30% by weight, and particularly preferably 10 to 30% by weight. It is preferable that the additive and the binder of the present invention are contained in the same layer.

For the purpose of further improving the sensitivity, cyclic acid anhydrides, phenols and organic acids can be used in combination. Cyclic acid anhydride include US Patent has been and phthalic anhydride described in 4,115,128 Pat, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-oxy - [delta ⁴ - tetrahydrophthalic anhydride, tetrachlorophthalic anhydride Acid, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride and the like can be used. As phenols, bisphenol A, p-nitrophenol, p-nitrophenol
Ethoxyphenol, 2,4,4'-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 4-hydroxybenzophenone, 4,4 ', 4 "
-Trihydroxytriphenylmethane, 4,4 ',
3 ", 4" -tetrahydroxy-3,5,3 ', 5'-
Tetramethyltriphenylmethane and the like can be mentioned. Further, as organic acids, JP-A-60-88942,
Sulfonic acids, such as those described in
There are sulfinic acids, alkyl sulfuric acids, phosphonic acids, phosphoric acid esters and carboxylic acids, and specifically, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethyl sulfate, phenylphosphonic acid, Phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, adipic acid, p-toluic acid, 3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, 4-cyclohexene-
Examples thereof include 1,2-dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, and ascorbic acid. The proportion of the cyclic acid anhydride, phenols and organic acids in the printing plate material is preferably 0.05 to 20% by weight, more preferably 0.1 to 15% by weight, and particularly preferably 0.1 to 15% by weight. 10% by weight.

In the printing plate material of the present invention,
To expand the stability of processing under development conditions, see
Nonionic surfactants described in JP-A-25251740 and JP-A-3-208514, and amphoteric surfactants described in JP-A-59-121044 and JP-A-4-13149 An activator can be added. Specific examples of the nonionic surfactant include sorbitan tristearate,
Sorbitan monopalmitate, sorbitan triolate, stearic acid monoglyceride, polyoxyethylene nonyl phenyl ether and the like can be mentioned. Specific examples of the surfactant include alkyl di (aminoethyl) glycine, alkyl polyaminoethyl glycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N, N
-Betaine type (for example, trade name "Amogen K": manufactured by Dai-ichi Kogyo Co., Ltd.) and the like. The proportion of the nonionic surfactant and amphoteric surfactant in the printing plate material is preferably 0.05 to 15% by weight, more preferably 0.1 to 15% by weight.
1 to 5% by weight.

In the printing plate material of the present invention, a printing-out agent for obtaining a visible image immediately after heating by exposure, and a dye or pigment as an image coloring agent can be added. Representative examples of the printing-out agent include a combination of a compound that releases an acid by heating upon exposure (photoacid releasing agent) and an organic dye that can form a salt. Specifically, a combination of o-naphthoquinonediazide-4-sulfonic acid halogenide and a salt-forming organic dye described in JP-A-50-36209 and JP-A-53-8128, −36223
No. 54-74728, No. 60-3626, No. 61-143748,
Combinations of trihalomethyl compounds and salt-forming organic dyes described in JP-A-61-151644 and JP-A-63-58440 can be exemplified. Such trihalomethyl compounds include oxazole-based compounds and triazine-based compounds, both of which have excellent temporal stability and give clear print-out images.

As the colorant for the image, other dyes can be used in addition to the above-mentioned salt-forming organic dyes. Suitable dyes, including salt-forming organic dyes, include oil-soluble dyes and basic dyes. 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 (all manufactured by Orient Chemical Industry Co., Ltd.), Victoria Pure Blue, crystal violet (CI42555), methyl Violet (CI42535), ethyl violet, rhodamine B (CI145170B), malachite green (CI42000), methylene blue (CI5201)
5) and the like. Also, JP-A-62-2932
The dyes described in JP-B-47 are particularly preferred. These dyes are used in an amount of 0.01 to 10 based on the total solid content of the printing plate material.
% By weight, preferably 0.1 to 3% by weight, can be added to the printing plate material. Further, a plasticizer is added to the printing plate material of the present invention, if necessary, in order to impart flexibility and the like to the coating film. For example, butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate,
An oligomer or polymer of trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic acid or methacrylic acid, or the like is used.

