JPH11218914A - Photosensitive image forming material for infrared laser - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the positive image forming material for infrared laser improved in the image forming performance of a recording layer and superior in printing resistance and good in the stability of sensitivity against the concen tration of a developing solution. SOLUTION: This image forming material is formed by successively laminating, on a support, (A) a layer containing >=50 wt.% a copolymer comprising structure units derived from at least one of monomers (a-1)-(1-3) as a copolymer component in an amount of >=10 mol.%, and (B) a layer containing a resin having phenolic hydroxyl groups an soluble in an alkaline aqueous solution in an amount of >=50 weight %, and the layer (B) contains a compound generating heat by light absorption. The above monomer is selected from the monomer (a-1) having a sulfonamide group whose N atom combines to at least one H atom and the one (a-2) having an active imino group represented by the formula and the one (a-3) selected from acrylamide, acrylate, hydroxystyrene, and the like having phenolic hydroxyl groups.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming material which can be used as an offset printing master, and more particularly to a so-called direct plate making infrared laser photosensitive image forming material which can make a plate directly from a digital signal from a computer or the like.

[0002]

2. Description of the Related Art In recent years, attention has been paid to a system for making a plate directly from digital data of a computer, and various techniques have been developed. In particular, the development of lasers in recent years has been remarkable. In particular, solid-state lasers and semiconductor lasers that emit light in the near-infrared to infrared regions can easily obtain high-power and small-sized lasers. It is very useful as an exposure light source for plate making.

[0003] In a conventionally known positive type lithographic printing plate material for an infrared laser for direct plate making, an alkali aqueous solution-soluble resin having a phenolic hydroxyl group such as a novolak resin is used. For example, Japanese Patent Application Laid-Open No. 7-28527
In JP-A No. 5 (1999) -2005, an image forming material in which a substance that absorbs light and generates heat, various onium salts, quinonediazide compounds, and the like are added to an aqueous alkaline solution having a phenolic hydroxyl group, such as a novolak resin, is proposed. I have. In these image forming materials, onium salts, quinonediazide compounds, and the like act as a dissolution inhibitor for an aqueous alkali-soluble resin in the image area, and are decomposed by heat in the non-image area so that the dissolution inhibiting ability is not exhibited and removed by development. To form an image. In such an image forming material, since onium salts, quinonediazide compounds, and the like have a light absorption region (350 to 500 nm) in the visible region, there is an inconvenience that the handling place is limited to a yellow lamp. Furthermore, onium salts, quinonediazide compounds, etc. are not necessarily compatible with alkaline aqueous solution-soluble polymer compounds or substances that absorb light and generate heat, and it is difficult to prepare a uniform coating solution. And it is difficult to obtain a stable image forming material.

In some cases, as in JP-B-46-27919, an image is formed using a novolak resin or the like without using a photosensitive compound. However, the novolak resin itself has a low solvent resistance, and a cleaner or the like is used. However, there were problems such as a decrease in printing durability due to the use of UV ink, and the inability to print with UV ink. Further, when a novolak resin is used without using a photosensitive compound, there is a disadvantage that the development latitude is extremely poor.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to improve the low image forming property of a recording layer using a polymer compound soluble in an aqueous alkali solution, to have no restriction on the handling place, and to improve the printing durability. An object of the present invention is to provide an infrared laser image forming material for direct plate making which is excellent and has good stability in sensitivity to the concentration of a developing solution, that is, good developing latitude.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies and as a result, by forming a specific layer structure using an alkali water-soluble polymer compound, the present invention can be used even under a white lamp. The present inventors have found that a photosensitive image-forming material whose development latitude is greatly improved can be obtained, and the present invention has been completed.

That is, the photosensitive image-forming material for an infrared laser of the present invention is prepared by coating a monomer (a)
1) a monomer having a sulfonamide group in which at least one hydrogen atom is bonded to a nitrogen atom in one molecule;
-2) In one molecule, a monomer having an active imino group represented by the following formula, (a-3) acrylamide, methacrylamide, acrylate, methacrylate, and hydroxystyrene having a phenolic hydroxyl group are selected from hydroxystyrene. Containing 50% by weight or more of a copolymer containing 10% by mole or more of at least one monomer as a copolymer component (hereinafter, this layer is appropriately referred to as (A) layer), and (B) phenol A layer containing 50% by weight or more of an alkali aqueous solution-soluble resin having a neutral hydroxyl group (hereinafter, this layer is appropriately referred to as a (B) layer) is sequentially laminated,
The layer containing at least 50% by weight or more of the (B) alkali aqueous solution-soluble resin having a phenolic hydroxyl group contains a compound that absorbs light and generates heat.

[0008]

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In the present invention, the photosensitive layer has a two-layer structure, and (A) (a-1) in one molecule,
A monomer having a sulfonamide group in which at least one hydrogen atom is bonded to a nitrogen atom (hereinafter, appropriately referred to as a monomer having a sulfonamide group), (a-2) an activity represented by the above formula in one molecule A monomer having an imino group (hereinafter appropriately referred to as a monomer having an imino group), (a-3) a monomer selected from acrylamide, methacrylamide, acrylate, methacrylate and hydroxystyrene having a phenolic hydroxyl group (Hereinafter, appropriately referred to as a monomer having a phenolic hydroxyl group), a copolymer containing 10 mol% or more of at least one monomer as a copolymerization component
By forming a layer containing 0% by weight or more, an intermediate layer having excellent printing durability and solvent resistance is formed.
Further, a layer containing at least 50% by weight of (B) an alkaline aqueous solution-soluble resin having a phenolic hydroxyl group is formed thereon, and this layer contains a compound that absorbs light and generates heat. Alkaline aqueous solution-soluble resins represented by this novolak resin have a strong interaction with compounds that absorb light and generate heat, have high sensitivity in image formation by exposure, and have a high effect of suppressing development of unexposed areas. A wide development latitude can be realized.

