JPH10207052A - Positive photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the positive photosensitive composition safe to white light and wide in development latitude and capable of forming a high-contrast image without lowering sensitivity and restraining image blurring due to printing. SOLUTION: This positive photosensitive composition contains a copolymer comprising structural units derived from an additionally polymerizable monomer having a fluoroaliphatic group substituted by fluorine for hydrogen, monomers each represented by the structures of formulae [1]-[4], and monomers represented by the structures of formulae [5]-[8], and these components amounting to >90weight% of the total copolymer components, and in formulae [1]-[8], A is an H or halogen atom or the like; W is an O atom or a -NR3 - group; R1 is an alkylene or arylene group; each of R2 and R3 is an alkyl group or the like; each of R4 -R6 is an alkyl or aryl group; each of Y and Z is an arylene group; X is a bonding group; U is a cyano or aryl group or the like; each of (l) and (m) is 0 or 1; and (n) is 1, 2, or 3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photosensitive composition suitable for the production of a lithographic printing plate, an IC circuit or a photomask. The present invention relates to a positive photosensitive composition having excellent acceptability. More specifically, a specific compound is added to a positive-type photosensitive composition that has been made highly sensitive by a conventionally known method, without deteriorating the sensitivity, showing a high-contrast image-forming property, and showing burn-out and whiteness. The present invention relates to a positive-type photosensitive composition having widened lamp safety and development tolerance.

[0002]

2. Description of the Related Art Photosensitive compositions containing an o-quinonediazide compound have been widely used industrially in the production of lithographic printing plates and in photoresist applications as very excellent positive photosensitive compositions. . Conventionally, various proposals have been made for techniques for increasing the sensitivity of an o-quinonediazide-based positive photosensitive composition, without deteriorating the sensitivity, showing a high-contrast image-forming property, and, at the same time, preventing burn-out. No satisfactory technology has been obtained in terms of white light safety and development tolerance. For example, when the amount of the o-quinonediazide compound is reduced, the sensitivity naturally rises, but the image becomes softer with the decrease, and there is a problem that the burn-out suppressing property, the safety of white light and the development tolerance are deteriorated. Was. When an o-quinonediazide compound is combined with a binder having a large alkali solubility, the sensitivity is increased as described above, but the image becomes softer, and the burn-out suppressing property, white light safety, and development acceptability are deteriorated. Had the problem that

On the other hand, as a system exhibiting higher sensitivity than an o-quinonediazide compound, a chemical amplification system in which an alkali-soluble group is protected with an acid-decomposable group as described in US Pat. No. 4,491,628, European Patent 249,139 and the like. Has been proposed and widely used. However, even in this case, a satisfactory image having high image forming properties and wide development tolerance has not been obtained. Here, that the image is soft means that there is a large difference between the number of steps at which the image starts to remain when exposed and developed through the step wedge and the number of steps at which the film completely remains.
Conversely, a high contrast image means that the difference between the number of steps at which the image starts to remain and the number of steps at which the film completely remains is small. Burning is caused by the fact that nitrogen gas generated by the decomposition of quinonediazide raises the lith film and makes perfect contact exposure impossible.In general, when the clear sensitivity is the same, the harder the image, the more blur Is easy to resolve.

[0004] White light safety indicates the stability of image sensitivity when a printing plate is exposed to white light such as a fluorescent light, and the higher the image contrast, the better the white light safety. This is related to the fact that quinonediazide is partially decomposed by white light. This is because the image becomes similar to the above. The step wedge is a strip-shaped film in which the density changes, for example, by 0.15 at each step, and is used to obtain the relationship between the exposure amount and the remaining amount of the photosensitive layer after development after exposure. The clear sensitivity means the sensitivity at which an image starts to be formed after exposure and development. Further, the development tolerance is a characteristic indicating the degree to which the image sensitivity after exposure and development changes when the concentration of the developer changes, and the smaller the sensitivity variation, the better the development tolerance.

Heretofore, techniques have been proposed to increase the sensitivity by adding a non-photosensitive compound to a photosensitive composition containing an o-quinonediazide compound, but each of them has a drawback. Is the current situation. For example, JP
Japanese Patent Publication No. 2-80022 proposes a method of increasing the sensitivity by adding a cyclic acid anhydride. However, in this method, although the effect of increasing the sensitivity is recognized, if an acid anhydride is added to such an extent that a sufficient increase in sensitivity can be obtained, the image becomes soft, and the safety of white light and the development tolerance are greatly deteriorated. JP-A-55-73045 proposes the addition of a condensation product of hydroxybenzophenone and formaldehyde in order to increase the sensitivity. In this case also,
The effect of increasing the sensitivity is recognized, as in the case of Japanese Patent Application Laid-Open No. H11-209, but if added to such an extent that a sufficient increase in sensitivity can be obtained, the image becomes similarly soft, and the safety of white light and the development tolerance deteriorate.

[0006]

Some methods for adding a surfactant have been proposed to solve these problems. For example, Japanese Patent Application Laid-Open No. Sho 59-121044 discloses a method of broadening the development tolerance by adding an amphoteric surfactant and an organoboron-based surfactant to a positive-working photosensitive composition having increased sensitivity. Also, JP-A-62-25
No. 1740 discloses a method of broadening the development tolerance by adding a nonionic surfactant to a positive-working photosensitive composition having increased sensitivity. However, although all of the methods had some effect of improving development tolerance, they were not sufficient, and if a sufficient effect was to be obtained, the sensitivity was lowered. In addition, no effects were obtained with respect to burn-out suppression and white light safety. In addition, Japanese Patent Application Laid-Open No. 62-2261
43, JP-A-3-172849, JP-A-8-15858
Japanese Patent Application Publication No. JP-A-2002-176131 describes a fluoropolymer having a fluoroaliphatic group, a polyoxyalkylene group or an anionic group as a surfactant. However, even when these polymers were used, there was no effect with respect to burnout suppression and white light safety. The present invention solves the above-mentioned problems of the prior art, shows a high contrast image forming property without lowering the sensitivity, and satisfies all of burn-out suppressing properties, white light safety, and development tolerance. An object of the present invention is to provide a positive photosensitive composition that can be used.

[0007]

Means for Solving the Problems As a result of diligent studies, the present inventors have found that the above object can be achieved by adding a specific fluorine-containing polymer to a positive photosensitive composition. . That is, the present invention relates to a component (1) having a fluorine atom as a fluorine-containing polymer, a component (2) having an acidic hydrogen atom, and a component (3) exhibiting lipophilicity.
Is added to the photosensitive composition in an amount of more than 90% by weight to the photosensitive composition. It has been found that a positive photosensitive composition having a wide tolerance is obtained. This means is particularly effective for increasing the contrast of a positive photosensitive composition which has been made highly sensitive by a conventionally known means. It has been found that blur control, white light safety, and development tolerance are improved.

That is, the object of the present invention is achieved by the following positive photosensitive composition. At least the following (1)
, A component represented by (2) and a component represented by (3) as copolymerization components, and the total weight of the components (1), (2) and (3) is all A positive photosensitive composition comprising a polymer compound in a range exceeding 90% of the component weight. (1) A monomer capable of addition polymerization having a fluoroaliphatic group in which a hydrogen atom is substituted by a fluorine atom (2) A monomer represented by the following structures [1] to [4]

[0009]

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In the formula, A represents a hydrogen atom, a halogen atom or an alkyl group. W is oxygen or —NR ₃ —, and R ₃ represents a hydrogen atom, an alkyl group, or an aryl group.
R ₁ represents an alkylene group or an arylene group which may have a substituent, and R ₂ represents a hydrogen atom, an alkyl group, or an aryl group. R ₄ represents an alkyl group or an aryl group. Y and Z represent an arylene group which may be the same or different.
X is a linking group, and represents a divalent organic group consisting of atoms selected from carbon, nitrogen, oxygen, sulfur, halogen, and hydrogen atoms. m and l represent an integer of 0 to 1, and n represents an integer of 1 to 3. (3) Monomers represented by the following structures [5] to [8]

[0011]

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W is oxygen or -NR _3- , and R ₃ represents a hydrogen atom, an alkyl group or an aryl group. R ₅ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, and R ₆ represents an alkyl group or an aryl group. U represents a cyano group, an aryl group, an alkoxy group, an aryloxy group, an acyloxymethyl group, a hetero ring containing a nitrogen atom, or —CH ₂ OCOR ₆ (R ₆ is as defined above). A has the same meaning as in the above [1] to [4].