The image recording material of the present invention can be usually produced by dissolving each of the above-mentioned components in a solvent and coating the solution 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-butyrolactone, toluene and the like can be mentioned. It is not limited. 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 ranges from 0.5 to 0.5 for photosensitive printing plates.
-5.0 g / m < ² > is preferable. As a method of applying,
Various methods can be used, and examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating. As the coating amount decreases, the apparent sensitivity increases, but the film characteristics of the photosensitive film deteriorate. In the photosensitive layer according to the invention, a surfactant for improving coating properties, for example, a fluorine-based surfactant described in JP-A-62-170950 can be added. A preferable addition amount is 0.01 to 1% by weight of the total printing plate material, more preferably 0.05 to 0.5%.
% By weight.

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 of the present invention,
Polyester film or aluminum plate is preferred,
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,
Examples include iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, and titanium. 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 ~
About 0.6 mm, preferably 0.15 mm to 0.4 m
m, 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 surface of the aluminum plate is performed by various methods, for example, a method of mechanically roughening the surface, a method of electrochemically dissolving the surface, and a method of selectively dissolving the surface chemically. It is performed by the method of causing. 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. Further, 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, if necessary, and then subjected to an anodic oxidation treatment, if desired, in order 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 for forming a porous oxide film can be used, and 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 to be used and 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.No. 2,714,
Nos. 066, 3,181,461, 3,280,734 and 3,
There is an alkali metal silicate (for example, sodium silicate aqueous solution) method as disclosed in 902,734. In this method, the support is immersed in an aqueous solution of sodium silicate or electrolytically treated. Also,
The potassium fluoride zirconate disclosed in 22063 and U.S. Pat.Nos. 3,276,868 and 4,153,461,
No. 4,689,272, a method of treating with polyvinyl phosphonic acid and the like are used.

The image recording material of the present invention is obtained by providing a positive printing plate material on a support. An undercoat layer may be provided between them, 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 phenylphosphonic acid optionally having a substituent Organic phosphonic acids such as naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid, phenylphosphoric acid which may have a substituent, naphthylphosphoric acid, alkylphosphoric acid and glycerophosphoric acid Organic phosphinic acid, optionally substituted phenylphosphinic acid, naphthylphosphinic acid, organic phosphinic acid such as alkylphosphinic acid and glycerophosphinic acid, amino acids such as glycine and β-alanine, and hydrochloric acid of triethanolamine Hydroxy such as salt -Alanine, and hydrochlorides of amines having a group may be used in combination of two or more.

This organic undercoat layer can be provided by the following method. That is, a method in which a solution obtained by dissolving the above organic compound in water or an organic solvent such as methanol, ethanol, or methyl ethyl ketone or a mixed solvent thereof is coated on an aluminum plate and dried, and a method in which water or methanol, ethanol, methyl ethyl ketone, or the like is used. A method in which an aluminum plate is immersed in a solution in which the above organic compound is dissolved in an organic solvent or a mixed solvent thereof to adsorb the above compound by immersing the aluminum plate, and then washed and dried with water or the like to provide an organic undercoat layer. . In the former method, a solution of the above organic compound having a concentration of 0.005 to 10% by weight can be applied by various methods. In the latter method, the concentration of the solution is 0.01 to 20% by weight, preferably 0.05 to 5% by weight, and the immersion temperature is 20 to 90 ° C, preferably 25%.
To 50 ° C., and the immersion time is 0.1 seconds to 20 minutes, preferably 2 seconds to 1 minute. The pH of the solution used for this is adjusted to pH 1 to 12 by a basic substance such as ammonia, triethylamine, potassium hydroxide, or an acidic substance such as hydrochloric acid or phosphoric acid.
It can also be adjusted to the range. Further, a yellow dye can be added for improving the tone reproducibility of the image recording material. The coating amount of the organic undercoat layer is suitably from ² to 200 mg / m ² , and preferably from 5 to 100 mg / m ² . If the coating amount is less than 2 mg / m ² , sufficient printing durability cannot be obtained. The same is true even if it is larger than 200 mg / m ² .

The positive type image recording material prepared as described above is usually subjected to image exposure and development processing. Examples of the light source of the actinic ray used for the image exposure include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, a carbon arc lamp, and the like. As radiation,
There are electron beams, X-rays, ion beams, far infrared rays, and the like. In addition, g-line, i-line, Deep-UV light, and high-density energy beam (laser beam) are also used. Laser beams include helium / neon laser, argon laser, krypton laser, helium / cadmium laser, K
rF excimer laser and the like can be mentioned. In the present invention, a light source having an emission wavelength in the near infrared to infrared region is preferable, and a solid-state laser and a semiconductor laser are particularly preferable.