In the vicinity of the support, heat generated by the compound that absorbs light and generates heat is applied to the support having high thermal conductivity before the temperature of the photosensitive layer in the exposed portion rises to an area sufficient to cause a reaction. And the development may not be performed efficiently. However, in the image forming material of the present invention, the layer (A) corresponding to the above-mentioned intermediate layer exists between the layer (B) and the support. And (B), the compound which absorbs light and generates heat can efficiently be used for development without diffusing the heat to the support, so that the sensitivity and development latitude are remarkably improved.

In the present invention, as described above, by adopting a two-layer structure as the photosensitive layer, the interaction between the alkali-soluble resin in the layer (B) and the compound which absorbs light and generates heat is excellent in the layer (B). Image formation becomes possible. This eliminates the necessity of adding a compound having a light absorption region (350 to 500 nm) in the visible region, such as onium salts and quinonediazide compounds, so that the device can be used under a white light, and the handling place is limited to a yellow light. No inconvenience. Further, since it is possible to form an image without using a thermal decomposition reaction such as an onium salt or a quinonediazide compound, heat is efficiently used for image formation, and the development latitude is remarkably improved.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. In the present invention, the polymer compound soluble in an aqueous alkali solution used for forming the layer (A) includes (a-1) a monomer having a sulfonamide group, (a-2) a monomer having an active imino group, and (a-3) At least one of the monomers having a phenolic hydroxyl group as a copolymer component
A copolymer containing 50% by weight or more of a copolymer containing at least 50% by mole (hereinafter, referred to as a "specific copolymer").

(A-1) As the monomer having a sulfonamide group, one molecule has at least one sulfonamide group having at least one hydrogen atom bonded to a nitrogen atom and at least one polymerizable unsaturated bond. And a monomer comprising a low-molecular compound having the same. 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).

[0014]

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Where X¹, X^TwoIs -O- or-
NR⁷Indicates-. R¹, R^FourIs a hydrogen atom or-
CH_ThreeRepresents R^Two, R^Five, R⁹, R¹², R¹⁶Each
Alkylene having 1 to 12 carbon atoms which may have a substituent
Group, cycloalkylene group, arylene group or aralkyl
Represents a len group. R^Three, R⁷, R¹³Are hydrogen atoms, respectively
C1-C12 alkyl which may have a substituent
Group, cycloalkyl group, aryl group or aralkyl group
Show. Also, R⁶, R¹⁷Has a substituent
C1-C12 alkyl group, cycloalkyl
Group, an aryl group, and an aralkyl group. R⁸, R^Ten, R
¹⁴Is a hydrogen atom or -CH_ThreeRepresents R¹¹, R^FifteenEach
1 to 12 carbon atoms which may have a single bond or a substituent
Alkylene group, cycloalkylene group, arylene group or
Represents an aralkylene group. Y¹, Y ^TwoIs a single bond
Or -CO-.

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

(A-2) The monomer having an active imino group includes a low-molecular compound having an active imino group represented by the following formula and one or more polymerizable unsaturated bonds in one molecule. Monomer.

[0018]

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Specific examples of such compounds include:
N- (p-toluenesulfonyl) methacrylamide, N
-(P-Toluenesulfonyl) acrylamide and the like can be suitably used.

The monomer corresponding to (a-3) 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.

In the photosensitive image-forming material of the present invention, the alkali water-soluble copolymer which can be used for the layer (A) formed adjacent to the support is selected from (a-1) to (a-3). It is necessary that at least one is contained as a copolymer component in an amount of 10 mol% or more, and more preferably 20 mol% or more. When the amount of the copolymer component is less than 10 mol%, the sensitivity is lowered due to low solubility in an alkali developer even after exposure, and the effects of using this copolymer component, such as printing durability and sensitivity improvement, are insufficient. Becomes

In addition, the copolymer (a-1)
To (a-3) and other copolymerizable components other than the monomer having a phenolic hydroxyl group described below.

As the other copolymer components, for example, the following monomers (1) to (12) can be used. (1) Acrylic esters having an aliphatic hydroxyl group, such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, and methacrylic esters. (2) 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; (3) 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. (4) acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-
Hexyl methacrylamide, N-cyclohexyl acrylamide, N-hydroxyethyl acrylamide, N-
Acrylamide or methacrylamide such as phenylacrylamide, N-nitrophenylacrylamide, and N-ethyl-N-phenylacrylamide. (5) 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.

(6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate. (7) Styrenes such as styrene, α-methylstyrene, methylstyrene, and chloromethylstyrene. (8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone. (9) Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene. (10) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile and the like. (11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide. (12) acrylic acid, methacrylic acid, maleic anhydride,
Unsaturated carboxylic acids such as itaconic acid;

In the present invention, the copolymer contained in the layer (A) preferably has a weight average molecular weight of 2,000 or more and a number average molecular weight of 500 or more. More preferably, the weight average molecular weight is 5,000 to 300,000, the number average molecular weight is 800 to 250,000, and the degree of dispersion (weight average molecular weight / number average molecular weight) is 1.1 to 10.

Each of the copolymers contained in the layer (A) may be used alone or in combination of two or more kinds. Preferably, it is used in an addition amount of 55% by weight or more. If the addition amount of the copolymer is less than 50% by weight, the printing durability of the image forming material is deteriorated. .

In the layer (A), in addition to the above copolymer, for example, a polymer compound having a phenolic hydroxyl group, specifically, a phenol formaldehyde resin, an m-cresol formaldehyde resin, a p-cresol formaldehyde resin, -/ P- mixed cresol formaldehyde resin, phenol / cresol (m-, p- or m
-/ P-mixing), and may contain a novolak resin such as a mixed formaldehyde resin or a pyrogallol acetone resin.

Further, as described in US Pat. No. 4,123,279, a phenol having an alkyl group having 3 to 8 carbon atoms as a substituent, such as t-butylphenol formaldehyde resin and octylphenol formaldehyde resin, and formaldehyde are used. May be used in combination. Such resins may be used alone or in combination of two or more.