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The vinyl monomers of the components (1), (2) and (3) which characterize the present invention will be described in more detail below. The fluoroaliphatic group in which the hydrogen atom of the component (1) is substituted by a fluorine atom is usually a saturated and generally monovalent or divalent aliphatic group. This includes straight, branched or cyclic. The fluoroaliphatic group is required to have a sufficient effect for the purpose of the present invention.
-20, preferably 6-12 carbon atoms, and 4
It has at least 0% by weight, preferably at least 50% by weight, of fluorine bonded to a carbon atom. Suitable fluoro-aliphatic _{groups, C n F 2n + 1 -} (n is 1 or more preferably an integer of 3 or more) substantially completely or fully fluorinated perfluoro aliphatic group such as (hereinafter, Rf Also abbreviated as a group)
It is.

The addition-polymerizable monomer part of the addition-polymerizable monomer having a fluoroaliphatic group in which a hydrogen atom on a carbon atom of the component (1) is fluorinated is a vinyl monomer having a radically polymerizable unsaturated group. A dimer is used. Among these vinyl monomers, preferred are acrylate, methacrylate, acrylamide, methacrylamide, styrene and vinyl. Specific examples of acrylates and methacrylates to which a fluoroaliphatic group is bonded include, for example, Rf-R'-OOC-C
(R ″) ＝ CH ₂ (where R ′ is, for example, a single bond, alkylene, sulfonamidoalkylene, or carbonamidoalkylene, and R ″ is a hydrogen atom, a methyl group,
A halogen atom or a perfluoroaliphatic group).

As specific examples of the above, for example, 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-bonded monomers, Reports Res. Lab. Asahi Glass C
o., Ltd., vol. 34, 1984, pp. 27-34, a macromer to which a fluoroaliphatic group is bonded can also be used. Further, as the fluoroaliphatic group-bonding monomer, a mixture having different lengths of perfluoroalkyl groups as shown in the following structural formula can be used.

[0016]

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The amount of these fluoroaliphatic group-containing vinyl monomers used in the fluorine-containing copolymer used in the present invention is 3 to 3 based on the weight of the copolymer.
70% by weight, preferably in the range of 7-40% by weight. The monomer used as the component (2) is represented by the following structures [1] to [4].

[0018]

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In the formula, A represents a hydrogen atom, a halogen atom or an alkyl group. W is oxygen or —NR ₃ —, and R ₃ represents a hydrogen atom, an alkyl group, or an aryl group.
R ₁ represents an alkylene group or an arylene group which may have a substituent, and R ₂ represents a hydrogen atom, an alkyl group, or an aryl group. R ₄ represents an alkyl group or an aryl group. Y and Z may be the same or different, and represent an arylene group. X is a linking group, and represents a divalent organic group consisting of atoms selected from carbon, nitrogen, oxygen, sulfur, halogen, and hydrogen atoms. m and l represent an integer of 0 to 1, and n represents an integer of 1 to 3. As a preferred range of the monomers represented by the structures [1] to [4], A is a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₃ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms. Group, 6-20 carbon atoms
Represents an aryl group. R ₁ is an alkylene group having 1 to 12 carbon atoms which may have a substituent, an arylene group having 6 to 20 carbon atoms, R ₂ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and 6 to 20 carbon atoms. Represents an aryl group. R ₄ represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. Y and Z each represent an arylene group having 6 to 20 carbon atoms.

In the general formulas [1] and [2], A is more preferably a hydrogen atom or a methyl group. More preferred alkyl groups represented by Y, R ₁ or R ₂ include alkyl groups having 1 to 20 carbon atoms such as methyl, ethyl and isopropyl, and more preferred aryl groups represented by Y, R ₁ or R ₂ Examples thereof include aryl groups having 6 to 18 carbon atoms such as phenyl and naphthyl. The arylene group or alkylene group represented by Y or R ₁ may have a substituent, and examples of the substituent include halogen atoms such as fluorine, chloro, and bromo; alkoxy groups such as methoxy and ethoxy; and phenoxy. And an amide group such as an acetamide, an alkoxycarbonyl group such as an ethoxycarbonyl group, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 18 carbon atoms. Preferred specific compounds of the component (2) are shown below.

[0021]

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[0022]

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The amount of these acidic group-containing vinyl monomers used in the fluorine-containing copolymer used in the present invention is 5 to 70% based on the weight of the copolymer.
%, Preferably in the range of 10 to 50% by weight.

The monomer used as the component (3) is
It is shown by the following structures [5]-[8].

[0025]

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[0026] W is oxygen or -NR, ₃ - a is, R ₃
Represents a hydrogen atom, an alkyl group or an aryl group. R ₅ represents an alkyl group which may have a substituent and an aryl group which may have a substituent, and R ₆ represents an alkyl group and an aryl group. U represents a cyano group, an aryl group, an alkoxy group, an aryloxy group, an acyloxymethyl group, or a hetero ring containing a nitrogen atom. A is the above [1]-
Represents the same thing as [4]. As a preferable range of the monomers represented by the structures [5] to [8], W is oxygen,
Or —NR ₃ —, wherein R ₃ is a hydrogen atom, having 1 to 2 carbon atoms.
0 represents an alkyl group and an aryl group having 6 to 20 carbon atoms.
R ₅ is an alkyl group having 1 to 8 carbon atoms which may have a substituent and an aryl group which may have a substituent, R ₆ is an alkyl group having 1 to 20 carbon atoms, and 6 to 20 carbon atoms. Represents an aryl group. 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 OCOR ₆ (R ₆
Is as defined above).

When R ₅ 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 aryl group such as phenoxy. Examples include an oxy group, a cyano group, an amide group such as acetamide, and an alkoxycarbonyl group such as an ethoxycarbonyl group. When R ₅ 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 (3) 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-phenyl Maleimide, N-
Chlorophenylmaleimide, N-tolylmaleimide, N
N-substituted maleimides such as -hydroxymaleimide and N-benzylmaleimide; allyl compounds such as allyl acetate, allyl caproate, allyl stearate and allyloxyethanol; ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether and methoxyethyl vinyl ether , Ethoxyethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, phenyl vinyl ether, tolyl vinyl ether, trinyl ethers such as 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 (3) are
It is a monomer represented by the structure [5] or [7].

Other addition-polymerized unsaturated compounds optionally used include Polymer Handbook 2nd ed.,
J. Brandrup, Wiley Interscience (1975) Chapter 2 Pa
ge 1 to 483 can be used. The amount of these vinyl monomers used in the fluorinated copolymer of the present invention is 5 to 80% by weight, preferably 10 to 70% by weight, based on the weight of the copolymer.
The fluoropolymer 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 an acidic group-containing 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. Alternatively, if necessary, another addition-polymerizable unsaturated compound can be added to produce the compound in the same manner as described above.

Hereinafter, specific examples of the structure of the fluoropolymer according to the present invention will be described. The numbers in the formulas indicate the molar ratios of the monomer components to be written.

[0031]

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[0032]

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[0033]

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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.
0, preferably 6,000-100,
Up to 000 can be used. Next, other components required for preparing the positive photosensitive composition of the present invention will be described.