As the developer and replenisher for the image recording material of the present invention, conventionally known aqueous alkaline solutions can be used. For example, sodium silicate, potassium silicate, tertiary
Sodium phosphate, same potassium, same ammonium, second
Sodium phosphate, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium bicarbonate, potassium, ammonium, sodium borate, potassium, ammonium, sodium hydroxide, ammonium, potassium, and lithium And the like. Further, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine,
Organic alkaline agents such as diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine and pyridine are also used. These alkali agents are 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 silicate components.
An alkali metal silicate described in JP-B-57-7427 is effectively used.

Further, in the case of 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 PS plates 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 required 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 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 a post-process when the image recording material of the present invention is used as a printing plate, these processes can be used in various combinations.

In recent years, in the plate making / printing industry, automatic developing machines for printing plates have been widely used in order to rationalize and standardize plate making operations. This automatic developing machine generally comprises a developing section and a post-processing section, and comprises a device for transporting a printing plate, each processing solution tank and a spray device, and while pumping the exposed printing plate horizontally, each pumped by a pump. The developing process is performed by spraying a processing liquid from a spray nozzle. Recently, a method has been known in which a printing plate is immersed and conveyed by a submerged guide roll or the like in a processing liquid tank filled with a processing liquid to perform processing. 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 case where the image recording material of the present invention is used as a photosensitive lithographic printing plate will be described. If the lithographic printing plate obtained by image exposure, development, washing and / or rinsing and / or gumming has unnecessary image portions (for example, film edge marks of the original film), unnecessary portions are unnecessary. Erasing of the image portion is performed. Such erasing is preferably carried out by applying an erasing liquid as described in, for example, Japanese Patent Publication No. 2-13293, to an unnecessary image portion, leaving it for a predetermined time, and then rinsing with water. A method described in JP-A-59-174842, in which active light guided by an optical fiber is applied to an unnecessary image portion and then developed, can also be used.

The lithographic printing plate obtained as described above can be subjected to a printing step after applying a desensitized gum if desired, but when it is desired to obtain a lithographic printing plate having even higher printing durability. Is subjected to a burning process. When burning a lithographic printing plate, before burning,
No. 2518, No. 55-28062, JP-A No. 62-31859, No. 61-
It is preferable to treat with a surface-regulating liquid as described in each publication of 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 coating 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 burned (for example, a burning processor sold by Fuji Photo Film Co., Ltd .: "BP-130").
0 "). The heating temperature and time in this case depend on the type of the component forming the image,
The temperature is preferably in the range of 180 to 300 ° C. for 1 to 20 minutes.

The burned lithographic printing plate can be subjected to conventional treatments such as washing with water and gumming if necessary. However, a surface conditioning solution containing a water-soluble polymer compound or the like can be used. When is used, 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.

[0091]

Hereinafter, the present invention will be described with reference to Examples.
The scope of the present invention is not limited to these examples.

[Synthesis of Fluorine-Containing Polymer] Synthesis Example 1 2- (Perfluorooctyl) ethyl acrylate 4
6.6 g, 28.8 g of N- (4-sulfamoylphenyl) methacrylamide, 18.9 g of (n) -nonyl methacrylate and 180 g of dimethylacetamide
Place in a 00 ml three-necked flask and stir under nitrogen flow.
It was kept at 5 ° C. 3.73 g of 2,2'-azobis (2,4-dimethylvaleronitrile) was added and stirring was continued. After 4 hours, the temperature was raised to 68 ° C. and maintained for 1 hour. After completion of the reaction, the reaction solution was cooled to room temperature, and the reaction solution was poured into 400 ml of water. The precipitated solid was collected by filtration and dried. Yield 32.5 g, GP
By C, this solid was a high molecular compound having a weight average molecular weight of 23,000. Synthesis Examples 2-3 The polymers shown in Table 1 were synthesized in the same manner as in Synthesis Example 1. Further, a compound (polymer) for a comparative example was synthesized in the same manner.