In the composition constituting the layer (A), various additives can be further added, if necessary, in addition to the copolymer. For example, onium salts, o-quinonediazide compounds, aromatic sulfone compounds, aromatic sulfonic acid ester compounds and other substances that are thermally decomposable and that substantially reduce the solubility of the alkali water-soluble polymer compound when not decomposed. The combined use is preferred 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. 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. Examples of the o-quinonediazide compound used in the present invention include those described in J. Am. The compounds described in "Light-Sensitive Systems" by John Coleyer (John Wiley & Sons. Inc.), pages 339-352, can be used, but are particularly suitable for reacting with various aromatic polyhydroxy compounds or aromatic amino compounds. Preference is given to sulfonic esters or sulphonamides of quinonediazides. Also, benzoquinone (1,2)-as described in JP-B-43-28403.
Diazidesulfonic acid chloride or naphthoquinone-
Esters of (1,2) -diazide-5-sulfonic acid chloride with pyrogallol-acetone resin, U.S. Pat.
Esters of benzoquinone- (1,2) -diazidosulfonic acid chloride or naphthoquinone- (1,2) -diazido-5-sulfonic acid chloride and phenol-formaldehyde resin described in 046,120 and 3,188,210 are also used. It is preferably 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.

The addition amount of the o-quinonediazide compound is preferably 1 to 50% by weight, more preferably 5 to 30% by weight, and particularly preferably 10 to 3% by weight, based on the total solid content 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.

The counter ions of the onium salts include 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.

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 layer constituting material (A) is preferably 0.05 to 20% by weight, more preferably 0.1 to 15% by weight, and particularly preferably 0 to 15% by weight. 0.1 to 10% by weight.

In the present invention, a fatty acid having a large carbon number called a wax or a derivative thereof can be added to the layer (A) in order to improve the stability before development. An alkyl or alkenyl group having 6 to 32 carbon atoms (e.g., n-hexyl group, n-heptyl group, n
-Octyl group, n-nonyl group, n-decyl group, linear alkyl group such as n-undecyl group, branched alkyl group such as 14-methylpentadecyl group, 16-methylheptadecyl group, 1-hexenyl group , 1-heptenyl group, 1-
Fatty acids and fatty acid esters having an alkenyl group such as an octenyl group and a 2-methyl-1-heptenyl group) are preferable, and among these, from the viewpoint of solubility in a coating solvent, an alkyl group or an alkenyl group having 25 or less carbon atoms Are preferred. Specific examples of compounds that can be used include fatty acids such as enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, Nonadecanoic acid, arachinic acid, behenic acid, lignoceric acid, cerotic acid, heptacosanoic acid, montanic acid, melicic acid, laccelic acid, undecylenic acid, oleic acid, elaidic acid, setreic acid, erucic acid, brassic acid and the like. Fatty acid esters include methyl, ethyl, propyl, butyl, dodecyl, phenyl and naphthyl esters of these fatty acids. Examples of thiofatty acid esters include methyl thioester, ethyl thioester, propyl thioester, butyl thioester, and benzyl thioester of these fatty acids. Examples of the fatty acid amide include amides, methylamides, and ethylamides of these fatty acids.

Each of these compounds may be used alone or in combination of two or more. 0.02 to 10% by weight, preferably 0.1 to 10% by weight, based on the total solid content of the printing plate material.
It is used in an amount of 2 to 10% by weight, particularly preferably 2 to 10% by weight. When the amount of the compound represented by the general formula (A) is less than 0.02% by weight, the development stability against damage becomes insufficient, and when the amount is 10% by weight, the effect is saturated. Absent.

Further, in the material constituting the layer (A), Japanese Patent Application Laid-Open No. 62-251740 discloses a method for increasing the stability of processing under development conditions.
And non-ionic surfactants described in JP-A-3-208514, and amphoteric surfactants described in JP-A-59-121044 and JP-A-4-13149. 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 surfactant include alkyl di (aminoethyl) glycine, alkyl polyaminoethyl glycine hydrochloride, 2-alkyl-N-
Carboxyethyl-N-hydroxyethylimidazolinium betaine or N-tetradecyl-N, N-betaine type (for example, trade name "Amogen K": Daiichi Kogyo Co., Ltd.)
Manufactured). The proportion of the nonionic surfactant and amphoteric surfactant in the (A) layer constituting material is as follows:
The content is preferably 0.05 to 15% by weight, more preferably 0.1 to 15% by weight.
1 to 5% by weight.

A printing-out agent for obtaining a visible image immediately after heating by exposure and a dye or a pigment as an image coloring agent can be added to the layer constituting material (A) in the present invention. 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, the 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, 54-74728, 60-3626, 61-1437
Combinations of trihalomethyl compounds and salt-forming organic dyes described in JP-A Nos. 48, 61-151644 and 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% based on the total solid content of the component (A).
It can be added at a ratio of 10 to 10% by weight, preferably 0.1 to 3% by weight.

Further, a plasticizer can be added to the material constituting the layer (A), if necessary, in order to impart flexibility to the coating film. For example, butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic acid or methacrylic acid Oligomers and polymers are used. Further, a long-chain fatty acid ester, a long-chain fatty acid amide, or the like may be added to improve the film strength.

In the layer constituting material of the present invention, a surfactant for improving coating properties, for example, JP-A-62-170950
A fluorine-based surfactant such as that described in JP-A No. 2-2,086 can be added. The preferable addition amount is 0.01 to 1% by weight of the total material constituting the layer, more preferably 0.05 to 0.
5% by weight.