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-based 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 excluding the solvent. Next, other components required for preparing the positive photosensitive composition according to the present invention will be described.

As the positive type photosensitive composition, any one can be used as long as its solubility or swelling property in a developing solution changes before and after exposure, and a typical example thereof is an o-quinonediazide compound. For example, in the case of a positive photosensitive composition containing an alkali-soluble resin and an o-quinonediazide compound, the o-quinonediazide compound is a compound having at least one o-quinonediazide group,
Those which increase the solubility in an alkaline aqueous solution by actinic rays are preferred.

As such a structure, various structures are known. For example, “Light-Sensiti” by J. KOSAR
ve Systems "(John Wiley & Sons, Inc, 1965) P.
336-page 352.

As the positive photosensitive composition, sulfonic acid esters of various hydroxyl compounds and o-benzoquinonediazide or o-naphthoquinonediazide are particularly preferable.

Examples of the o-quinonediazide compound as described above include, for example, an ester of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride with a phenol-formaldehyde resin or a cresol-formaldehyde resin; US Pat. No. 3,635. , 709, 1,2-naphthoquinone-2-diazide-
Ester of 5-sulfonyl chloride and pyrogallol acetone resin; 1,2-naphthoquinone-2-diazide-5 described in JP-B-63-13528.
Esters of sulfonyl chloride and resorcin-benzaldehyde resin; 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride and resorcin-pyrogallol-acetone co-condensation resin described in JP-B-62-44,257. Of ester;
1,127-naphthoquinone-2-polyester having a hydroxyl group at the terminal described in US Pat.
Diazide-5-sulfonyl chloride esterified with a homopolymer of N- (4-hydroxyphenyl) methacrylamide or another copolymerizable monomer described in JP-B-50-24641 Copolymer obtained by esterifying 1,2-naphthoquinone-2-diazido-5-sulfonyl chloride;
4-29,922 ester of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride with bisphenol-formaldehyde resin;
P- described in JP-B-52-36,043
Hydroxystyrene homopolymers or copolymers with other copolymerizable monomers have 1,2-naphthoquinone-2
-Diazide-5-sulfonyl chloride esterified; 1,2-naphthoquinone-2-diazide-5
There are esters of sulfonyl chloride with polyhydroxybenzophenone.

Other known o-quinonediazide compounds that can be used in the present invention include JP-A-63-80,2525.
4, JP-A-58-5,737, JP-A-57-11
No. 1,530, JP-A-57-111,531, JP-A-57-114,138, JP-A-57-142,635
No., JP-A-51-36,129, JP-B-62-3,4
No. 11, JP-B-62-51,459, JP-B-51-4
No. 83 and the like described in each specification can be mentioned. The content of the o-quinonediazide compound is usually 5 to 5% based on the total solid content of the photosensitive composition.
It is 60% by weight, more preferably 10 to 40% by weight.

The photosensitive composition other than o-quinonediazide includes a compound in which an alkali-soluble group is protected by an acid-decomposable group (a group having the property of being decomposed by an acid) and a photoacid generator (a compound which generates an acid by a trading company of radiation). ), A chemically amplified photosensitive composition comprising a combination of the above. Known photoacid generators can be used in the chemical amplification system.

For example, SISchlesinger, Photogr.Sci.E
ng., 18,387 (1974), TSBal etal, Polymer, 21,423 (198
0) etc., U.S. Pat.No.4,069,055
No. 4,069,056, ammonium salts described in JP-A-3-140,140, etc., DCNecker et al., Macromolecules, 17,2468
(1984), CSwen et al, Teh, Proc.Conf.Rad.Curing ASI
A, p478 Tokyo, Oct (1988), U.S. Pat.No. 4,069,055,
4,069,056, etc., phosphonium salts, JVCrivello
etal, Macromorecules, 10 (6), 1307 (1977), Chem. & Eng.Ne
ws, Nov. 28, p31 (1988), European Patent No. 104,143, U.S. Patent No. 339,049, No. 410,201, JP-A-2-150,848, JP-A-2-296,514, etc.
llo etal, Polymer J. 17, 73 (1985), JVCrivello eta
lJOrg.Chem., 43, 3055 (1978), WRWatt et al., J. Polym
er Sci., Polymer Chem. Ed., 22, 1789 (1984), JVCrivel
lo etal, Polymer Bull., 14,279 (1985), JVCrivello e
tal, Macromorecules, 14 (5), 1141 (1981), JVCrivello
etal, J. Polymer Sci., Polymer Chem. Ed., 17, 2877 (197
9), EP 370,693, U.S. Patent 3,902,114, EP 233,567, 297,443, 297,442, U.S. Pat.
No. 60,013, 4,734,444, 2,833,827, Dokoku Patent No.
2,904,626, 3,604,580, 3,604,581, etc., sulfonium salts, JVCrivello etal, Macromorecule
s, 10 (6), 1307 (1977), JVCrivello etal, J. PolymerSc
Selenonium salts described in i., Polymer Chem.Ed., 17, 1047 (1979), etc., CSWenetal, Teh, Proc. Conf. Rad. Curing ASI
A, p478 Tokyo, Oct (1988), etc., onium salts such as arsonium salts, U.S. Pat.No. 3,905,815, JP-B-46-4605
No., JP-A-48-36281, JP-A-55-32070, JP-A-60-2
39736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62-212401, JP-A-63-70243
No., organic halogen compounds described in JP-A-63-298339, K. Meier et al., J. Rad.Curing, 13 (4), 26 (1986), TP
Gill et al., Inorg.Chem., 19, 3007 (1980), D. Astruc, Ac
c. Chem. Res., 19 (12), 377 (1896), organometallics / organic halides described in JP-A-2-14145, etc., S. Hayase et al.
J. Polymer Sci., 25, 753 (1987), E. Reichmanis et al., J. Ph
olymer Sci., Polymer Chem. Ed., 23, 1 (1985), QQZhu et.
al, J. Photochem., 36, 85, 39, 317 (1987), B. Amit et al, Tet
rahedron Lett., (24) 2205 (1973), DHR Barton et al., J.
Chem Soc., 3571 (1965), PM Collins et al., J. Chem. SoC.,
Perkin I, 1695 (1975), M. Rudinstein et al, Tetrahedron
Lett., (17), 1445 (1975), JWWalker etal J. Am. Chem. So
c., 110,7170 (1988), SCBusman et al, J.Imaging Techno
l., 11 (4), 191 (1985), HM Houlihan et al, Macormolecule
s, 21, 2001 (1988), PM Collins et al., J. Chem. Soc., Chem.
Commun., 532 (1972), S. Hayase et al, Macromolecules, 18,
1799 (1985), E. Reichmanis et al., J. Electrochem. Soc., So
lid State Sci.Technol., 130 (6), FMHoulihan etal, Ma
cromolcules, 21, 2001 (1988), European Patent No. 0290,750,
046,083, 156,535, 271,851, 0,388,343
No. 3,901,710, 4,181,531, U.S. Pat.
-198538, JP-A-53-133022 and the like, a photoacid generator having a 0-nitrobenzyl-type protecting group, M. TUNOOK etal,
Polymer Preprints Japan, 35 (8), G. Berner et al., J. Rad.
Curing, 13 (4), WJMijs et al, Coating Technol., 55 (69
7), 45 (1983), Akzo, H. Adachi et al, Polymer Preprints,
Japan, 37 (3), European Patent Nos. 0199,672, 84515, 19
No. 9,672, No. 044,115, No. 0101,122, U.S. Pat.
No. 8,564, 4,371,605, 4,431,774, JP-A-64-18
No. 143, JP-A-2-245756, compounds capable of generating sulfonic acid by photodecomposition represented by iminosulfonate and the like described in Japanese Patent Application No. 3-140109 and the like, described in JP-A-61-166544 and the like. The disulfone compound of the above can be mentioned.

Among the compounds capable of decomposing upon irradiation with actinic rays or radiation to generate an acid, those which are particularly effectively used are described below. (1) The following general formula (PAG) substituted with a trihalomethyl group
The oxazole derivative represented by 1) or the general formula (PA)
An S-triazine derivative represented by G2).

[0044]

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

[0046]

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[0047]

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

[0049]

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

R ³ , R ⁴ and R ⁵ each independently represent a substituted or unsubstituted alkyl group or aryl group. Preferred are an aryl group having 6 to 14 carbon atoms, an alkyl group having 1 to 8 carbon atoms, and substituted derivatives thereof. Preferred substituents are an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a nitro group, a carboxyl group, a hydroxy group and a halogen atom for the aryl group, and a substituent for the alkyl group. An alkoxy group having 1 to 8 carbon atoms, a carboxyl group, and an alkoxycarbonyl group.

[0052] Z ^- represents a counter anion, for example BF ₄ ^-, As
_{^{F 6 -, PF 6 -,}} SbF 6 -, SiF 6 2-, ClO 4 -, CF 3 SO 3 - perfluoroalkane sulfonate anion such as, pentafluorobenzenesulfonic acid anions, naphthalene-1-sulfonic acid anion But not limited thereto, such as a polynuclear aromatic sulfonic acid anion, an anthraquinone sulfonic acid anion, and a sulfonic acid group-containing dye.

Also, two of R ³ , R ⁴ and R ⁵ and A
r ¹ and Ar ² may be bonded via a single bond or a substituent.

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

[0055]

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[0056]

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The above onium salts represented by the general formulas (PAG3) and (PAG4) are known, for example, JW Knap
czyk etal, J. Am. Chem. Soc., 91, 145 (1969), AL
Maycok et al., J. Org.Chem., 35, 2532, (1970), B.
Goethas etal, Bull.Soc.Chem.Belg., 73, 546, (19
64), HM Leicester, J. Ame. Chem. Soc., 51, 3587.
(1929), JV Crivello et al, J. Polym. Chem. Ed.,
18, 2677 (1980), U.S. Pat. Nos. 2,807,648 and 4,247,473, JP-A-53-101,33.
It can be synthesized by the method described in No. 1 or the like.

(3) Disulfone derivatives represented by the following formula (PAG5) or iminosulfonate derivatives represented by the following formula (PAG6).

[0059]

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

[0061]

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[0062]

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The amount of the compound which decomposes upon irradiation with actinic rays or radiation to generate an acid is usually 0.0
It is used in the range of 0.01 to 40% by weight, preferably 0.0
It is used in an amount of 1 to 20% by weight, more preferably 0.1 to 5% by weight. The content of these photoacid generators is generally 0.1 to 30% by weight, preferably 1 to 10% by weight, based on the total solids of the photosensitive composition.

Compounds having an alkali-soluble group protected by an acid-decomposable group include -CO-C- or -CO-Si-.
It is a compound having a bond, and the following examples can be given. a) comprising at least one group of orthocarboxylic acid esters and / or carboxylic acid amide acetals, wherein the compounds can be polymerizable, said groups occurring as crosslinking elements in the main chain or as lateral substituents B) an oligomeric or polymeric compound containing a repeating acetal and / or ketal group in the main chain; c) a compound containing at least one enol ester or N-acylaminocarbonate group; d) a β-keto ester Or a cyclic acetal or ketal of β-keto amide,

E) a compound containing a silyl ether group, f) a compound containing a silyl enol ether group, g) an aldehyde or ketone component
Monoacetals or monoketals having a solubility of 0.1-100 g / l, h) ethers of tertiary alcohols, and i) carboxylic esters and carbonates of tertiary allylic or benzylic alcohols.

Compounds of the type (a) which can be cleaved by acids as components of the radiation-sensitive mixture are described in German Offenlegungsschrift 2,
610,842 and 2,928,636. Mixtures containing compounds of type (b) are described in German Patents 2,306,248 and 2,71
No. 8,254. Compounds of class (c) are described in EP-A-0,006,626 and EP-A-0,006,627. Compounds of class (d) are described in EP-A-0,202,
The compounds which are described in DE 196 and used as class (e) are described in DE-A 3,544,165 and DE 3,601,264. Compounds of class (f) are described in German Offenlegungsschrift 3,730,78
No. 5,730,783, and compounds of type (g) are described in German Offenlegungsschrift 3,734.
No. 0,783. Compounds of type (h) are described, for example, in US Pat. No. 4,603,101, and compounds of type (i) are described, for example, in US Pat.
491,628 and a paper by JM Frechet et al. (J. Im.
aging Sci. 30 , 59-64 (1986)). The content of the compound protected by the acid-decomposable group is usually 1 to 60% by weight, more preferably 5 to 40% by weight, based on the total solid content of the photosensitive composition.

Examples of the water-insoluble synthetic resin soluble in an alkaline aqueous solution (hereinafter referred to as an alkali-soluble resin) include phenol-formaldehyde resin, cresol-formaldehyde resin, phenol-cresol-formaldehyde co-condensation resin, phenol-modified xylene resin,
In addition to polyhydroxystyrene, polyhalogenated hydroxystyrene, a copolymer of N- (4-hydroxyphenyl) methacrylamide, a copolymer of hydroquinone monomethacrylate, a sulfonylimide polymer described in JP-A-7-28244, And carboxyl group-containing polymers described in JP-A-7-36184. Other acrylic resins containing a phenolic hydroxyl group as disclosed in JP-A-51-34711, acrylic resins having a sulfonamide group described in JP-A-2-866, and urethane-based resins. Various alkali-soluble polymer compounds can also be used. These alkali-soluble polymer compounds have a weight average molecular weight of 50.
0 to 20,000 and number average molecular weight of 200 to 60,00
0 is preferred.

The alkali-soluble high molecular compound is
They may be used alone or in combination of two or more, and are used in an amount of 80% by weight or less of the total composition. Furthermore,
As described in U.S. Pat. No. 4,123,279, a phenol having a C3-8 alkyl group as a substituent, such as t-butylphenol formaldehyde resin or octylphenol formaldehyde resin, and formaldehyde are used. It is preferable to use a condensate in combination in order to improve the oil sensitivity of the image. Such an alkali-soluble resin is generally used in an amount of 90% by weight or less based on the total weight of the composition.

In the photosensitive composition, if necessary,
A cyclic acid anhydride for increasing sensitivity, a printing-out agent for obtaining a visible image immediately after exposure, a dye as an image coloring agent, and other fillers can be added.

It is preferable to add cyclic acid anhydrides, phenols, and organic acids to the photosensitive composition of the present invention in order to increase sensitivity. The cyclic acid anhydride U.S. Pat phthalic anhydride as described in 4,115,128 Pat, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-oxy - [delta ⁴ -
Examples include tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, and pyromellitic anhydride. As phenols, bisphenol A, p-nitrophenol, p-ethoxyphenol,
2,3,4-trihydroxybenzophenone, 4-hydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 4,4,4 "-trihydroxy-triphenylmethane, 4,4 ', 3", 4 " -Tetrahydroxy-3,5,3 ', 5'-tetramethyltriphenylmethane and the like.

As the organic acids, JP-A-60-8894
2, sulfonic acids, sulfinic acids, alkyl sulfates, phosphonic acids, phosphinic acids, phosphoric esters, carboxylic acids, and the like described in JP-A No. 2-96755 and JP-A-2-96755. 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, 1,4-cyclohexene-2,2- Examples thereof include dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, and ascorbic acid. The above cyclic acid anhydrides,
The proportion of phenols and organic acids in the photosensitive composition is preferably from 0.05 to 15% by weight, more preferably from 0.1 to 5% by weight.

Examples of the printing-out agent for obtaining a visible image immediately after exposure include a combination of a photosensitive compound which releases an acid upon exposure and an organic dye which forms a salt with an acid and changes color. it can.

Examples of the photosensitive compound that releases an acid upon exposure include, for example, o-naphthoquinonediazide-4-sulfonic acid halogenide described in JP-A-50-36209; No. 223, trihalomethyl-2-pyrone and trihalomethyl-s-triazine; various o-naphthoquinonediazide compounds described in JP-A-55-62,444; 77,742, 2-trihalomethyl-5-aryl-1,3,4-oxadiazole compounds; diazonium salts and the like. These compounds can be used alone or as a mixture, and the amount added is based on the total weight of the composition.
A range from 0.3 to 15% by weight is preferred.

In the photosensitive composition of the present invention, at least one kind of an organic dye which changes its color tone by interacting with a photolysis product of a compound which generates an acidic substance by photolysis is used. Such organic dyes include diphenylmethane, triarylmethane,
Thiazine-based, oxazine-based, phenazine-based, xanthene-based, anthraquinone-based, iminonaphthoquinone-based, and azomethine-based dyes can be used. Specifically, it is as follows. Brilliant Green, Eosin, Ethyl Violet, Erythrosin B, Methyl Green,
Crystal violet, basic fuchsin, phenolphthalein, 1,3-diphenyltriazine, alizarin red S, thymolphthalein, methyl violet 2B, quinaldine red, rose bengal, thymol sulfophthalein, xylenol blue, methyl orange, orange IV, Diphenylthiocarbazone, 2,7
-Dichlorofluorescein, paramethyl red, Congo red, benzopurpurine 4B, α-naphthyl red, Nile blue 2B, Nile blue A, phenacetaline, methyl violet, malachite green, parafuchsin, oil blue # 603 [Orient Chemical Industry Co., Ltd. Oil Pink # 312 [Orient Chemical Industry Co., Ltd.], Oil Red 5B [Orient Chemical Industry Co., Ltd.], Oil Scarlet # 308 [Orient Chemical Industry Co., Ltd.], Oil Red OG [Orient Chemical Co., Ltd.] Industrial Co., Ltd.), Oil Red RR (Orient Chemical Co., Ltd.), Oil Green # 502 (Orient Chemical Co., Ltd.), Spiron Red BEH Special (Hodogaya Chemical Co., Ltd.), Victoria Pure Blue BOH [Hodogaya Chemical Sangyo Co., Ltd.], Patent Pure-Blue [Sumitomo Sangoku Chemical Co., Ltd.], Sudan Blue II [BASF], m-cresol purple, cresol red, rhodamine B, rhodamine 6G, first acid violet R , Sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carbostearylamino-4-p-dihydrooxyethyl-amino-
Phenyliminonaphthoquinone, p-methoxybenzoyl-p'-diethylamino-o'-methylphenyliminoacetanilide, cyano-p-diethylaminophenyliminoacetanilide, 1-phenyl-3-methyl-4
-P-diethylaminophenylimino-5-pyrazolone, 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone and the like.

Particularly preferred organic dyes are triarylmethane dyes. Triarylmethane dyes are disclosed in JP-A-62-293471 and Japanese Patent Application No. 4-1128.
Those having a sulfonic acid compound as a counter anion as shown in JP-A-44-44 are particularly useful. These dyes can be used alone or as a mixture, and the addition amount is preferably 0.3 to 15% by weight based on the total weight of the photosensitive composition. Further, if necessary, it can be used in combination with other dyes and pigments, and its use amount is 70% by weight or less, more preferably 50% by weight or less based on the total weight of the dyes and pigments.

In the composition of the present invention, various resins having a hydrophobic group, such as octylphenol / formaldehyde resin, t-butylphenol / formaldehyde resin, t
-Butylphenol-benzaldehyde resin, rosin-modified novolak resin, and o of these modified novolak resins
-Naphthoquinonediazide sulfonic acid ester and the like; depending on various purposes, such as a plasticizer for improving the flexibility of the coating film, such as dibutyl phthalate, dioctyl phthalate, butyl glycolate, tricresyl phosphate, and dioctyl adipate. Various additives can be added. The amount of these additives is preferably in the range of 0.01 to 30% by weight based on the total weight of the composition.

Further, a known resin for further improving the abrasion resistance of the film can be added to these compositions. These resins include, for example, a polyvinyl acetal resin, a polyurethane resin, an epoxy resin, a vinyl chloride resin, a nylon, a polyester resin, an acrylic resin, and the like, and can be used alone or in combination. The addition amount is preferably in the range of 2 to 40% by weight based on the total weight of the composition.

Further, in the photosensitive composition of the present invention, in order to widen the latitude of development, Japanese Patent Application Laid-Open No.
Non-ionic surfactants described in JP-A-251740 and JP-A-4-68355;
An amphoteric surfactant as described in JP-A-9-121044 and JP-A-4-13149 can be added. Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, monoglyceride stearate, polyoxyethylene sorbitan monooleate, polyoxyethylene nonyl phenyl ether, and the like. Specific examples of the activator include alkyl di (aminoethyl) glycine, alkyl polyaminoethyl glycine hydrochloride, Amogen K (trade name, Daiichi Kogyo Co., Ltd.)
N-tetradecyl-N, N-betaine type), 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine, Levon 15 (trade name, Sanyo Chemical Co., Ltd., alkylimidazoline) Is mentioned. The proportion of the nonionic surfactant and amphoteric surfactant in the photosensitive composition is preferably 0.05 to 15% by weight, more preferably 0.1 to 5% by weight.

Improvement of coated surface quality: In the photosensitive composition of the present invention, a surfactant for improving the coated surface quality, for example, fluorine as described in JP-A-62-170950. A system surfactant can be added.
The preferable addition amount is 0.001 to 1.
0% by weight, and more preferably 0.005 to 0.5% by weight.

The following yellow dyes can be added to the photosensitive composition of the present invention. e) represented by the general formula [I], [II] or [III], wherein the absorbance at 417 nm is 70% of the absorbance at 436 nm
Yellow dye

[0081]

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In the formula [I], R₁And R_TwoAre independently
A hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group or
Represents an alkenyl group. Also R₁And R_TwoForms a ring
Is also good. R_Three, R_Four, R_FiveAre each independently a hydrogen atom,
It represents an alkyl group having 1 to 10 carbon atoms. G₁, G_TwoIs it
Each independently an alkoxycarbonyl group, an aryloxyca
Rubonyl group, acyl group, arylcarbonyl group, alkyl
Luthio, arylthio, alkylsulfonyl, a
Reelsulfonyl group or fluoroalkylsulfonyl group
Is shown. G₁And G_TwoMay form a ring. further
R₁, R_Two, R _Three, R_Four, R_Five, G₁, G_TwoOne of
One or more sulfonic acid groups, carboxyl groups,
Honamide group, imide group, N-sulfonylamido group,
Enol hydroxyl group, sulfonimide group or its metal
Has salts, inorganic or organic ammonium salts. Y is O,
S, NR (R is a hydrogen atom or an alkyl group or aryl
), Se, -C (CH_Three)_Two-, -CH = CH-
Represents a divalent atomic group selected, n₁Indicates 0 or 1.

[0083]

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[Wherein, R₆And R₇Are each independently hydrogen
Atom, alkyl group, substituted alkyl group, aryl group, substituted
Aryl group, heterocyclic group, substituted heterocyclic group, allyl group or
Represents a substituted allyl group;₆And R₇Together with it
May form a ring with the carbon atom to which it is attached. n
_TwoRepresents 0, 1 or 2. G_ThreeAnd G_FourAre each
Independently, hydrogen atom, cyano group, alkoxycarbonyl
Group, substituted alkoxycarbonyl group, aryloxycal
Bonyl group, substituted aryloxycarbonyl group, acyl
Group, substituted acyl group, arylcarbonyl group, substituted aryl
Carbonyl group, alkylthio group, arylthio group,
Rukylsulfonyl group, arylsulfonyl group, fluoro
Represents an alkylsulfonyl group. Where G _ThreeAnd G_FourBut
They do not become hydrogen atoms at the same time. G_ThreeAnd G_FourWhat is
Consists of non-metallic atoms together with the carbon atoms to which they are attached
A ring may be formed. ] Furthermore, R₆, R₇, G_Three, G_FourOne or more of one or more
Sulfonic acid group, carboxyl group, sulfonamide group,
Mido group, N-sulfonylamido group, phenolic hydroxyl
Group, sulfonimide group, or its metal salt, inorganic or organic
Has an ammonium salt.

[0085]

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R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , and R ₁₃ may be the same or different and may be a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkoxyl group, Group, acyl group, cyano group,
It represents an alkoxycarbonyl group, an aryloxycarbonyl group, a nitro group, a carboxyl group, a chloro group, or a bromo group.

When a lithographic printing plate photosensitive material is obtained from the photosensitive composition containing a fluorine-containing surfactant of the present invention, it is first provided on a suitable support. The photosensitive composition containing the fluorinated surfactant of the present invention is dissolved or dispersed in the following organic solvents alone or as a mixture, applied to a support, and dried.

As the organic solvent, any known organic solvents can be used.
Those in the range of -160 ° C are selected from the advantages in drying. Of course, it is better to select one in which the surfactant of the present invention dissolves.

Examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, n- or iso-propyl alcohol, n- or iso-butyl alcohol, diacetone alcohol, acetone, methyl ethyl ketone, methyl propyl ketone, and methyl butyl ketone. , Methyl amyl ketone, methyl hexyl ketone, diethyl ketone, diisobutyl ketone, cyclohexanone,
Ketones such as methylcyclohexanone and acetylacetone, benzene, toluene, xylene, cyclohexane,
Hydrocarbons such as methoxybenzene, ethyl acetate,
acetates such as n- or iso-propyl acetate, n- or iso-butyl acetate, ethyl butyl acetate, hexyl acetate, methylene dichloride, ethylene dichloride, halides such as monochlorobenzene, isopropyl ether, n-butyl ether, dioxane, Ethers such as dimethyldioxane and tetrahydrofuran, ethylene glycol, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, diethyl cellosolve, cellosolve acetate, butyl cellosolve, butyl cellosolve acetate, methoxymethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol Dieci Ether, propylene glycol,
Polyhydric alcohols such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, 3-methyl-3-methoxybutanol and derivatives thereof, dimethyl sulfoxide, N , N-dimethylformamide and the like are preferably used alone or in combination. And
The concentration of the solid content in the composition to be applied is suitably 2 to 50% by weight.

As a method for applying the composition of the present invention, for example, methods such as roll coating, dip coating, air knife coating, gravure coating, gravure offset coating, hopper coating, blade coating, wire doctor coating, spray coating and the like are used. The weight after drying is preferably 0.3 to 4.0 g / m ² . As the coating amount decreases, the exposure amount for obtaining an image may be small,
The film strength decreases. As the coating amount increases, the exposure amount is required but the photosensitive film becomes strong. For example, when used as a printing plate, a printing plate having a high printable number (high printing durability) can be obtained.

The drying of the photosensitive composition applied on the support is usually performed with heated air. Heating is 30
C. to 200.degree. C., particularly preferably 40 to 140.degree. In addition to a method in which the drying temperature is kept constant during the drying, a method in which the temperature is gradually increased may be performed.

In some cases, good results can be obtained by dehumidifying the dry air. The heated air is applied at a rate of 0.1 m / sec to 30 m / sec, particularly 0.5 m / sec to 2
It is preferable to supply at a rate of 0 m / sec.

Matt layer: A mat layer is provided on the surface of the photosensitive layer provided as described above in order to reduce the time required for evacuation during contact exposure using a vacuum printing frame and to prevent printing blur. Preferably, it is provided. More specifically,
-125805, JP-B-57-6582, 61-
A method of providing a mat layer as described in each of JP-A-28986 and a method of heat-fusing a solid powder as described in JP-B-62-62337.

The support used for the photosensitive lithographic printing plate or the like is a dimensionally stable plate-like material, and includes those which have been used as the support of the printing plate. Can be. Examples of such a support include paper, paper laminated with plastics (eg, polyethylene, polypropylene, polystyrene, etc.), eg, a metal plate such as aluminum (including aluminum alloy), zinc, iron, copper, etc., eg, diacetate. Cellulose, cellulose triacetate,
Films of plastics such as cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc .; paper or plastic on which the above metal is laminated or vapor-deposited Although a film is included, an aluminum plate is particularly preferable. The aluminum plate includes a pure aluminum plate and an aluminum alloy plate. Various aluminum alloys can be used, and for example, an alloy of aluminum with a metal such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, or nickel is used. These compositions also contain some negligible amount of impurities in addition to some iron and titanium.

The support is subjected to a surface treatment as required.
For example, in the case of a photosensitive lithographic printing plate, on the surface of the support,
A hydrophilic treatment is performed. In the case of a support having a surface of a metal, particularly aluminum, a surface treatment such as graining, immersion in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, or anodizing is performed. Is preferred. Also, U.S. Pat.
As described in US Pat. No. 14,066, an aluminum plate grained and then immersed in an aqueous solution of sodium silicate, and an aluminum plate as described in US Pat. No. 3,181,461 is anodized. Those that have been immersed in an aqueous solution of an alkali metal silicate after the oxidation treatment are also suitably used. The anodizing treatment, for example,
In an electrolytic solution in which an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, boric acid, or an organic acid such as oxalic acid or sulfamic acid or an aqueous solution or a non-aqueous solution of these salts is used singly or in combination of two or more, a current is supplied to an aluminum plate as an anode. Is carried out by flowing.

Also, silicate electrodeposition as described in US Pat. No. 3,658,662 is effective. These hydrophilic treatments are performed not only to make the surface of the support hydrophilic, but also to prevent harmful reactions with the photosensitive composition provided thereon and to improve the adhesion with the photosensitive layer. It is done to improve. Prior to graining the aluminum plate, if necessary, the surface may be subjected to a pretreatment to remove rolling oil on the surface and to expose a clean aluminum surface. For the former, solvents such as trichlene, surfactants and the like are used. For the latter, a method using an alkali etching agent such as sodium hydroxide or potassium hydroxide is widely used.

As the graining method, any of mechanical, chemical and electrochemical methods is effective. Examples of the mechanical method include a ball polishing method, a blast polishing method, and a brush polishing method in which an aqueous dispersion slurry of an abrasive such as pumice is rubbed with a nylon brush, and the chemical method is disclosed in JP-A-54-31187. A method of immersing in a saturated aqueous solution of an aluminum salt of a mineral acid as described in the official gazette is suitable, and as an electrochemical method, a method of alternating current electrolysis in an acidic electrolyte such as hydrochloric acid, nitric acid or a combination thereof is used. Is preferred. Among such surface roughening methods, particularly, a surface roughening method combining mechanical surface roughening and electrochemical surface roughening as described in Japanese Patent Application Laid-Open No. 55-137993, Is preferred because of its strong adhesion to the support. The graining by the above-described method is preferably performed in a range where the center line surface roughness (Ha) of the surface of the aluminum plate is 0.3 to 1.0 μ. The aluminum plate thus grained is washed with water and chemically etched as required.

The etching solution is usually selected from aqueous solutions of bases or acids which dissolve aluminum. In this case, a film different from aluminum derived from the etchant component must not be formed on the etched surface. Preferred examples of the etching agent include sodium hydroxide, potassium hydroxide, trisodium phosphate, disodium phosphate, tripotassium phosphate, and dipotassium phosphate as basic substances; and sulfuric acid and persulfuric acid as acidic substances. , Phosphoric acid, hydrochloric acid, and salts thereof. Metals having a lower ionization tendency than aluminum, such as salts of zinc, chromium, cobalt, nickel, and copper, are not preferable because they form unnecessary films on the etched surface. When the concentration of the etchant and the temperature of the etchant are set, the dissolution rate of the aluminum or alloy to be used is determined by the immersion time.
Most preferably, it is carried out at a rate of from 0.3 g to 40 g / m ² per minute, but it may be higher or lower.

The etching is performed by immersing the aluminum plate in the above-mentioned etching solution or by applying the etching solution to the aluminum plate.
The treatment is preferably performed so as to be in the range of 10 to 10 g / m ² . As the etching agent, it is desirable to use an aqueous solution of a base because of its high etching rate. In this case, since a smut is generated, a normal desmutting process is performed. The acid used for desmut treatment is
Nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, hydrofluoric acid and the like are used. The etched aluminum plate is optionally washed with water and anodized. The anodic oxidation can be performed by a method conventionally used in this field. Specifically, when a direct current or an alternating current is applied to aluminum in an aqueous solution or a non-aqueous solution of sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid or the like or a combination of two or more thereof, the aluminum support An anodized film can be formed on the body surface.

The anodizing treatment conditions cannot be generally determined because they vary depending on the electrolytic solution used, but generally the concentration of the electrolytic solution is 1 to 80% by weight and the liquid temperature is 5 to 70%.
° C, current density 0.5-60 amps / dm ² , voltage 1-10
0V and an electrolysis time of 30 seconds to 50 minutes are appropriate. Among these anodizing treatments, in particular, British Patent No. 1,4
Anodizing at high current density in sulfuric acid as described in U.S. Pat.
The method of anodizing phosphoric acid as an electrolytic bath described in US Pat. No. 661 is preferable. Roughened as above,
Further, the anodized aluminum plate may be subjected to a hydrophilization treatment as necessary. Preferred examples thereof include U.S. Pat. Nos. 2,714,066 and 3,181,461.
Alkali metal silicates such as those disclosed in US Pat.
There is a method of treating with potassium fluoride zirconate disclosed in Japanese Patent No. 3 and polyvinyl phosphonic acid as disclosed in US Pat. No. 4,153,461.

Organic Undercoat Layer: It is preferable to provide an organic undercoat layer before coating the photosensitive layer on the photosensitive lithographic printing plate of the present invention in order to reduce the remaining photosensitive layer in the non-image area. Examples of the organic compound used in the organic undercoat layer include carboxymethyl cellulose, dextrin, gum arabic,
-Phosphonic acids having an amino group such as -aminoethylphosphonic acid, phenylphosphonic acid which may have 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; Organic phosphoric 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 hydrochloride of triethanolamine And the like, but may be used in combination of two or more.

In addition, at least one compound selected from a group of high molecular compounds having a structural unit represented by the following general formula [IV] in the molecule, such as poly (p-vinylbenzoic acid), can be used.

[0103]

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In the general formula [IV], R ₁ represents a hydrogen atom, a halogen atom or an alkyl group, preferably a hydrogen atom, a chlorine atom or an alkyl group having 1 to 4 carbon atoms. Particularly preferably, it represents a hydrogen atom or a methyl group. R ₂ and R ₃ each independently represent a hydrogen atom, a hydroxyl group,
Halogen atom, an alkyl group, a substituted alkyl group, an aromatic group, substituted aromatic group, -R _4, -COOR _5, -CONHR
₆ , -COR ₇ or -CN, or R ₂ and R ₃
May combine to form a ring. Here, R _{4 to} R ₇ each represent an alkyl group or an aromatic group. More preferably, R ₂ and R ₃ are each independently a hydrogen atom, a hydroxyl group, a chlorine atom,
Alkyl group having 1 to 4 carbon atoms, a phenyl group, -R _4, -
_{COOR 5, -CONHR 6, -COR 7} , a -CN, wherein R ₄ to R ₇ is a 1-4 alkyl group or a phenyl group having a carbon number. Particularly preferred R ₂ and R ₃ are each independently a hydrogen atom, a hydroxyl group, a methyl group or a methoxy group.

X represents a hydrogen atom, a metal atom, NR₈R₉R_TenR
₁₁Where R₈~ R₁₁Is each independently hydrogen
Atom, alkyl, substituted alkyl, aromatic, substituted
Represents an aromatic group, or R₈And R₉Combine to form a ring
May be. X is more preferably a hydrogen atom, a monovalent metal atom.
Child, NR₈R₉R_TenR₁₁Where R₈~ R₁₁Is
Each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms
Or a phenyl group. Particularly preferred X is a hydrogen atom
Child, sodium, potassium or NR₈R₉R_TenR ₁₁The table
And where R₈~ R₁₁Is independently a hydrogen atom,
Represents a methyl group or an ethyl group. n represents an integer of 1 to 3
Preferably represents 1 or 2, more preferably 1
Represent.

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. 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 organic compound, and thereafter, washed with water or the like and dried to form an organic undercoat layer. Is the way. 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. For example, any method such as bar coater coating, spin coating, spray coating, and curtain coating may be used. In the latter method, the concentration of the solution is 0.01 to 20% by weight, preferably 0.05 to 20% by weight.
-5% by weight, the immersion temperature is 20-90 ° C., preferably 25-50 ° C., and the immersion time is 0.1 second-20 minutes,
Preferably it is 2 seconds to 1 minute.

The pH of the solution used is adjusted by a basic substance such as ammonia, triethylamine or potassium hydroxide or an acidic substance such as hydrochloric acid or phosphoric acid.
It can also be used in the range of ~ 12. Further, a yellow dye can be added for improving the tone reproducibility of the photosensitive lithographic printing plate. The coating amount of the organic undercoat layer after drying is 2 to 2
00 mg / m ² is suitable, preferably 5 to 100 mg / m ²
It is. 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 .

Back coat: A back coat is provided on the back surface of the support, if necessary. As such a back coat, a coating layer comprising a metal oxide obtained by hydrolyzing and polycondensing an organic polymer compound described in JP-A-5-45885 and an organic or inorganic metal compound described in JP-A-6-35174. Is preferably used.
Among these coating layers, Si (OCH ₃ ) ₄ and Si (OC ₂ H ₅ )
₄ , Si (OC ₃ H ₇ ) ₄ , Si (OC ₄ H ₉ ) ₄ , etc., silicon alkoxy compounds are easily available at a low cost, and the metal oxide coating layer obtained therefrom has excellent developing solution resistance. And particularly preferred.

[0109]

The present invention will be further described below with reference to Synthesis Examples and Examples. However, the present invention is not limited by these examples. Synthesis Example 1 2- (perfluorooctyl) ethyl acrylate 4
6.6 g, 28.8 g of N- (4-sulfamoylphenyl) methacrylamide, 17.6 g of 2-ethylhexyl methacrylate and 180 g of dimethylacetamide
Was placed in a 500 ml three-necked flask and kept at 65 ° C. while stirring under a nitrogen stream. 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 the reaction,
After cooling to room temperature, the reaction was poured into 400 ml of water. The precipitated solid was collected by filtration and dried. Yield 30.1
g, by GPC, this solid was a high molecular compound having a weight average molecular weight of 28,000. Synthesis Examples 2 to 4 The polymers shown in Table 1 were synthesized in the same manner as in Synthesis Example 1. Further, the compound (polymer) of Comparative Example was synthesized in the same manner.

[0110]

[Table 1]

[Examples 1 to 4, Comparative Examples 1 to 3] (All percentages in the following examples are% by weight unless otherwise specified.) JIS having a thickness of 0.24 mm
A 1050 aluminum plate was brush-grained with a rotating nylon brush shown below, while supplying a suspension of water and pamistone having an average particle size of about 2.1 μm to the aluminum surface. The first brush has a bristle length of 100 mm, a bristle diameter of 0.95 mm, and a flocking density of 70 tresses / cm ² , and the second brush has a bristle length of 80 mm, a bristle diameter of 0.295 mm, and a flocking density of 670 tresses / cm ^2.
Met. The rotation of each of the brush rolls was 250 rpm. After washing well with brush graining, the film was immersed in 10% sodium hydroxide at 60 ° C. for 25 seconds for etching, washed with running water, washed with 20% nitric acid and washed with water. These were subjected to electrolytic surface roughening treatment in a 1% aqueous nitric acid solution at an anode electricity of 160 clones / dm ² using a sine wave alternating current under the condition of V _A = 12.7 V. When its surface roughness was measured, it was found to be 0.79 μm.
( _Ra display). Subsequently, after immersion in a 1% aqueous sodium hydroxide solution at 40 ° C. for 30 seconds, immersion in a 30% aqueous sulfuric acid solution and desmut treatment at 60 ° C. for 40 seconds, a current density of 2 A / dm ^{2 in} a 20% aqueous sulfuric acid solution Was anodized with a direct current so as to have an oxide film weight of 1.6 g / m ^{2 to} prepare a substrate.

An undercoating solution (A) having the following composition was applied to the surface of the substrate thus treated, and dried at 80 ° C. for 30 seconds. The coating amount after drying was 10 / m ² . Undercoat solution (A) β-alanine 0.10 g methanol 40 g pure water 60 g Thus, substrate (I) was produced. Next, the photosensitive solution shown in the following Table 2 was applied on the substrate (I) by rod coating at 12 ml / m ^{2 and} dried at 100 ° C. for 1 minute to obtain a positive photosensitive lithographic printing plate. Application amount after drying is 1.15
g / m ² . In order to further shorten the vacuum adhesion time, a mat layer was formed as described in JP-B-61-28986.

[0113]

[Table 2]

The photosensitive lithographic printing plate thus produced was evaluated by the following method. Sensitivity: Step wedge manufactured by Fuji Photo Film Co., Ltd. (density difference between each step is 0.15)
Through a 3 kW metal halide lamp from a distance of 1 m for 1 minute, and using a PS processor 900U manufactured by Fuji Photo Film Co., Ltd. at 30 ° C.
For 12 seconds, the molar ratio of SiO ₂ / K ₂ O is 1.16,
₂ Developed with an aqueous solution having a concentration of 1.4%, and expressed by the number of clear stages (the number of the stage where the composition eluted). The higher the number of stages, the higher the sensitivity. The gradation represents the difference between the number of clear stages and the solid stage (the number of stages where the composition was not eluted) of the sample for which the sensitivity was evaluated. A lower value indicates a higher contrast. The development tolerance is p based on the developer described above.
Exposure and development were performed in the same manner as in the above sensitivity except that a liquid in which H was increased or decreased by 0.2 was used, and the change in the number of solid plates due to pH was shown. The smaller this value is, the better the development tolerance is. Table 4 shows the results.

[0115]

[Table 3]

[0116]

[Table 4]

As can be seen from Table 4, Examples 1 to 4
Has a high contrast without deteriorating the sensitivity, and has good development tolerance. [Examples 5 to 7, Comparative Example 4] JIS having a thickness of 0.24 mm
Surface of A1050 aluminum plate with nylon brush and 4
After graining using an aqueous suspension of 00 mesh pumistone, it was thoroughly washed with water. 7 in 10% sodium hydroxide
After etching by immersion at 0 ° C. for 60 seconds, the substrate was washed with running water, neutralized with 20% HNO ₃ , and washed with water. This is V _A = 1
1% using a sinusoidal alternating current under the condition of 2.7V
The electrolytic surface roughening treatment was performed in a nitric acid aqueous solution at an anode electricity of 160 clones / dm ² . The measured surface roughness was 0.6 μm ( _Ra display). Continue to 30%
After desmutting 2 minutes immersed 55 ° C. in aqueous H ₂ SO _4, 20% H ₂ SO ₄ current in an aqueous solution density of 14A / d
The substrate [A] was prepared by anodic oxidation in m ² and an anodized film amount equivalent to 2.5 g / m ² and washing with water. Substrate [A]
Was treated with a 2.5 wt% aqueous solution of sodium silicate at 30 ° C. for 20 seconds and washed with water to form a substrate [B].

The undercoat liquid (I) having the following composition was applied to the surface of the substrate [B] treated in this manner, and dried at 70 ° C. for 10 seconds. The coating amount after drying was 15 mg / m ² . (I) Polyvinyl benzoic acid (Mw 42000) 0.3 g Methanol 100 g Water 1 g Next, the same photosensitive layer and mat layer as in Examples 1 to 4 were provided on this substrate.

The photosensitive lithographic printing plate thus prepared was evaluated by the following method. Sensitivity is a step wedge manufactured by Fuji Photo Film Co., Ltd. (density difference of each step is 0.15)
Through a 3 kW metal halide lamp from a distance of 1 m for 30 seconds, and then using a PS processor 900U manufactured by Fuji Photo Film Co., Ltd. at 30 ° C.
For 12 seconds, the developer a shown in Table 5 below (pH about 13.
0) and developed, and expressed by the number of clear steps. The higher the number of stages, the higher the sensitivity. The gradation represents the difference between the number of clear steps and the number of solid steps of the sample for which the sensitivity was evaluated. A lower value indicates a higher contrast. The development tolerance was expressed by the same exposure and development as described above except that a solution whose pH was increased or decreased by 0.2 with respect to the above-described developer was used, and the change in the number of solid steps due to the pH was shown. The smaller this value is, the better the development tolerance is.

[0120]

[Table 5]

The results are shown in Table 6.

[0122]

[Table 6]

As can be seen from Table 8, even when the support and the developing solution were changed, Examples 5 to 7 exhibited a high contrast without lowering the sensitivity and had a good development tolerance.

[0124]

The positive photosensitive composition of the present invention, by containing a specific fluorine-containing polymer, exhibits a high contrast image forming property without lowering its sensitivity, and also has burn-in and white light. A wide range of safety and development tolerances were satisfactory.

Claims (1)

[Claims] 1. A composition comprising at least a component represented by (1), a component represented by (2) and a component represented by (3) as a copolymer component, and (1), (2)
And (3) a positive photosensitive composition comprising a polymer compound having a total weight of more than 90% of the total weight of the components. (1) an addition-polymerizable monomer having a fluoroaliphatic group in which a hydrogen atom is substituted by a fluorine atom (2) a monomer represented by the following structures [1] to [4]: In the formula, A represents a hydrogen atom, a halogen atom or an alkyl group. W is oxygen or —NR ₃ —, and R ₃ represents a hydrogen atom, an alkyl group, or an aryl group. R ₁ represents an alkylene group or an arylene group which may have a substituent, and R ₂ represents a hydrogen atom, an alkyl group, or an aryl group. R ₄ represents an alkyl group or an aryl group. Y and Z represent an arylene group which may be the same or different. X is a linking group, and represents a divalent organic group consisting of atoms selected from carbon, nitrogen, oxygen, sulfur, halogen, and hydrogen atoms. m and l are 0
And n represents an integer of 1 to 3. (3) Monomers represented by the following structures [5] to [8]: W is oxygen or —NR ₃ —, and R ₃ represents a hydrogen atom, an alkyl group, or an aryl group. R ₅ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, and R ₆ represents an alkyl group or an aryl group. U is a cyano group, an aryl group, an alkoxy group, an aryloxy group,
Represents an acyloxymethyl group, a heterocyclic ring containing a nitrogen atom, or —CH ₂ OCOR ₆ (R ₆ is as defined above). A has the same meaning as in the above [1] to [4].