[0093]

[Table 1]

[Synthesis of Specific Copolymer] Synthesis Example 4
1) 31.0 g (0.36 mol) of methacrylic acid, 39.1 g (0.36 mol) of ethyl chloroformate and 200 ml of acetonitrile were placed in a 500 ml three-necked flask equipped with a stirrer, a condenser and a dropping funnel. The mixture was stirred while cooling in an ice-water bath. To this mixture, 36.4 g (0.36 mol) of triethylamine was dropped by a dropping funnel over about 1 hour. After the addition, the ice-water bath was removed, and the mixture was stirred at room temperature for 30 minutes.

To the reaction mixture was added 51.7 g (0.30 mol) of p-aminobenzenesulfonamide, and the mixture was stirred for 1 hour while warming to 70 ° C. in an oil bath. After completion of the reaction, the mixture was added to 1 liter of water while stirring the water, and the resulting mixture was stirred for 30 minutes. The mixture was filtered to remove the precipitate, which was then washed with 500 m of water.
Then, the slurry was filtered and the obtained solid was dried to obtain a white solid of N- (p-aminosulfonylphenyl) methacrylamide (yield 46.9 g).

Next, 4.61 g of N- (p-aminosulfonylphenyl) methacrylamide was placed in a 20 ml three-necked flask equipped with a stirrer, a condenser and a dropping funnel.
92 mol), and 2.94 g (0.02 g) of ethyl methacrylate.
58 mol), 0.80 g (0.015 g) of acrylonitrile
Mol) and 20 g of N, N-dimethylacetamide, and the mixture was stirred while being heated to 65 ° C. in a hot water bath. This mixture was mixed with “V-65” (manufactured by Wako Pure Chemical Industries, Ltd.).
0.15 g was added, and the mixture was stirred for 2 hours under a nitrogen stream while maintaining at 65 ° C. N- (p-
Aminosulfonylphenyl) methacrylamide 4.61
g, 2.94 g of ethyl methacrylate, 0.80 g of acrylonitrile, N, N-dimethylacetamide and "V-
65 "and a mixture of 0.15 g was added dropwise with a dropping funnel over 2 hours. After the addition was completed, the resulting mixture was further stirred at 65 ° C. for 2 hours. After completion of the reaction, 40 g of methanol was added to the mixture, and the mixture was cooled. The obtained mixture was added to 2 liters of water while stirring the water, and the mixture was stirred for 30 minutes, and the precipitate was taken out by filtration and dried. 15 g of a white solid was obtained. The weight average molecular weight (polystyrene standard) of this specific copolymer 1 was determined by gel permeation chromatography to be 53,000.
It was 0.

[Preparation of Substrate] Aluminum having a thickness of 0.3 mm
Plate (material 1050) is washed with trichlorethylene
Degreased, nylon brush and 400 mesh pumice
Use a water suspension to grain this surface and wash well with water.
Was cleaned. Put this plate in 25% sodium hydroxide aqueous solution at 45 ° C.
Immerse in the solution for 9 seconds to perform etching, and after washing with water,
It was immersed in 20% nitric acid for 20 seconds and washed with water. Grain at this time
The amount of etching on the standing surface is about 3 g / m ^TwoMet. next
This plate was subjected to a current density of 15 A / dm using 7% sulfuric acid as an electrolyte.
^Two3g / m^TwoAfter the DC anodic oxide coating of
And dried, and then the following undercoating liquid was applied,
Dry at 0 ° C. for 1 minute. The amount of coating after drying is 10mg
/ M^TwoMet.

Undercoating liquid β-alanine 0.5 g Methanol 95 g Water 5 g

Further, the substrate was treated with a 2.5% by weight aqueous solution of sodium silicate at 30 ° C. for 10 seconds, the following undercoating solution was applied, and the coating film was dried at 80 ° C. for 15 seconds to obtain a substrate. The coating amount of the coating film after drying was 15 mg / m ² . Undercoat liquid The following compound 0.3 g Methanol 100 g Water 1 g

[0100]

Embedded image

Example 1 The following photosensitive solution 1 was prepared.
The obtained substrate was coated with the photosensitive solution 1 at a coating amount of 1.8 g / m2.
² to obtain a lithographic printing plate.

Photosensitive solution 1 Fluorine-containing polymer P-6 0.03 g Specific copolymer 1 0.75 g m, p-cresol novolak (m, p ratio = 6/4, weight average molecular weight 3,500, unreacted) Cresol 0.5% by weight) 0.25 g p-toluenesulfonic acid 0.003 g tetrahydrophthalic anhydride 0.03 g cyanine dye A (the following structure) 0.017 g The counter ion of Victoria Pure Blue BOH is 1-naphthalenesulfonic acid anio 0.015 g Megafac F-177 (manufactured by Dainippon Ink and Chemicals, Inc., fluorine surfactant) 0.05 g γ-butyl lactone 10 g methyl ethyl ketone 10 g 1-methoxy-2-propanol 1 g

[0103]

Embedded image

The resulting lithographic printing plate was evaluated for development stability against damage. Table 2 shows the evaluation results.

(Development Stability to Trauma) The obtained lithographic printing plate was exposed at a main scanning speed of 5 m / sec using a semiconductor laser having an output of 500 mW, a wavelength of 830 nm and a beam diameter of 17 μm (1 / e ² ). Using a continuous load type scratch strength tester "SB62 type" (manufactured by Shinto Kagaku Co., Ltd.), "No. 5C" manufactured by Advantech Toyosha Co., Ltd. was applied to a 1 cm square flat surface hitting the plate of a scratching jig. Paste the filter paper and add 10
With a load of 0 g, the film was scratched at a speed of 6 cm / sec, and developed with a developing solution DP-4 (1: 8) manufactured by Fuji Photo Film Co., Ltd. for 30 seconds. The evaluation was performed according to the following criteria. When the photosensitive film at the scratched portion is completely dissolved; × When the photosensitive film at the scratched portion is partially dissolved; 場合 When the photosensitive film at the scratched portion is not completely dissolved; ○

[0106]

[Table 2]

(Examples 2 and 3, Comparative Examples 1 and 2) Except that fluorine-containing polymers P-2, P-5, R-1, and R-2 were used instead of fluorine-containing polymer P-6, respectively. A lithographic printing plate was obtained in the same manner as in Example 1. The resulting lithographic printing plate was evaluated for development stability against damage in the same manner as in Example 1. Table 2 shows the evaluation results.

From Table 2, it can be seen that the stability against trauma in the state before development was significantly improved by the addition of the specific fluorine-containing polymer.

[0109]

According to the present invention, there is provided a positive photosensitive composition for an infrared laser for direct plate making, which is stable in a state before development and excellent in handleability.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Koichi Kawamura 4,000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture Inside Fujisha Shin Film Co., Ltd.

Claims (2)

[Claims] 1. A positive photosensitive composition for an infrared laser comprising the following (a) to (c). (A) a substance that absorbs light and generates heat; (b) a resin soluble in an aqueous alkali solution having a phenolic hydroxyl group; (c) a fluorine-containing polymer containing at least the following (1) to (3) as a copolymerization component; ) An addition-polymerizable fluorine-containing monomer having a fluoroaliphatic group in which a hydrogen atom on a carbon atom is substituted by a fluorine atom in a side chain, (2) a monomer represented by the following structures [1] to [4] Embedded image [In the formula, A ¹ represents a hydrogen atom, a halogen atom or an alkyl group, W represents oxygen or —NR ¹ —, R ¹ represents a hydrogen atom, an alkyl group, or an aryl group, and R ² represents a substituent. R ³ represents an alkyl group or an aryl group which may have an alkyl group or an aryl group which may have a substituent; U represents a cyano group, an aryl group, an alkoxy group, an aryloxy group, or an acyloxy group; Represents a methyl group, a heterocycle containing a nitrogen atom, or —CH ₂ OCOR ³ (R ³ is as defined above). (3) It has an acidic hydrogen atom, and the acidic hydrogen atom has an acidic group bonded to the nitrogen atom Addition polymerizable monomer 2. The positive photosensitive composition for an infrared laser according to claim 1, further comprising (d) a copolymer containing at least one of the following (4) to (6) as a copolymer component in an amount of 10 mol% or more. Stuff. (4) A monomer having a sulfonamide group in which at least one hydrogen atom is bonded to a nitrogen atom in one molecule. (5) A monomer having an active imino group represented by the following formula in one molecule. ] (6) acrylamide, methacrylamide, acrylate, methacrylate, or hydroxystyrene each having a phenolic hydroxyl group