When the image forming material of the present invention is used as a negative type, it is necessary to add a substance which is crosslinked by an acid in order to form an alkali-insoluble film (image area). Examples of the substance which is preferably used in the photosensitive layer of the present invention and which is crosslinked by an acid include (a) a compound having two or more hydroxymethyl groups, alkoxymethyl groups, epoxy groups or vinyl ether groups in the molecule, and these groups are benzene. A compound bonded to a ring, (b) an N-hydroxymethyl group,
Compounds having an N-alkoxymethyl group or an N-acyloxymethyl group, (c) epoxy compounds and the like can be mentioned. (A) Compounds having two or more hydroxymethyl groups, alkoxymethyl groups, epoxy groups or vinyl ether groups in the molecule, and these groups are bonded to a benzene ring, specifically include methylolmelamine and resole resin,
Epoxidized novolak resins, urea resins, and the like are included. Further, compounds described in "Crosslinking Agent Handbook" (written by Shinzo Yamashita and Tosuke Kaneko, Taiseisha Co., Ltd.) are also preferable. In particular, a phenol derivative having two or more hydroxymethyl groups or alkoxymethyl groups in the molecule is preferable because the strength of an image portion when an image is formed is good. Specifically, a resole resin can be used.

However, the cross-linking agents which are cross-linked by these acids are unstable to heat, and the storage stability after the preparation of the image recording material is not so good. On the other hand, the molecule has 3 to 5 benzene rings which have two or more hydroxymethyl groups or alkoxymethyl groups linked to the benzene ring in the molecule and may have a substituent, and further have a molecular weight of 1 to 5. The phenol derivative having a molecular weight of 200 or less has good stability during storage and is most preferably used in the present invention. The alkoxymethyl group of the phenol derivative is preferably one having 6 or less carbon atoms.
Specifically, a methoxymethyl group, an ethoxymethyl group, n-
Preferred are a propoxymethyl group, an i-propoxymethyl group, an n-butoxymethyl group, an i-butoxymethyl group, a sec-butoxymethyl group, and a t-butoxymethyl group. Further, a 2-methoxyethoxy group and 2-methoxy-1-
Like propyl groups, alkoxy-substituted alkoxy groups are also preferred.

A phenol derivative having a hydroxymethyl group can be obtained by reacting a corresponding phenol compound having no hydroxymethyl group with formaldehyde in the presence of a base catalyst. At this time, the reaction is preferably performed at a reaction temperature of 60 ° C. or lower in order to prevent resinification and gelation. Specifically, it can be synthesized by a method described in JP-A-6-28067, JP-A-7-64285, or the like.

The phenol derivative having an alkoxymethyl group can be obtained by reacting the corresponding phenol derivative having a hydroxymethyl group with an alcohol in the presence of an acid catalyst. At this time, the reaction is preferably performed at a reaction temperature of 100 ° C. or less in order to prevent resinification and gelation. Specifically, it can be synthesized by a method described in European Patent EP632003A1 or the like.

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

As the epoxy compound (c), there can be mentioned a monomer, dimer, oligomer or polymer epoxy compound 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.

In the present invention, when a crosslinking agent capable of crosslinking by an acid is used, the amount added is preferably 5 to 70% in the solid content of the layer (A).
% By weight, preferably 10 to 65% by weight. If the amount of the crosslinking agent that is crosslinked by the acid is less than 5% by weight, the film strength of the image portion when the image is recorded is deteriorated, and if it exceeds 70% by weight, the stability during storage is not preferable. The crosslinking agents that are crosslinked by these acids may be used alone or in combination of two or more.

The coating amount of all the materials constituting the layer (A) applied on the support of this image forming material is 0.5 to 4.0.
g / m ² , preferably 0.5 g / m ²
If it is less than 4.0, the effect of improving the printing durability will be insufficient, and it will be 4.0.
g / m ² , which is not preferable.

In the image-forming material of the present invention, (B) an alkali aqueous solution-soluble resin having a phenolic hydroxyl group of 50 wt. % Is formed.

The resin having a phenolic hydroxyl group, which is a main component constituting the layer (B), includes, for example, phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, m- /
Novolak resins such as p-mixed cresol-formaldehyde resin and phenol / cresol (m-, p-, or m- / p-mixed) mixed formaldehyde resin can be mentioned.

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.

The layer (B) contains, together with the resin having a phenolic hydroxyl group, a compound that absorbs light and generates heat. The compound that absorbs this light and generates heat is
There is a light absorption region in the infrared region of 700 or more, preferably 750 to 1200 nm.
It refers to a material that exhibits heat conversion ability. Specifically, various pigments or dyes that absorb light in this wavelength range and generate heat can be used. As pigments, commercially available pigments and Color Index (CI) Handbook, “Latest Pigment Handbook”
(Edited by Japan Pigment Technology Association, 1977), "Latest Pigment Application Technology" (CMC Publishing, 1986), and "Printing Ink Technology", CMC Publishing, 1984.

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 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),
"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,
Ball mill, impeller, disperser, KD mill,
A colloid mill, a dynatron, a three-roll mill, a pressure kneader and the like can be mentioned. 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 and JP-A-60-63744; And the cyanine dyes described in British Patent No. 434,875.

As a dye, US Pat. No. 5,156,
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
(B) 0.01 to 50% by weight, preferably 0.1 to 10% by weight, based on the total solid content of the layer constituting material, particularly preferably 0.5 to 10% by weight for dyes, and particularly preferably 3 to 10% for pigments. 0.1 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. It is essential that these dyes or pigments are added to the layer (B), but they may be added to other layers, for example, the layer (A) described above.

In the present invention, as a compound that absorbs light contained in the layer (B) and generates heat by absorbing light, the compound is compatible with a resin having a phenolic hydroxyl group, which is a constituent material of the layer (B), to thereby form an alkali of the resin. A compound that reduces the solubility in water and reduces the solubility-lowering effect by heating can also be added, and examples of the compound include those represented by the following general formula (I).

[0063]

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The compound has the property of absorbing light to generate heat, has an absorption range in the infrared region of 700 nm to 1200 nm, has good compatibility with the resin soluble in an aqueous alkali solution, and has a basic property. It is a dye, interacts with the resin to have a group that interacts with an alkaline water-soluble resin such as an ammonium group and an iminium group in the molecule,
Its alkali water solubility can be controlled and can be suitably used in the present invention.

In the general formula (I), R _{1 to} R ₄ each independently represent a hydrogen atom or a carbon atom which may have a substituent.
12 represents an alkyl group, an alkenyl group, an alkoxy group, a cycloalkyl group, or an aryl group, and R ₁ and R ₂ , and R ₃ and R ₄ may be bonded to each other to form a ring structure.
Here, as R _{1 to} R ₄ , specifically, a hydrogen atom,
Examples include a methyl group, an ethyl group, a phenyl group, a dodecyl group, a naphthyl group, a vinyl group, an allyl group, and a cyclohexyl group. When these groups have a substituent, examples of the substituent include a halogen atom, a carbonyl group, a nitro group, a nitrile group, a sulfonyl group, a carboxyl group, a carboxylic acid ester, and a sulfonic acid ester.
R _{5 to} R ₁₀ each independently represent an alkyl group having 1 to 12 carbon atoms which may have a substituent, wherein R _{5 to} R ₁₀
Specific examples include a methyl group, an ethyl group, a phenyl group, a dodecyl group, a naphthyl group, a vinyl group, an allyl group, and a cyclohexyl group. When these groups have a substituent, examples of the substituent include a halogen atom, a carbonyl group, a nitro group, a nitrile group, a sulfonyl group, a carboxyl group, a carboxylic acid ester, and a sulfonic acid ester.

R _{11 to} R ₁₃ each independently represent a hydrogen atom,
Represents a halogen atom or an alkyl group having 1 to 8 carbon atoms which may have a substituent, wherein R ₁₂ may be bonded to R ₁₁ or R ₁₃ to form a ring structure, and m> In the case of 2, a plurality of R ₁₂ may be bonded to each other to form a ring structure.
As R _{11 to} R ₁₃ , specifically, a chlorine atom, a cyclohexyl group, a cyclopentyl ring in which R ₁₂ is bonded to each other,
And a cyclohexyl ring. When these groups have a substituent, examples of the substituent include a halogen atom, a carbonyl group, a nitro group, a nitrile group, a sulfonyl group, a carboxyl group, a carboxylic acid ester, and a sulfonic acid ester. M represents an integer of 1 to 8, and preferably 1 to 3. R _{14 to} R ₁₅ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms which may have a substituent, and R ₁₄ is bonded to R ₁₅ to form a ring structure. When m> 2, a plurality of R ₁₄ may be bonded to each other to form a ring structure. R
Specific examples of _{14 to} R ₁₅ include a chlorine atom, a cyclohexyl group, a cyclopentyl ring and a cyclohexyl ring formed by bonding R _{14 to} each other. When these groups have a substituent, the substituent may be a halogen atom,
Carbonyl group, nitro group, nitrile group, sulfonyl group,
Examples thereof include a carboxyl group, a carboxylic acid ester, and a sulfonic acid ester. M represents an integer of 1 to 8,
Preferably it is 1-3.

[0067] In the general formula (I), X ^- Specific examples of the anion is represented by, perchloric acid, tetrafluoroboric acid, hexafluorophosphoric acid, triisopropyl naphthalenesulfonic acid, 5-nitro -o -Toluenesulfonic acid, 5-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 and paratoluenesulfonic acid. Among them, alkyl aromatic sulfonic acids such as hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid and 2,5-dimethylbenzenesulfonic acid are particularly preferable.

The compound represented by the general formula (I) is a compound generally called a cyanine dye. Specifically, the following compounds are suitably used, but the present invention is not limited to these specific examples. Not something.

[0069]

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In the present invention, when a compound such as the above-mentioned cyanine dye is used in the layer (B), the amount of the compound added is 99/1 to 7 with respect to the alkali aqueous solution-soluble resin.
The range of 0/30 is preferable from the viewpoint of sensitivity, and 99/1 to 99/1.
A range of 75/25 is more preferred.

Various additives can be further added to the composition constituting the layer (B), if necessary.
As the additives that can be used in the layer (B), the various additives described above can be similarly mentioned as those that can be added to the composition constituting the layer (A). When the present invention is used as a negative-type image forming material, it is preferable to add a crosslinking agent to the layer (B) in the same manner as the layer (A).

Usually, these photosensitive layers can be produced by dissolving each of the above-mentioned components in a solvent and applying the solution on a support. At the interface between the layers, compatibility occurs due to the influence of a solvent or the like, and a situation where the (A) layer and the (B) layer are not clearly separated may occur, and the effect of the present invention may be reduced. Therefore, in producing the image forming material of the present invention, it is necessary to form the two layers separately.

As this method, for example, a method utilizing the difference in solvent solubility between the copolymer contained in the layer (A) and the alkali-soluble resin contained in the layer (B), and the second layer was applied. Thereafter, a method of rapidly drying and removing the solvent may be used. Hereinafter, these methods will be described in detail, but the method of applying the two layers separately is not limited thereto.

The method of utilizing the difference in solvent solubility between the copolymer contained in the layer (A) and the resin soluble in an aqueous alkali solution contained in the layer (B) can be obtained by applying (A) ) A solvent system in which both the specific copolymer contained in the layer and the copolymer used in combination with the specific copolymer are insoluble. Thereby, even if the two-layer coating is performed, each layer can be clearly separated into a coating film. For example, a copolymer containing, as a copolymerization component, a specific monomer constituting the component (A) insoluble in a solvent that dissolves an aqueous alkali-soluble resin such as methyl ethyl ketone or 1-methoxy-2-propanol is selected. (A) The layer (A) mainly composed of the copolymer is coated and dried using a solvent system that dissolves the copolymer constituting the layer component, and then the layer (B) mainly composed of an alkali aqueous solution-soluble resin. To methyl ethyl ketone or 1
By applying using a solvent that does not dissolve the component (A) such as -methoxy-2-propanol, it is possible to form two layers.

On the other hand, the method for drying the solvent very quickly after the application of the second layer is to blow high-pressure air from a slit nozzle installed substantially at right angles to the running direction of the web, or to apply a heating medium such as steam. This can be achieved by applying heat energy as conduction heat from the lower surface of the web from the roll (heating roll) supplied inside, or by combining them. FIG. 1 shows a configuration example of an apparatus for performing continuous coating and drying used when forming a second layer (B) after forming a layer by coating and drying the first layer (A). FIG.
This apparatus uses, for example, a roughened aluminum web as a support, and forms a second layer on a first-layer coated product in which a first layer is previously coated on the support.

The apparatus shown in FIG. 1 comprises a coating head 2 for applying a coating solution for a second layer to a coating material 1 for a first layer, and a first drying zone for performing drying by hot air and high-pressure drying by blowing high-pressure air. And a second drying zone 4 for drying with hot air. The first drying zone 3 has an air supply port 5 for sending hot air and a high-pressure air for high-speed drying. A device 9, a heat exchanger 10, a pressure gauge 11, a high-pressure air blowing nozzle 12, air volume adjusting dampers 18 and 19, and an exhaust port 6 for discharging hot air out of the system are provided. The second drying zone 4 is provided with an air supply port 7 for sending hot air and an exhaust port 8 for discharging the hot air out of the hot air system. Further, guide rolls 13 to 17 for conveying the aluminum web 1 are provided at appropriate positions of the apparatus.

In such an apparatus, the coating material 1 for the first layer ((A) layer) continuously running at 5 to 150 m / min is applied with the coating liquid for the second layer ((B) layer) by the coating head 2. ~40ml / m ²
, And then guided to the first drying zone 3, where drying proceeds with respect to the first layer coating 1 at a temperature of usually 50 to 150 ° C. The evaporated solvent gas accompanies the hot air and is discharged out of the system through the exhaust port 6. At the stage where drying by hot air is performed near the entrance in the first drying zone 3, the second layer coating film is usually in an undried state.

The undried second-layer coating film is dried very quickly by the high-speed air blown from the high-speed blowing nozzle 12 installed at the transport position thereof at a substantially right angle to the traveling direction of the first-layer coating product 1. Is done.

The high-speed blowing nozzle 12 has a compressor
Or a high-pressure air generator 9 comprising a high-pressure blower.
The generated high-pressure air is heated at 50 ° C. to 2
Heat to 0 ° C and adjust to the desired value with air volume control dampers 18 and 19.
After adjusting to the air volume, supply. This allows the desired temperature and
The high pressure air in the form of a slit with a wind speed and
Striking in a very short time
The second layer can be formed by quickly evaporating the solvent.
Normally, the pressure inside the nozzle 12 of the high pressure wind is 300 mmAq (H _TwoO)
~ 3kg / cm^TwoAnd preferably 1000 mmAq to 1 kg / cm^Two
It is. Wind speed of the blowing wind from the high-speed blowing nozzle 12
Is about 20 m / s to 300 m / s. In addition, high-speed balloon
The width between slits of the chisel 12 is about 0.1 mm to 5 mm.
However, a range of 0.3 mm to 1 mm is desirable. More high pressure wind
The spray angle on the first layer coating 1 is 0 ^o~ 90^oWell
But 10^o~ 60^oIs preferred. Mao, book of nozzles
The number is two in the figure display, but 1 to
It can be about eight.

Thus, high-speed drying is performed in the first drying zone 3 to form a coating film for the second layer. Thereafter, the first layer coated material on which the second layer is formed is guided to the second drying zone, and is heated by hot air at 100 ° C. to 150 ° C. from the air supply port 7. Thereby, the amount of the residual solvent remaining in the film in a trace amount is controlled in the range of 30 to 200 mg / m ² . The dissolved solvent gas is exhausted from the exhaust port 8 to the outside of the system together with the hot air. Then, a desired two-layer coating can be achieved by these drying operations.

In the formation of the photosensitive layer of the image forming material of the present invention, the latter method may be carried out by drying with a heating roll instead of drying with high-speed air as described above. As an apparatus in this case, for example, the high-pressure air generator 9, heat exchanger 10, pressure gauge 11, high-pressure air blowing nozzle 12, and air volume adjusting dampers 18 and 19 in FIG. Is a heating roll.
In such a case, by supplying a heating medium such as steam to the inside of the roll, the surface temperature of the roll is raised to 80 ° C to 200 ° C.
Can be heated. Heat energy is generated between the surface of the heating roll and the aluminum web of the first layer coating material 1.
And drying becomes possible.

Furthermore, the method of removing the rapid solvent can be carried out by using both drying by high-speed air and drying by heating roll. In this case, the device
For example, in FIG. 1, a guide roller 14 having the same heating roll as described above may be used, and the solvent can be more rapidly evaporated.

In the above example as shown in FIG.
After drying with hot air in the drying zone 3, drying with hot air and drying with high-pressure air or drying with a heating roll are performed simultaneously. However, the first hot-air drying is omitted, and immediately after coating, high-pressure air is used. Drying may be performed.

In the production of the image forming material of the present invention, it is preferable to continuously apply and dry using a coating and drying apparatus as shown in FIG. The first layer is also coated and dried by installing the same device as that for the second layer upstream of the second layer coating and drying device. It is preferable to provide a roughening means upstream of the coating head of the drying apparatus and to perform the continuous operation by continuously running the support in order to improve productivity.

The photosensitive image-forming material of the present invention contains at least 50% by weight of a copolymer containing at least one of (A) (a-1) to (a-3) as a copolymer component in an amount of 10 mol% or more. The ratio of the layer to be formed and the layer containing (B) the alkaline aqueous solution-soluble novolak resin in an amount of 50% by weight or more is as follows:
Although optional, the weight ratio is preferably in the range of 10:90 to 95: 5, particularly preferably in the range of 20:80 to 90:10.

The photosensitive solution to be coated on the support is used by dissolving these components in a suitable solvent. The concentration of the above components (total solids including additives) in the solvent is preferably 1 to 5
0% by weight. As a method of applying, various methods can be used. For example, bar coater application, spin coating, spray application, curtain application, dip application,
Examples include air knife application, blade application, roll application, and the like. As the coating amount decreases, the apparent sensitivity increases, but the film characteristics of the photosensitive film deteriorate.

The support used in the present invention is a dimensionally stable plate-like material such as paper, plastic (for example, polyethylene, polypropylene, polystyrene, etc.) laminated paper, metal plate ( For example, aluminum, zinc, copper, etc.), plastic films (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate,
Cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), and 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 for removing the rolling oil on the surface is performed. 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.

Anodizing treatment conditions 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. If the amount of the anodic oxide film is less than 1.0 g / m ² , the printing durability is insufficient or the non-image area of the image forming material is easily damaged, and the ink adheres to the damaged area during printing. So-called "scratch dirt" tends to occur. After the anodizing treatment, the aluminum surface is subjected to a hydrophilic treatment as necessary. U.S. Pat.
Nos. 4,066, 3,181,461, 3,280,734 and
There is an alkali metal silicate (for example, sodium silicate aqueous solution) method as disclosed in US Pat. No. 3,902,734. In this method, the support is immersed in an aqueous solution of sodium silicate or electrolytically treated. In addition, Tokiko Sho 36
Potassium fluoride zirconate disclosed in U.S. Pat.No. 2,220,63 and U.S. Pat.
No. 4,689,272, and a method of treating with polyvinyl phosphonic acid.

The image-forming material of the present invention comprises a support having thereon a layer (A) and a layer (B) as a photosensitive layer.
If necessary, an undercoat layer can be provided between the layer (A) and the support. 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 phosphoric acid, phenylphosphinic acid optionally having a substituent,
Naphthylphosphinic acid, organic phosphinic acids such as alkylphosphinic acid and glycerophosphinic acid, amino acids such as glycine and β-alanine, and hydrochlorides of amines having a hydroxy group such as hydrochloride of triethanolamine, and the like, You may mix and use 2 or more types.

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 may be added for improving the tone reproducibility of the image forming 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 . In the image forming material of the present invention, a protective layer may be provided on the photosensitive layer if necessary. Examples of the protective layer component include polyvinyl alcohol and a mat material used for a general photosensitive image forming material.

The image forming material prepared as described above is usually subjected to image exposure and development processing. In the present invention, a light source having an emission wavelength of 700 nm or more in a near-infrared to infrared region is preferable as a light source of an active light beam used for image exposure, and a solid-state laser and a semiconductor laser are particularly preferable.

As a developing solution and a replenishing solution for the image forming material of the present invention, conventionally known alkaline aqueous 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.

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 the post-processing when the image forming material of the present invention is used as a printing plate, these processings 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 forming 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 an unnecessary image portion (for example, a film edge mark of the original film), it is 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 desensitizing gum as required, but when the lithographic printing plate is desired to have a 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, but 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.

[0100]

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 Component (A) Copolymer Synthesis Example 1 (Copolymer 1) 31.0 g (0.36 mol) of methacrylic acid, chloroform 39.1 g (0.36 mol) of ethyl acid and 200 ml of acetonitrile were added, and 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 this 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, 5.04 g of N- (p-aminosulfonylphenyl) methacrylamide was placed in a 100 ml three-necked flask equipped with a stirrer, a condenser and a dropping funnel.
210 mol), and 2.05 g (0.05 g) of ethyl methacrylate.
180 mol), acrylonitrile 1.11 g (0.02
1 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 5.04
g, 2.05 g of ethyl methacrylate, 1.11 g of acrylonitrile, 20 g of N, N-dimethylacetamide, and 0.15 g of "V-65" were dropped by 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, methanol 40
g was added to the mixture, the mixture was cooled, and the obtained mixture was poured into 2 liters of water while stirring the water. After stirring the mixture for 30 minutes, the precipitate was taken out by filtration and dried to obtain 15 g of a white solid. I got The weight average molecular weight of this copolymer 1 (polystyrene standard) was measured by gel permeation chromatography and found to be 53,000.
It was 0.

Synthesis Example 2 (Copolymer 2) In the polymerization reaction of Synthesis Example 1, 5.04 g (0.02 g) of N- (p-aminosulfonylphenyl) methacrylamide was used.
Polymerization reaction was carried out in the same manner as in Synthesis Example 1 except that N- (p-hydroxyphenyl) methacrylamide was changed to 3.72 g (0.0210 mol), and the weight average molecular weight (polystyrene standard) was 47,000. Was obtained.

[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.

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

Example 1 The following photosensitive solution A1 was applied to the obtained substrate and dried at 100 ° C. for 2 minutes to form a layer (A). The coating amount after drying was 1.4 g / m ² . Then, the following photosensitive solution B1
And dried at 100 ° C. for 2 minutes to form a layer (B), thereby obtaining a lithographic printing plate. The total coating amount of the photosensitive solution after drying was 2.0 g / m ² .

Photosensitive solution A1 copolymer 1 0.75 g Cyanine dye A 0.04 g p-toluenesulfonic acid 0.002 g Tetrahydrophthalic anhydride 0.05 g Victoria Pure Blue (BOH counter anion is converted to 1-naphthalene sulfonic acid anion Dye) 0.015 g Fluorosurfactant (Megafac F-177, manufactured by Dainippon Ink and Chemicals, Inc.) 0.02 g γ-butyl lactone 8 g Methyl ethyl ketone 7 g 1-methoxy-2-propanol 7 g Photosensitive solution B1 m, p-cresol novolak (m / p ratio = 6/4, weight average molecular weight 4000) 0.25 g cyanine dye A 0.05 g n-dodecyl stearate 0.02 g fluorinated surfactant (MegaFac F-177, (Manufactured by Dainippon Ink and Chemicals, Inc.) 0.05 g methyl ethyl keto 7g 1-Methoxy-2-propanol 7g

Example 2 The following photosensitive solution A2 was applied to the obtained substrate by coating.
After drying at 0 ° C. for 2 minutes, a layer (A) was formed. The coating amount after drying was 1.5 g / m ² . Thereafter, the following photosensitive solution B2 was applied and dried by the following method. That is, using the drying zone shown in FIG. 1 and spraying high pressure air of 3000 mmAq from the slit nozzle 12 immediately after application,
The guide roll 14 was changed to a heating roll and heating at 130 ° C. was also performed to form the layer (B), thereby obtaining a lithographic printing plate. The total coating amount of the photosensitive solution after drying was 2.0 g / m ² . Photosensitive solution A2 m, p-cresol novolak (m / p ratio = 6/4, weight average molecular weight 4000) 0.75 g copolymer 2 0.10 g cyanine dye B 0.3 g 2,6-bishydroxymethyl-p- Cresol 0.02 g p-toluenesulfonic acid 0.005 g tetrahydrophthalic anhydride 0.01 g Victoria Pure Blue (a dye in which the counter anion of BOH is converted to 1-naphthalenesulfonic acid anion) 0.015 g fluorinated surfactant (Megafax F-177, manufactured by Dainippon Ink and Chemicals, Inc.) 0.02 g Methyl ethyl ketone 12 g 1-methoxy-2-propanol 10 g Photosensitive solution B2 m, p-cresol novolak (m / p ratio = 6/4, weight average molecular weight 4000) ) 0.25 g cyanine dye B 0.07 g n-dodecyl stearate 0.0 2 g Fluorosurfactant (Megafac F-177, manufactured by Dainippon Ink and Chemicals, Inc.) 0.05 g Methyl ethyl ketone 7 g 1-methoxy-2-propanol 7 g

Comparative Example 1 Only the photosensitive solution A1 used in Example 1 was applied to the obtained substrate, and dried at 100 ° C. for 2 minutes to form a photosensitive layer to obtain a lithographic printing plate. The coating amount after drying is 1.4 g /
m ² .

Comparative Example 2 Of the photosensitive solution A1 used in Example 1,
Except that copolymer 1 was replaced by m, p-cresol novolak (m / p ratio = 6/4, weight average molecular weight: 4000), the same coating was applied and dried at 100 ° C. for 2 minutes to obtain a photosensitive layer. Was formed to obtain a lithographic printing plate. The coating amount after drying was 1.4 g / m ² .

[Performance evaluation of lithographic printing plates] The lithographic printing plates of Examples 1 and 2 and Comparative Examples 1 and 2 prepared as described above were evaluated for performance according to the following criteria. Table 1 shows the evaluation results.

(Sensitivity and Development Latitude) 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 ). Fuji Photo Film Co., Ltd.
Automatic developing machine (Fuji Photo Film Co., Ltd .: “PS”) charged with a developer, DP-4 and a rinse liquid FR-3 (1: 7).
Processor 900VR "). At this time, DP-4 was used in two levels, one diluted 1: 8 and one diluted 1: 6, and the line width of the non-image portion obtained with each developer was measured. The irradiation energy of the laser corresponding to was determined, and this was defined as the sensitivity. The difference between the standard 1: 8 dilution and 1: 6 dilution was recorded. The smaller the difference is, the better the development latitude is, and if it is 20 mJ / cm ² or less, it is at a practical level. (Printing durability) Using a lithographic printing plate developed with DP-4 (1: 8), a Heidel KOR-
Printing was performed on high-quality paper using a D machine. Printing was performed while wiping the plate surface with a cleaner solution (Fuji Photo Film Co., Ltd .: “Plate Cleaner CL2”) every 5000 prints. Table 1 shows the final number of printed sheets. Here, the final number of printed sheets is the number of sheets until the photosensitive layer of the lithographic printing plate causes a film reduction and ink is not partially applied, that is, a so-called plate jump.

[0114]

[Table 1]

From Table 1, the planographic printing plates according to the present invention are:
It has a photosensitive layer having a two-layer structure of the layer (A) and the layer (B), and has excellent development latitude and printing durability, and good sensitivity as compared with Comparative Examples 1 and 2. I understand. On the other hand, the comparative example in which only the layer (A) was the photosensitive layer was inferior in the development latitude, and the comparative example 2 in which the copolymer having the specific monomer of the present invention was not used had extremely low printing durability. .

[0116]

According to the photosensitive image forming material for an infrared laser of the present invention, the low image forming property of the recording layer using a polymer compound soluble in an aqueous alkali solution is improved, and there is no restriction on the handling place. The effect is that the sensitivity to the concentration of the developing solution, that is, the developing latitude is good, and that it can be suitably used with good sensitivity for an image forming material for direct plate making having excellent printing durability.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram showing one embodiment of a continuous coating and drying apparatus used for manufacturing an image forming material of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 First layer coating material 2 Coating head 3 1st drying zone 4 2nd drying zone 5 Inlet (1st drying zone) 6 Exhaust port (1st drying zone) 7 Inlet (2nd drying zone) 8 Exhaust port ( (2nd drying zone) 9 high-pressure air generator 10 heat exchanger 11 pressure gauge 12 high-pressure air blowing nozzle 13, 14, 15, 16, 17 guide roll 18, 19 air volume adjustment damper

Claims (1)

[Claims] 1. A method comprising the steps of: (A) forming a monomer (a)
(A-1) a layer containing 50% by weight or more of a copolymer containing 10% by mole or more of at least one of (a-3) as a copolymer component; (A-2) a monomer having an active imino group represented by the following formula in one molecule; and (a-2) a monomer having a sulfonamide group having at least one hydrogen atom bonded thereto. (A-3) A monomer selected from acrylamide, methacrylamide, acrylate, methacrylate and hydroxystyrene having a phenolic hydroxyl group, and (B) a resin soluble in an aqueous alkali solution having a phenolic hydroxyl group in an amount of 50 wt. And a layer containing at least 50% by weight or more of the (B) alkali aqueous solution-soluble resin having a phenolic hydroxyl group, and a compound that absorbs light and generates heat. A photosensitive image-forming material for an infrared laser, comprising: