JPH11133593A - Photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive lithographic printing plate showing a high-contrast image forming property and good ink depositing property without decreasing sensitivity, and further to provide a photosensitive lithographic printing plate with improved vacuum adhesion property by high formability of a mat layer. SOLUTION: This printing plate has a positive photosensitive layer containing a polymer compd. on a supporting body. The polymer compd. contains (1) an addition-polymerizable monomer having fluoro-aliphatic groups with substitution of fluorine atoms for hydrogen atoms and (2) one or more kinds of addition- polymerizable monomers having acidic hydrogen atoms as the copolymer component. The surface contact angle of the photosensitive layer is >=105 deg.. Further, a mat layer is formed on the photosensitive layer by spraying an aq. soln. prepared by dissolving or dispersing a mat-forming agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive lithographic printing plate, and more particularly, to a photosensitive lithographic printing plate having improved in-coatability, imparting high sensitivity and high contrast image forming properties, and having little sludge formation in a developing solution. Further, the present invention relates to a photosensitive lithographic printing plate having improved vacuum adhesion by forming a high mat.

[0002]

2. Description of the Related Art A photosensitive composition containing an o-quinonediazide compound has been industrially used as a lithographic printing plate as a very excellent positive photosensitive composition and as a photoresist. Conventionally, as a technique for improving the inking property of a positive photosensitive lithographic printing plate, a photosensitive composition containing an o-quinonediazide compound is added with an acrylic polymer or a novolak polymer into which a long-chain alkyl group is introduced. Thus, a method for making the surface of a photosensitive layer lipophilic is known. However, when these polymers are used, there is a problem that sensitivity is reduced and sludge is generated in a developing solution.

On the other hand, when exposing the photosensitive lithographic printing plate to light through the original image, the original image is completely adhered to the surface of the photosensitive layer of the photosensitive printing plate so that the exposed image is not blurred due to a gap between the two. In order to perform exposure, a photosensitive printing plate and an original image are superimposed and arranged between a rubber sheet and a pressure-bonded glass, and a vacuum is applied between the rubber sheet and the pressure-bonded glass to make them adhere to each other (hereinafter referred to as a “vacuum adhesion method”). ) Has been done.

In this vacuum contact method, as described in JP-A-51-111102, a method for shortening the vacuum time for shortening the plate making operation and perfecting the contact is described in JP-A-51-111102. A method of forming (matting) a micropattern composed of a non-coated portion and a non-coating portion has been performed.
A method of spraying an aqueous liquid in which a resin is dissolved or dispersed, as described in JP-A-58-58, is known.

[0005] However, if the surface roughness of the photosensitive printing plate is increased for the purpose of further shortening the vacuum time, the close contact between the photosensitive printing plate and the original image becomes incomplete, and the sharpness of the image decreases. There is a problem that so-called burning blur occurs. Therefore, matting has been performed within a range that can achieve both the reduction of the vacuum time and the problem of burning blur. Also,
Increasing the concentration of the matting agent in the matting liquid and increasing the particle size are also effective in shortening the vacuum contact time, but all of these methods have a large amount of the matting agent consumed and have drawbacks.

[0006]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to solve the above-mentioned problems of the prior art, to provide a high-sensitivity image forming property without lowering the sensitivity, and to provide a photosensitive material having a good inking property. To provide a lithographic printing plate. Another object of the present invention is to provide an excellent photosensitive lithographic printing plate which has a reduced vacuum adhesion time due to high mat forming ability and does not cause burning.

[0007]

Means for Solving the Problems As a result of intensive studies by the present inventors, the above object is achieved by the following constitutions (1) and (2). (1) An addition-polymerizable monomer (1) having a fluoroaliphatic group in which a hydrogen atom is substituted by a fluorine atom in a side chain, and an acid group having an acidic hydrogen atom, wherein the acidic hydrogen atom is bonded to a nitrogen atom. A polymer compound containing, as a copolymerization component, at least one (2) selected from an addition-polymerizable monomer having a phenolic hydroxyl group and an addition-polymerizable monomer having a -COOH group. Having a positive photosensitive layer,
A photosensitive lithographic printing plate wherein the photosensitive layer has a surface contact angle value of 105 ° or more. (2) The photosensitive lithographic printing plate as described in (1) above, further comprising a mat layer formed on the photosensitive layer by spraying an aqueous liquid in which a mat forming agent is dissolved or dispersed.

That is, according to the present invention, the specific fluorine-containing polymer is contained so that the surface contact angle of the photosensitive layer is 10
By setting the angle to 5 ° or more, it is possible to achieve an improvement in the inking property and to obtain a high mat forming ability without lowering the sensitivity or generating sludge.

Here, the surface contact angle value of the photosensitive layer is determined on a PS plate (without matting) before coating the photosensitive layer.
Pure water is gently dropped in air, and the contact angle is measured by a contact angle meter. The preferred surface contact angle value in the present invention is from 107 to 125 °.

JP-A-62-226143, JP-A-3-226143
No. 172849 and JP-A-8-15858 describe a fluorine-containing surfactant having a fluoroaliphatic group, a polyoxyalkylene group or an anionic group, and these fluorine-containing polymers may be used. However, there was a problem that a good effect of improving the inking property could not be obtained, and that when used in a large amount for the purpose of improving the inking property, a decrease in sensitivity and generation of sludge were caused.

Further, in the present invention, a mat layer is formed by spraying an aqueous liquid in which a mat forming agent is dissolved or dispersed on a photosensitive layer containing the above-mentioned specific fluorine-containing polymer, followed by drying. In the case where fine droplets are formed on the surface of the photosensitive layer by spraying, a high matte (surface roughness) is formed within a range where baking is not caused, so that the vacuum adhesion time is remarkably increased. It is something to shorten.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The positive photosensitive layer of the present invention will be described. First, the polymer compound (fluoropolymer) contained in the positive photosensitive layer will be described. 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 preferably 3 to 20, preferably 6 to 12, in order to exert a sufficient effect for the purpose of the present invention.
And at least 40% by weight of preferably 5
It has 0% by weight or more of fluorine bonded to a carbon atom. Suitable fluoro-aliphatic groups, C _n F _{2n + 1} -
(N is an integer of 1 or more, preferably 3 or more) and is a substantially completely or fully fluorinated perfluoroaliphatic group (hereinafter, also abbreviated as an Rf group).

The addition-polymerizable monomer part of the addition-polymerizable monomer having a fluoroaliphatic group in which a hydrogen atom on a carbon atom is fluorinated as the component (1) 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 having a fluoroaliphatic group bonded thereto 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. )).

Specific examples of these are disclosed in US Pat. Nos. 2,803,615, 2,642,416, and 282.
No. 6564, No. 3102103, No. 328290
No. 5, No. 3,304,278, JP-A-6-2562.
No. 89, JP-A-62-1116, JP-A-62-487
No. 72, JP-A-63-77574, JP-A-62-36
657 and the Chemical Society of Japan 1985 (No.
10) Those described on pages 1884-1888. In addition to these fluoroaliphatic group-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.

[0015]

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The amount of the fluoroaliphatic group-containing vinyl monomer 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.

Preferred examples of the acidic group-containing vinyl monomer having an acidic hydrogen atom as the component (2) and having the acidic hydrogen atom bonded to a nitrogen atom include the following structure [1]
To [2].

[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.

In a preferred range of the monomers represented by the structures [1] and [2], A is a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms, R ₃ is a hydrogen atom, 1 to 2 carbon atoms. 20 represents an alkyl group and an aryl group having 6 to 20 carbon atoms. 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,
Represents an aryl group having 6 to 20 carbon atoms. R ₄ has 1 to 1 carbon atoms
20 represents an alkyl group and an aryl group having 6 to 20 carbon atoms.

In the above structures [1] and [2], A
Is more preferably a hydrogen atom or a methyl group. More preferred alkyl groups represented by R ₂ , R ₃ or R ₄ include alkyl groups having 1 to 20 carbon atoms such as methyl, ethyl and isopropyl, and more preferably represented by R ₂ , R ₃ or R ₄ Examples of the aryl group include aryl groups having 6 to 18 carbon atoms such as phenyl and naphthyl. The arylene group or alkylene group represented by R ₁ may have a substituent, and examples of the substituent include halogen atoms such as fluorine, chloro and bromo, methoxy, ethoxy,
An alkoxy group such as phenoxy, an cyano group, an amide group such as 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. And the like.

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

The above structure [1] to component (2)
Examples of addition-polymerizable monomers having an acidic hydrogen atom represented by [2] and having an acidic group in which the acidic hydrogen atom is bonded to a nitrogen atom include specific examples (M-1) to (M-8) below.
However, the present invention is not limited to this.

[0024]

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The monomer capable of addition polymerization having a phenolic hydroxyl group as the component (2) has the following structure [3]:
The monomer represented by [4] or [5] can be mentioned.

[0026]

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Wherein A represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms. R ₃ represents a hydrogen atom,
Represents an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms. Y and Z may be the same or different, and represent an arylene group having 6 to 20 carbon atoms. X
Is a linking group; carbon, nitrogen, oxygen, sulfur, halogen,
It represents a divalent organic group consisting of atoms selected from hydrogen atoms. m represents an integer of 0 or 1, and n represents an integer of 1 or 3. In the monomer having a phenolic hydroxyl group represented by ()), A is preferably a hydrogen atom, a halogen atom or a methyl or ethyl group, and more preferably a hydrogen atom or a methyl group. R ₃ is preferably a hydrogen atom, an alkyl group such as a methyl group or an ethyl group, and particularly preferably a hydrogen atom. Y and Z are phenylene or naphthylene which may have a substituent, and phenylene is particularly preferred. As the substituent, an alkyl group such as methyl and ethyl, a halogen atom such as chlorine, and an alkoxy group such as methoxy are advantageously used. X represents an alkylene, an ester bond, an amide bond, a sulfonamide bond, -OCO-, -OCO
N- and a combination thereof are preferable, m is an integer of 0 or 1, and n is preferably an integer of 1 or 2.

In the structures [3] to [5],
The monomers [3] and [4] are more preferable. The amount of the monomer having a phenolic hydroxyl group represented by the structure [3] to [5] used in the fluorine-containing copolymer used in the present invention is 5 to 80% by weight based on the weight of the copolymer. And preferably in the range of 10 to 70% by weight.

The above structure [3] to component (2)
Examples of the addition-polymerizable monomer having a phenolic hydroxyl group represented by [5] include specific examples (M-9) to
(M-25), but the invention is not limited thereto.

[0030]

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[0031]

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[0032]

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The monomer capable of addition polymerization having a carboxyl group as the component (2) may have at least one —COOH group in the molecule of the monomer, and may have an addition-polymerizable group. Any structure can be used. The amount of the addition-polymerizable monomer having a carboxyl group used in the fluorine-containing copolymer used in the present invention is 1 to 70% by weight, preferably 3 to 30% by weight based on the weight of the copolymer. % By weight. A specific example (M-2)
6) to (M-34), but the invention is not limited thereto.

[0034]

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The fluorine-containing polymer of the present invention may further comprise, if necessary, the following structures [6] to

It may contain the monomer component represented by [9]. The component (3) has an effect of suppressing the development of the photosensitive composition, particularly in a low-exposed portion of the printing plate, and thus has an effective function of increasing the high contrast effect of the present invention.

[0036]

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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 and 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, an acyloxymethyl group, or a heterocyclic ring containing a nitrogen atom, or —CH ₂ OCOR ₆ (R
₆ is as defined above). A is the above [1] to [5]
Represents a synonym for. Structure [6]-

As a preferable range of the monomer represented by [9], W is oxygen or —NR ₃ —, and R ₃ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or 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 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).

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-substituted maleimides such as N-phenylmaleimide, N-chlorophenylmaleimide, N-tolylmaleimide, N-hydroxymaleimide, N-benzylmaleimide; allyl compounds such as allyl acetate, allyl caproate, allyl stearate and allyloxyethanol Ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxy Ethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, phenyl vinyl ether, tolyl vinyl ether,
Hinyl ethers such as diethylaminoethyl vinyl ether; vinyl esters such as vinyl acetate, vinyl butyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenyl acetate, vinyl acetoacetate, vinyl benzoate, and vinyl chlorobenzoate; Styrene, α-methylstyrene,
Methylstyrene, dimethylstyrene, chloromethylstyrene, ethoxymethylstyrene, hydroxystyrene,
Styrenes such as chlorostyrene and bromostyrene; N-
Vinylpyrrolidone, N-vinylpyridine, acrylonitrile and the like.

Particularly preferred among these components (3) are the monomers represented by the structures [6] and [8].

Other optional addition-polymerized unsaturated compounds include Polymer Handbook 2nd ed.,
J. Brandrup, Wiley Interscience (1975) Chapter 2 Pa
ge 1 to 483 can be used. The amount of these vinyl monomers used in the fluorine-containing 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 a vinyl monomer having an acidic hydrogen atom bonded to a nitrogen atom are commonly used in an organic solvent. Can be produced by adding a radical polymerization initiator of the formula (1) and thermally polymerizing the same. Alternatively, if necessary, another addition-polymerizable unsaturated compound can be added to produce the compound in the same manner as described above.

Specific examples of the structure of the fluoropolymer according to the present invention (P-1) to (P-21) can be given below, but the present invention is not limited thereto.
The numbers in the formula indicate the molar ratio of each monomer component.

[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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The molecular weight of the fluorine-containing polymer used in the present invention ranges from 3,000 to 200,0 as an average molecular weight.
00, preferably 4,000 to 10
Up to 000 can be used. Further, the preferred addition amount of the fluorine-containing polymer used in the present invention,
0.1 to 10% by weight based on the solid content of the coating solution,
More preferably, the content is 0.3 to 5% by weight.

Next, components other than the fluorine-containing polymer of the present invention, which are necessary for preparing the photosensitive composition for a positive photosensitive layer of 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 developer changes before and after exposure, and typical examples thereof include 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.

Various structures are known as such, for example, “Light-Sensitive” by J. KOSAR.
Systems "(John Wiley & Sons, Inc, 1965) P.33
See pages 6 to 352 for details.

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

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 described in JP-B-62-44257.
-Sulfonyl chloride and resorcinol-pyrogallol.
Esters with acetone co-condensation resin; JP-B-56-451
No. 27, which is obtained by esterifying 1,2-naphthoquinone-2-diazido-5-sulfonyl chloride to a polyester having a hydroxyl group at a terminal, described in JP-B-50-24641.
1-Naphthoquinone-2-diazido-5-sulfonyl chloride esterified to a homopolymer of-(4-hydroxyphenyl) methacrylamide or a copolymer with another copolymerizable monomer; -2
No. 9922, an ester of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride with a bisphenol-formaldehyde resin;
1,2-Naphthoquinone-2-diazide-5-sulfonyl chloride was esterified to a homopolymer of p-hydroxystyrene or a copolymer with another copolymerizable monomer described in JP-A-2-36043. thing;
There are esters of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride with polyhydroxybenzophenone.

Other known o-quinonediazide compounds usable in the present invention include JP-A-63-80254.
JP-A-58-5737 and JP-A-57-11153.
0, JP-A-57-111531, and JP-A-57-11
No. 4138, JP-A-57-142635, JP-A-Sho 51
-36129, JP-B-62-3411, JP-B-62
-51459 and JP-B-51-483 can be used. The content of the o-quinonediazide compound is usually from 5 to 60% by weight, more preferably from 10 to 40% by weight, based on the total solid content of the photosensitive composition.

As the photosensitive composition other than o-quinonediazide, a chemically amplified photosensitive material comprising a combination of a compound in which an alkali-soluble group is protected with an acid-decomposable group and a photoacid generator can be used.

As the photoacid generator used in the chemical amplification system, known photoacid generators can be used. For example, SIS
chlesinger, Photogr.Sci.Eng., 18,387 (1974), TSBa
l et al, Polymer, 21,423 (1980) and the like diazonium salts, U.S. Pat.Nos. 4,069,055 and 4,069,056,
Ammonium salt described in No. 140,140, DCNecker eta
l, Macromolecules, 17, 2468 (1984), CSWen et al, Te
h, Proc.Conf.Rad.Curing ASIA, p478 Tokyo, Oct (198
8), U.S. Pat.Nos. 4,069,055 and 4,069,056, phosphonium salts described in JVCrivello et al, Macromorecule
s, 10 (6), 1307 (1977), Chem. & Eng. News, Nov. 28, p31 (19
88), European Patent No. 104,143, U.S. Patent No. 339,049, No. 410,201, JP-A-2-150,848, iodonium salts described in JP-A-2-296,514, etc.

JVCrivello et al, Polymer J. 17, 73 (19
85), JVCrivello et al, J. Org.Chem., 43, 3055 (197
8), WRWatt et al, J. Polymer Sci., Polymer Chem. E
d., 22, 1789 (1984), JVCrivello et al, Polymer Bul
l., 14,279 (1985), JVCrivello etal, Macromorecule
s, 14 (5), 1141 (1981), JVCrivello et al, J. PolymerS
ci., Polymer Chem. Ed., 17, 2877 (1979), EP 370,
693, U.S. Patent 3,902,114, EP 233,567,
No. 297,443, No. 297,442, U.S. Pat.No. 4,933,377,
No. 410,201, No. 339,049, No. 4,760,013, No. 4,734,4
No. 44, No. 2,833,827, Dokoku Patent No. 2,904,626, No. 3,60
No. 4,580, the sulfonium salt described in 3,604,581 and the like,

JVCrivello et al, Macromorecules, 10
(6), 1307 (1977), JVCrivello et al, J. PolymerSci., P
selenonium salts described in Olymer Chem. Ed., 17, 1047 (1979), etc., CSWen et al, 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, etc., K. Meier et al, J. Rad. Curing, 13 (4), 26 (1986), T.
P. Gill et al, Inorg.Chem., 19, 3007 (1980), D. Astruc,
Acc.Chem.Res., 19 (12), 377 (1896), organometallic / organic halides described in JP-A-2-14145 and the like,

S. Hayase et al, J. Polymer Sci., 25, 753
(1987), E. Reichmanis et al, J. Polymer Sci., Polymer
Chem. Ed., 23, 1 (1985), QQZhu et al, J. Photoche
m., 36, 85, 39, 317 (1987), B. Amit et al, Tetrahedron L
ett., (24) 2205 (1973), DHR Barton et al, J. Chem So
c., 3571 (1965), PMCollins et al, J. Chem.SoC., Perk
inI, 1695 (1975), M. Rudinstein et al, Tetrahedron Le
tt., (17), 1445 (1975), JWWalker et al, J. Am. Chem. S
oc., 110, 7170 (1988), SCBusman et al, J. Imaging Te
chnol., 11 (4), 191 (1985), HMHoulihan et al, Macorm
olecules, 21, 2001 (1988), PM Collins et al, J. Chem.
Soc., Chem. Commun., 532 (1972), S. Hayase etal, Macrom
olecules, 18, 1799 (1985), E. Reichmanis et al, J. Elec
trochem.Soc., Solid State Sci.Technol., 130 (6), FM
Houlihan et al, Macromolcules, 21, 2001 (1988), EP 0290,750, EP 046,083, EP 156,535, EP 271,
No. 851, No. 0,388,343, U.S. Pat.No. 3,901,710, No. 4,1
81,531, JP-A-60-198538, a photoacid generator having an o-nitrobenzyl-type protecting group described in JP-A-53-133022, etc.

M. TUNOOK et al, Polymer Preprints Japa
n, 35 (8), G. Berner et al, J. Rad. Curing, 13 (4), WJM
ijs et al, Coating Technol., 55 (697), 45 (1983), Akz
o, H. Adachi et al, Polymer Preprints, Japan, 37 (3),
European Patent Nos. 0199,672, 84515, 199,672, 04
No. 4,115, No. 0101,122, U.S. Pat.No. 4,618,564, No. 4,
Nos. 371,605 and 4,431,774, JP-A-64-18143, JP-A-Hei.
2-245756, a compound that generates sulfonic acid upon photodecomposition represented by iminosulfonate and the like described in Japanese Patent Application No. 3-140109, a disulfone compound and the like described in JP-A-61-166544 and the like. 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 will be described below. The following general formula (PAG1) substituted with a trihalomethyl group
An oxazole derivative represented by the general formula (PAG)
An s-triazine derivative represented by 2).

[0064]

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In the formula, R ₁₁ represents a substituted or unsubstituted aryl group or alkenyl group, and R ₁₂ 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.

[0066]

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[0067]

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

[0069]

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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 ₁₃ , R ₁₄ and R ₁₅ 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.

[0072] 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.

Further, two of R ₁₃ , R ₁₄ and R ₁₅ and Ar 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.

[0075]

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[0076]

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The above onium salts represented by the general formulas (PAG3) and (PAG4) are known, for example, JW Knap
czyk et al, J. Am. Chem. Soc., 91, 145 (1969), A.
L. Maycok et al, J. Org. Chem., 35, 2532, (1970)
, B. Goethas et al, Bull. Soc. Chem. Belg., 73, 5
46, (1964), HM Leicester, J. Ame. Chem. Soc., 5
1, 3587 (1929), JV Crivello et al, J. Polym. Che
m. Ed., 18, 2677 (1980); U.S. Pat. No. 2,807,6.
Nos. 48 and 4,247,473, JP-A-53-1
No. 01,331 and the like.

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

[0079]

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In the formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group. R ₁₆ 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.

[0081]

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[0082]

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The amount of the compound capable of decomposing upon irradiation with actinic rays or radiation to generate an acid is usually 0.03% based on the total weight of the photosensitive composition (excluding the coating solvent).
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 in which an alkali-soluble group is 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 light-sensitive mixture are described in DE-A-2,610,842 and DE-A-2,928,636. Mixtures containing compounds of type (b) are described in German Patents 2,306,248 and
718,254. 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, such as those disclosed in JP-A-51-34711, acrylic resins having a sulfonamide group, and urethane-based resins described in JP-A-2-866. Also, various alkali-soluble polymer compounds can be used. These alkali-soluble polymer compounds have a weight average molecular weight of 50.
0 to 200,000 and number average molecular weight of 200 to 60,0
00 is preferred. These alkali-soluble polymer compounds 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.

Further, as described in US Pat. No. 4,123,279, a compound having an alkyl group having 3 to 8 carbon atoms as a substituent, such as a t-butylphenol formaldehyde resin and an octylphenol formaldehyde resin. It is preferable to use a condensate of phenol and formaldehyde in combination 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.

In the photosensitive composition of the present invention, it is preferable to add a cyclic acid anhydride, a phenol or an organic acid to increase the sensitivity. Cyclic acid anhydride include U.S. Pat phthalic anhydride as described in No. 4,115,128 specification, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-oxy - [delta ⁴ - tetrahydrophthalic anhydride, tetrachlorophthalic Examples include phthalic 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, and more preferably from 0.1 to 8% 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 which releases an acid upon exposure include o-naphthoquinonediazide-4-sulfonic acid halogenide described in JP-A-50-36209; and JP-A-53-36223. The described trihalomethyl-2-virone and trihalomethyl-
s-Triazine; trihalomethyl compound described in JP-A-63-58440; JP-A-55-624
No. 44, various o-naphthoquinonediazide compounds; 2-trihalomethyl-5-aryl-1,3,3, described in JP-A-55-77742.
4-oxadiazole compounds; diazonium salts and the like. These compounds can be used alone or as a mixture, and the amount added is preferably in the range of 0.3 to 15% by weight based on the total weight of the composition.

In the photosensitive composition of the present invention, at least one or more kinds of organic dyes which change the color tone by interacting with a photolysis product of a compound which generates an acidic substance by photolysis are 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 (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red 5B (manufactured by Orient Chemical Industry Co., Ltd.), Oil Scarlet # 308 (manufactured by 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 [manufactured by Hodogaya Chemical Industry Co., Ltd.], Patent Pure-Blue [manufactured by Sumitomo Mikuni Chemical Industry Co., Ltd.], Sudan Blue II [manufactured by BASF], m-cresol purple, cresol red, rhodamine B, rhodamine 6G , First acid violet R, sulforhodamine B, auramine, 4-p-die Le aminophenyl Imi nona naphthoquinone, 2-carboxy anilino -4-p-diethylaminophenyl imino nona naphthoquinone, 2-carbomethoxy stearyl amino -4-p-dihydroxy-ethyl - 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-62-293247 and Japanese Patent Application No. 4-11284.
Those having a sulfonic acid compound as a counter anion as shown in the specification of JP-A No. 4 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. Also can be used with other dyes and pigments as needed,
70% by weight based on the total weight of dyes and pigments
Or less, more preferably 50% by weight or less.

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 a 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 development latitude, 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, stearic acid monoglyceride, polyoxyethylene sorbitan monooleate,
Specific examples of the amphoteric surfactant include alkyl di (aminoethyl) glycine, alkyl polyaminoethyl glycine hydrochloride, and Amogen K (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). N-tetradecyl-N, N-betaine type),
2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine, Levon 15 (trade name, manufactured by Sanyo Chemical Co., Ltd., alkylimidazoline system) and the like. 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.

In the photosensitive composition of the present invention, a surfactant for improving the coated surface quality, for example, a surfactant described in
A fluorine-based surfactant as described in JP-A-170950 can be added. The preferable addition amount is 0.001 to 1.0% by weight of the total photosensitive composition, 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. Represented by the general formula [I], [II] or [III],
yellow dye whose absorbance at m is 70% or more of the absorbance at 436 nm

[0103]

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In the formula [I], R ₂₁ and R ₂₂ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group or an alkenyl group. R ₂₁ and R ₂₂ may form a ring. R ₂₃ , R ₂₄ and R ₂₅ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. G ₁ and G ₂ each independently represent an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an arylcarbonyl group, an alkylthio group, an arylthio group, an alkylsulfonyl group,
It represents an arylsulfonyl group or a fluoroalkylsulfonyl group. G ₁ and G ₂ may form a ring. Further, at least one of R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , G ₁ , and G ₂ has at least one sulfonic acid group, carboxyl group, sulfonamide group, imide group, N-sulfonylamide group. A phenolic hydroxyl group, a sulfonimide group, or a metal salt thereof,
Has inorganic or organic ammonium salts. Y is O, S, N
R (R is a hydrogen atom or an alkyl group or an aryl group), Se, —C (CH ₃ ) ₂ —, or —CH ＝ CH— represents a divalent atomic group, and n ₁ represents 0 or 1.

[0105]

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[Wherein, R ₂₆ and R ₂₇ each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a heterocyclic group, a substituted heterocyclic group, an allyl group or a substituted allyl group. And R ₂₆ and R ₂₇ may together form a ring together with the carbon atom to which they are attached. n ₂ represents 0, 1 or 2. G ₃ and G ₄ are each independently a hydrogen atom, a cyano group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, an aryloxycarbonyl group, a substituted aryloxycarbonyl group, an acyl group, a substituted acyl group, an arylcarbonyl group, a substituted arylcarbonyl Group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, and fluoroalkylsulfonyl group. However, G ₃ and G ₄ are not simultaneously hydrogen atoms. G ₃ and G ₄ may form a ring composed of a non-metallic atom together with the carbon atom to which they are bonded. And at least one of R ₂₆ , R ₂₇ , G ₃ and G ₄ has at least one sulfonic acid group, carboxyl group, sulfonamide group,
It has an imide group, an N-sulfonylamide group, a phenolic hydroxyl group, a sulfonimide group, or a metal salt or an inorganic or organic ammonium salt thereof.

[0107]

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R ₂₈ , R ₂₉ , R ₃₀ , R ₃₁ , R ₃₂ , and R ₃₃ 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 the photosensitive lithographic printing plate of the present invention is obtained from the photosensitive composition containing the above-mentioned fluoropolymer, it is first provided on a suitable support. The photosensitive composition containing the fluoropolymer of the present invention is dissolved or dispersed in one or a mixture of the following organic solvents, applied to a support, and dried.

As the organic solvent, any known organic solvents can be used, but the boiling point is 40 ° C. to 200 ° C., particularly 60 ° C.
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.

Examples of the method for applying the photosensitive composition include roll coating, dip coating, air knife coating, gravure coating, gravure offset coating, hopper coating, blade coating, wire doctor coating, spray coating, and the like. It is preferably from 0.3 to 4.0 g / m ^{2 in} terms of weight afterwards. As the amount of coating decreases, the amount of exposure for obtaining an image may be small, but the film strength is reduced. 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.

In the present invention, a high mat is formed by spraying (spraying) an aqueous liquid in which a mat forming agent is dissolved or dispersed on the surface of the photosensitive layer provided as described above. Thus, it is possible to shorten the vacuum contact time in the contact exposure using the vacuum printing frame, and to favorably prevent burning blur. When the photosensitive layers are on both surfaces of the support, it is preferable to form a mat layer on the photosensitive layers on both surfaces.

The coating solution applied to the surface of the photosensitive printing plate is as follows:
An aqueous liquid in which a mat forming agent is dissolved or dispersed, which can be easily removed at the time of development without exerting a physical or chemical adverse effect on the photosensitive material constituting the photosensitive layer, and is used. Any material may be used as long as it does not react with the developer.

Examples of the mat forming agent include gum arabic, glue, gelatin, casein, and celluloses (for example, viscose, methylcellulose, ethylcellulose, hydroxycellulose) as described in JP-A-51-111102. Cellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, etc.), starches (eg, soluble starch, modified starch, etc.), polyvinyl alcohol, polyethylene oxide, polyacrylic acid, polyacrylamide, polyvinyl methyl ether,
Epoxy resin, phenolic resin (particularly preferably novolak type phenolic resin), polyamide (for example, methanol, ethanol, isopropanol, butanol, t
A polyamide soluble in alcohols having 1 to 6 carbon atoms, such as butanol, amyl alcohol, and hexanol), resins such as polyvinyl butyral, and acrylics as described in JP-A-57-34558. Copolymer of acid ester and acrylic acid or methacrylic acid,
Styrene, acrylate, copolymer of acrylic acid or methacrylic acid, acrylate, styrene,
Copolymers of acrylonitrile and the like with acrylic acid or methacrylic acid, maleic acid, itaconic acid and the like, and vinyl polymers such as polyvinyl alcohol, polyvinyl acetate and polyvinylpyrrolidone are exemplified.

In the present invention, these resins are appropriately selected,
An aqueous liquid is obtained by dissolving or dispersing in water by a conventionally known method. As a solvent, in addition to water as the main component,
It may contain a low-boiling organic solvent that does not dissolve the photosensitive layer components.

Further, when light passes through the mat formed at the time of exposure, the photosensitive layer in the mat forming portion may not be sufficiently photodegraded due to light scattering. It may be added inside.

Further, the aqueous liquid contains a filler such as another water-soluble substance, fine inorganic powder, or polymer powder, which does not affect the photosensitive layer or the attached droplets. Is also good. As the filler, for example, silicon dioxide, zinc oxide,
Titanium oxide, zirconium oxide, glass particles, alumina, polymer particles (for example, polymethyl methacrylate,
Particles such as polystyrene and phenolic resin). These can be used in combination of two or more.

As an example of a method for preparing an aqueous liquid, for example, the above-mentioned resin (mat-forming agent) is emulsified in water with a surfactant in the same manner as in a usual method for synthesizing a latex. It may be an aqueous dispersion obtained by emulsion polymerization using a polymerization initiator such as potassium sulfate, or a copolymer of acrylic acid, methacrylic acid, maleic acid, a part of itaconic acid, etc. as a sodium salt, a potassium salt or an ammonium salt. May be used. The concentration of the resin in the aqueous liquid is preferably 10 to 30% by weight, more preferably 13 to 22% by weight.

Such an aqueous liquid (aqueous solution or aqueous dispersion)
Can be applied to the surface of the photosensitive layer by a known method such as an air spray method, an airless spray method, an electrostatic air spray method, and an electrostatic atomizing electrostatic coating method.
The aqueous liquid of the mat former sprayed on the surface of the photosensitive layer is then dried. Drying is performed by a usual method, for example, a method of blowing hot air.

The resin (mat forming agent) thus adhered to the surface of the photosensitive layer preferably has a height of 1 to 20 μm.
m, more preferably 2 to 10 μm, and the size (width) is preferably 5 to 200 μm, more preferably 10 to 30 μm.
m, the amount is preferably 1 to 1000 pieces / mm ² , preferably 5 to 500 pieces / mm ² , and more preferably 30 to 50 pieces / mm ^2.
Range.

The support used for the photosensitive lithographic printing plate or the like is a dimensionally stable plate-like material, and includes those conventionally used as a support for a 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 method as described above has a center line surface roughness (Ra) of the surface of the aluminum plate of 0.3 to 1.0 μm.
It is preferable that the application is performed in such a range as follows.

The grained aluminum plate is washed with water and chemically etched as necessary. The etching solution is usually selected from aqueous solutions of bases or acids that 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. Most preferably, these etchants are used so that the dissolution rate of the aluminum or alloy used is from 0.3 gram to 40 g / m ² per one minute of immersion time at the setting of the concentration and temperature of use. It can be higher or lower than this.

The etching is carried out 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:
Washed and anodized as needed. 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 to be 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.

The aluminum plate which has been roughened and anodized as described above may be subjected to a hydrophilizing treatment, if necessary. A preferred example is US Pat.
Alkali metal silicates such as those disclosed in U.S. Pat. Nos. 4,066 and 3,181,461, such as aqueous sodium silicate or potassium fluorozirconate disclosed in JP-B-36-22063 and U.S. Pat. There is a method of treating with polyvinyl phosphonic acid as disclosed in US Pat. No. 4,153,461.

It is preferable to provide an organic undercoat layer on the photosensitive lithographic printing plate of the present invention before coating the photosensitive layer 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 2-aminoethylphosphonic acid, phenylphosphonic acid which may have a substituent, and naphthyl. Organic phosphonic acids such as phosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid, and organic acids such as phenylphosphoric acid, naphthylphosphoric acid, alkylphosphoric acid and glycerophosphoric acid which may have a substituent Phosphoric acid, optionally substituted phenylphosphinic acid, naphthylphosphinic acid, organic phosphinic acids such as alkylphosphinic acid and glycerophosphinic acid, amino acids such as glycine and β-alanine, and hydrochloride of triethanolamine and the like Hydroxy Although selected from such as hydrochloric acid salt of an amine having a group, it may be used as a mixture of two or more thereof.

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 a molecule, such as poly (p-vinylbenzoic acid), can be used.

[0135]

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In the general formula [IV], R ₄₁ 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 ₄₂ and R ₄₃ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, a substituted alkyl group, an aromatic group, a substituted aromatic group, -OR ₄₄ , -COOR ₄₅ , -CO
It may represent NHR ₄₆ , —COR ₄₇ or —CN, or R ₄₂ and R ₄₃ may combine to form a ring. Where R ₄₄
To R ₄₇ each represents an alkyl group or an aromatic group. More preferred R ₄₂ and R ₄₃ are each independently a hydrogen atom, a hydroxyl group, a chlorine atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, -OR ₄₄ , -COOR ₄₅ , -CONHR ₄₆ , -CO
R ₄₇ and —CN, wherein R _{44 to} R _{47 each} have 1 to 4 carbon atoms.
Alkyl groups or phenyl groups. Particularly preferred R ₄₂ and R ₄₃ are each independently a hydrogen atom, a hydroxyl group, a methyl group or a methoxy group.

X is a hydrogen atom, a metal atom, NR₄₈R₄₉R₅₀
R₅₁Where R₄₈~ R₅₁Are each independently water
Element atom, alkyl group, substituted alkyl group, aromatic group, substitution
Represents an aromatic group, or R₄₈And R₄₉Combine to form a ring
You can do it. More preferred X is a hydrogen atom, monovalent gold
Genus atom, NR₄₈R₄₉R₅₀R₅₁Where R₄₈~ R
₅₁Are each independently a hydrogen atom, an alkyl having 1 to 4 carbons.
It is a kill group or a phenyl group. Particularly preferred X is water
Elementary atom, sodium, potassium or NR₄₈R ₄₉R₅₀R
₅₁Where R₄₈~ R₅₁Is each independently hydrogen
Represents an atom, a methyl group, or an ethyl group. n is an integer of 1 to 3
Represents, preferably represents 1 or 2, more preferably
Represents 1.

The 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 applied to an aluminum plate and dried to provide water or methanol, ethanol, methyl ethyl ketone, or the like. A solution in which the above organic compound is dissolved in an organic solvent or a mixed solvent thereof is immersed in an aluminum plate 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 adjusting the pH with 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. Further, this solution has the following general formula (1)
Compounds represented by 0) can also be added. Formula (10) (HO) _m -R _1- (COOH) n wherein R ₁ represents an arylene group having 14 or less carbon atoms which may have a substituent, and m and n are independently 1 to 3 Represents an integer. Specific examples of the compound represented by the general formula (1) include 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, salicylic acid, 1-hydroxy-2-naphthoic acid,
2-hydroxy-1-naphthoic acid, 2-hydroxy-3
-Naphthoic acid, 2,4-dihydroxybenzoic acid, 10-
Hydroxy-9-anthracenecarboxylic acid and the like. The coating amount of the organic undercoat layer after drying is 1 to 100 mg /
m ² is suitable, and preferably ² to 70 mg / m ² . If the coating amount is less than 1 mg / m ² , sufficient printing durability cannot be obtained. The same is true even if it is larger than 100 mg / m ² .

On the back surface of the support, a back coat is provided 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 , Si (OC ₂ H ₅ ) ₄ , Si (OC ₃ H)
₇ ) ₄ , Silicon alkoxy compounds such as Si (OC ₄ H ₉ ) ₄ are inexpensive and easily available, and the metal oxide coating layer obtained therefrom is particularly preferred because of its excellent developer resistance.

The PS plate thus obtained was passed through a transparent original image using a carbon arc lamp, a mercury lamp, a metal halide lamp,
After being exposed by an actinic ray using a xenon lamp, a tungsten lamp or the like as a light source, it is developed.

Preferred as the developer for the photosensitive lithographic printing plate of the present invention are (a) at least one saccharide selected from non-reducing sugars and (b) at least one base, and a pH of 9.0 to 9.0. The developer is in the range of 13.5. Hereinafter, the developer will be described in detail. In the present specification, unless otherwise specified, the developing solution means a developing solution (a developing solution in a narrow sense) and a developing replenisher.

The main components of this developer are preferably at least one compound selected from non-reducing sugars and at least one base, and the pH of the solution is preferably in the range of 9.0 to 13.5. . Such non-reducing sugars are saccharides having no free aldehyde group or ketone group and exhibiting no reducibility, trehalose-type oligosaccharides in which reducing groups are bonded to each other, glycosides in which the reducing groups of saccharides are bonded to non-saccharides. It is classified as a sugar alcohol reduced by hydrogenation of a body and a saccharide, and both are suitably used. Trehalose-type oligosaccharides include saccharose and trehalose, and examples of glycosides include alkyl glycosides, phenol glycosides, and mustard oil glycosides. As sugar alcohols, D, L-arabit,
Rebit, Xylit, D, L-Sorbit, D, L-
Mannit, D, L-idit, D, L-talit, zuricit and allozurcit. Further, maltitol obtained by hydrogenation of disaccharide and reductant (reduced starch syrup) obtained by hydrogenation of oligosaccharide are preferably used. Particularly preferred non-reducing sugars among these are sugar alcohols and saccharose, especially D-sorbit,
Saccharose and reduced starch syrup are preferred because they have a buffering action in an appropriate pH range and are inexpensive.

These non-reducing sugars can be used alone or in combination of two or more kinds, and their ratio in the developing solution is preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight. is there. Below this range, a sufficient buffering effect cannot be obtained, and at concentrations above this range, it is difficult to achieve high concentration, and there is a problem of cost increase. When a reducing sugar is used in combination with a base, there is a problem that the color changes to brown with the lapse of time, and the pH gradually lowers, thereby deteriorating the developability.

As the base to be combined with the non-reducing sugar, conventionally known alkaline agents can be used. For example, sodium hydroxide, potassium, lithium, trisodium phosphate, potassium, ammonium, disodium phosphate, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium hydrogencarbonate, potassium, ammonium And inorganic alkali agents such as sodium borate, potassium and ammonium. Also, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, Organic alkali agents such as ethyleneimine, ethylenediamine and pyridine are also used.

These alkaline agents are used alone or in combination of two or more. Preferred among these are sodium hydroxide and potassium hydroxide, because
This is because adjusting these amounts with respect to the non-reducing sugar enables pH adjustment in a wide pH range. Further, trisodium phosphate, potassium phosphate, sodium carbonate, potassium phosphate and the like are also preferable since they themselves have a buffering action. These alkaline agents are added so that the pH of the developing solution is in the range of 9.0 to 13.5, and the amount of the alkaline agent is the desired pH,
Although it is determined by the type and amount of non-reducing sugar, a more preferable pH range is 10.0 to 13.2.

Further, an alkaline buffer consisting of a weak acid other than saccharides and a strong base can be used in combination with the developer. The weak acid used as such a buffer is preferably one having a dissociation constant (pKa) of 10.0 to 13.2. Such weak acids include IONISATION CONSTAN published by Pergamon Press
Selected from those described in TS OF ORGANIC ACIDS IN AQUEOUS SOLUTION and the like, for example, 2,2,3,3-tetrafluoropropanol-1 (PKa 12.74),
Alcohols such as trifluoroethanol (12.37) and trichloroethanol (12.24), pyridine-2-aldehyde (12.68), pyridine-4
Aldehydes such as -aldehyde (12.05), salicylic acid (13.0), 3-hydroxy-2-naphthoic acid (12.84), catechol (12.6), and gallic acid (12.05). 4), sulfosalic acid (11.
7), 3,4-dihydroxysulfonic acid (12.
2), 3,4-dihydroxybenzoic acid (11.9)
4), 1,2,4-trihydroxybenzene (11.
82), hydroquinone (11.56), pyrogallol (11.34), o-cresol (10.3)
3), resorcinol (11.27), p-cresol (10.27), m-cresol (10.09)
Compounds having a phenolic hydroxyl group, such as

2-butanone oxime (12.45);
Acetoxime (12.42), 1,2-cycloheptanedione dioxime (12.3), 2-hydroxybenzaldehyde oxime (12.10), dimethylglyoxime (11.9), ethanediamide dioxime (11.37) and acetophenone oxime (11.37).
Oximes such as 35) and adenosine (12.5
6), inosine (12.5) and guanine (12.
3), cytosine (12.2), hypoxanthine (1)
2.1), nucleic acid-related substances such as xanthine (11.9), and diethylaminomethylphosphonic acid (12.
32), 1-amino-3,3,3-trifluorobenzoic acid (12.29), isopropylidene diphosphonic acid (12.10), 1,1-ethylidene diphosphonic acid (11.54) , 1,1-ethylidene diphosphonic acid 1
-Hydroxy (11.52), benzimidazole (12.86), thiobenzamide (12.8),
Weak acids such as picoline thioamide (12.55) and barbituric acid (12.5).

Among these weak acids, preferred are sulfosalicylic acid and salicylic acid. As the base to be combined with these weak acids, sodium hydroxide, ammonium hydroxide, potassium hydroxide and lithium hydroxide are preferably used.
These alkali agents are used alone or in combination of two or more. The above-mentioned various alkaline agents are used by adjusting the pH within a preferred range depending on the concentration and combination.

Various surfactants and organic solvents can be added to the developer, if necessary, for the purpose of accelerating the developability, dispersing the development residue and improving the ink affinity of the printing plate image area. Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants.

Preferred examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, and glycerin fatty acid partial esters. , Sorbitan fatty acid partial esters,
Pentaerythritol fatty acid partial ester, propylene glycol monofatty acid ester, sucrose fatty acid partial ester, polyoxyethylene sorbitan fatty acid partial ester, polyoxyethylene sorbitol fatty acid partial ester, polyethylene glycol fatty acid ester, polyglycerin fatty acid partial ester , Polyoxyethylenated castor oils, polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamides,
N. Non-ionic surfactants such as N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, and trialkylamine oxides;

Fatty acid salts, abietic acid salts, hydroxyalkanesulfonic acid salts, alkanesulfonic acid salts,
Dialkyl sulfosuccinates, linear alkylbenzene sulfonates, branched alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkylphenoxy polyoxyethylene propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-methyl- N-oleyltaurine sodium salt, N-alkylsulfosuccinic acid monoamide disodium salt, petroleum sulfonates, sulfated tallow oil, sulfates of fatty acid alkyl esters, alkyl sulfates, polyoxyethylene alkyl ether sulfates, Fatty acid monoglyceride sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, polyoxyethylene styryl phenyl ether sulfate salts, Alkyl phosphate salts, polyoxyethylene alkyl ether phosphate salts, polyoxyethylene alkyl phenyl ether phosphate salts, partially saponified styrene / maleic anhydride copolymers, partially olefin / maleic anhydride copolymers Anionic surfactants such as saponified products and naphthalene sulfonate formalin condensates; quaternary ammonium salts such as alkylamine salts and tetrabutylammonium bromide; cationic interfaces such as polyoxyethylene alkylamine salts and polyethylene polyamine derivatives. Activators, amphoteric surfactants such as carboxybetaines, aminocarboxylic acids, sulfobetaines, aminosulfates, and imidazolines. Among the surfactants mentioned above, the term "polyoxyethylene" can be read as a polyoxyalkylene such as polyoxymethylene, polyoxypropylene, or polyoxybutylene, and these surfactants are also included.

More preferred surfactants are fluorine-based surfactants containing a perfluoroalkyl group in the molecule. Such fluorosurfactants include perfluoroalkyl carboxylate, perfluoroalkyl sulfonate, anionic type such as perfluoroalkyl phosphate, amphoteric type such as perfluoroalkyl betaine,
Cationic and perfluoroalkylamine oxides such as perfluoroalkyltrimethylammonium salts, perfluoroalkylethylene oxide adducts, oligomers containing perfluoroalkyl groups and hydrophilic groups,
Non-ionic types such as oligomers containing perfluoroalkyl groups and lipophilic groups, oligomers containing perfluoroalkyl groups, hydrophilic groups and lipophilic groups, and urethanes containing perfluoroalkyl groups and lipophilic groups are included. The above surfactants can be used alone or in combination of two or more, and are added to the developer in an amount of 0.001 to 10% by weight, more preferably 0.01 to 5% by weight.

Various developing stabilizers can be used in the developing solution. As preferred examples thereof, Japanese Patent Application Laid-Open No.
Preferred examples include polyethylene glycol adducts of sugar alcohols described in JP-A-282079, tetraalkylammonium salts such as tetrabutylammonium hydroxide, phosphonium salts such as tetrabutylphosphonium bromide, and iodonium salts such as diphenyliodonium chloride. Further, Japanese Patent Application Laid-Open
Anionic or amphoteric surfactants described in JP-A-51324, water-soluble cationic polymers described in JP-A-55-95946, JP-A-56-1425
And water-soluble amphoteric polymer electrolytes described in JP-A-28.

Further, an organic boron compound to which an alkylene glycol has been added described in JP-A-59-84241, and a water-soluble surfactant of the polyoxyethylene / polyoxypropylene block polymerization type described in JP-A-60-111246. Japanese Patent Application Laid-Open No. Sho 60-129750, polyoxyethylene / polyoxypropylene-substituted alkylenediamine compounds, Japanese Patent Application Laid-Open No. Sho 61-215554, polyethylene glycol having a weight average molecular weight of 300 or more, and Japanese Patent Application Laid-Open No. Sho 63-175858. JP-A-2-39157 discloses a fluorine-containing surfactant having a cationic group, a water-soluble ethylene oxide addition compound obtained by adding 4 mol or more of ethylene oxide to an acid or alcohol, and a water-soluble polyalkylene compound. No.

An organic solvent is further added to the developer if necessary. As such an organic solvent, those having a solubility in water of about 10% by weight or less are suitable, and preferably selected from those having a solubility of 5% by weight or less. For example, 1-phenylethanol, 2-phenylethanol, 3-phenyl-1
-Propanol, 4-phenyl-1-butanol, 4-
Phenyl-2-butanol, 2-phenyl-1-butanol, 2-phenoxyethanol, 2-benzyloxyethanol, o-methoxybenzyl alcohol, m-methoxybenzyl alcohol, p-methoxybenzyl alcohol, benzyl alcohol, cyclohexanol,
-Methylcyclohexanol, 3-methylcyclohexanol, 4-methylcyclohexanol, N-phenylethanolamine, N-phenyldiethanolamine, and the like. The content of the organic solvent is 0.1 to 5% by weight based on the total weight of the used solution. The amount used is closely related to the amount used of the surfactant, and it is preferable to increase the amount of the surfactant as the amount of the organic solvent increases. This is because the amount of the surfactant is small, and if the amount of the organic solvent is large, the organic solvent is not completely dissolved, and therefore,
This is because good developability cannot be expected.

A reducing agent can be further added to the developer. This is to prevent stains on the printing plate, and is particularly effective when developing a negative photosensitive lithographic printing plate containing a photosensitive diazonium salt compound.Preferred organic reducing agents include thiosalicylic acid, hydroquinone, and methol. Phenol compounds such as methoxyquinone, resorcin and 2-methylresorcin; and amine compounds such as phenylenediamine and phenylhydrazine. Further preferred inorganic reducing agents include sodium salts, potassium salts, and ammonium salts of inorganic acids such as sulfurous acid, bisulfite, phosphorous acid, bisulfite, diphosphite, thiosulfate and dithionite. Salts and the like can be mentioned. Among these reducing agents, sulfites are particularly excellent in the stain prevention effect. These reducing agents are preferably contained in a range of 0.05 to 5% by weight with respect to the developing solution at the time of use.

An organic carboxylic acid can be further added to the developer. Preferred organic carboxylic acids have 6 to 6 carbon atoms.
20 aliphatic carboxylic acids and aromatic carboxylic acids. Specific examples of the aliphatic carboxylic acid include caproic acid, enantiic acid, caprylic acid, lauric acid, myristic acid, palmitic acid and stearic acid, and particularly preferred are alkanoic acids having 8 to 12 carbon atoms. . Further, unsaturated fatty acids having a double bond in the carbon chain or branched fatty acids may be used. The aromatic carboxylic acid is a compound in which a carboxyl group is substituted on a benzene ring, a naphthalene ring, an anthracene ring, or the like.
-Chlorobenzoic acid, p-chlorobenzoic acid, o-hydroxybenzoic acid, p-hydroxybenzoic acid, o-aminobenzoic acid, p-aminobenzoic acid, 2,4-dihydrobenzoic acid, 2,5-dihydroxybenzoic acid 2,6-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 3,5
-Dihydroxybenzoic acid, gallic acid, 1-hydroxy-
2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 2
-Hydroxy-1-naphthoic acid, 1-naphthoic acid, 2-
Although there are naphthoic acid and the like, hydroxynaphthoic acid is particularly effective.

The above aliphatic and aromatic carboxylic acids are preferably used as a sodium salt, potassium salt or ammonium salt in order to enhance water solubility. The content of the organic carboxylic acid in the developer used in the present invention is not particularly limited, but if the content is less than 0.1% by weight, the effect is not sufficient.
If it is 0% by weight or more, not only the effect cannot be further improved but also dissolution may be hindered when another additive is used in combination. Therefore, the preferred addition amount is 0.1 to 10% by weight, more preferably 0.5 to 4% by weight, based on the developer used.
% By weight.

The developing solution may further contain a preservative, if necessary.
Coloring agents, thickeners, defoamers, water softeners, and the like can be included. Examples of water softeners include polyphosphoric acid and its sodium, potassium, and ammonium salts, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid, 1,2-diaminocyclohexanetetraacetic acid. Aminopolycarboxylic acids such as acetic acid and 1,3-diamino-2-propanoltetraacetic acid and their sodium, potassium and ammonium salts, aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylene Phosphonic acid), triethylenetetraminehexa (methylenephosphonic acid), hydroxyethylethylenediaminetri (methylenephosphonic acid) and - hydroxy data ene-1,1-diphosphonic acid and their sodium salts, potassium salts and ammonium salts.

The optimum value of such a water softener varies depending on the chelation thereof, the hardness of the hard water used and the amount of the hard water. -5% by weight, more preferably 0.01-0.
It is in the range of 5% by weight. If the added amount is less than this range, the intended purpose is not sufficiently achieved, and if the added amount is larger than this range, an adverse effect on an image portion such as color omission appears. The remaining component of the developer is water. It is advantageous from the viewpoint of transportation that the developing solution is a concentrated solution in which the content of water is smaller than that at the time of use, and is diluted with water at the time of use. In this case, the concentration is suitably such that the components do not separate or precipitate.

As the developer for the photosensitive lithographic printing plate of the present invention, the developer described in JP-A-6-282079 can also be used. This is because an alkali metal silicate having a molar ratio of SiO ₂ / M ₂ O (M represents an alkali metal) of 0.5 to 2.0, and a sugar alcohol having 4 or more hydroxyl groups are added with 5 mol or more of ethylene oxide. Developer containing a water-soluble ethylene oxide addition compound obtained by the above method. Sugar alcohol is a polyhydric alcohol corresponding to one obtained by reducing an aldehyde group and a ketone group of a sugar to form primary and secondary alcohol groups, respectively. Shellfish examples of sugar alcohols include D, L-trait, erythritol, D, L-arabit, ribit, xylit, D, L-sorbit,
D, L-mannit, D, L-idit, D, L-talit, dursit, allozursit and the like, and further di-, tri-, tetra-, penta- and hexaglycerin condensed with a sugar alcohol. The water-soluble ethylene oxide adduct is obtained by adding 5 mol or more of ethylene oxide to 1 mol of the sugar alcohol. Further, propylene oxide may be block-copolymerized with the ethylene oxide-added compound, if necessary, as long as the solubility is acceptable. These ethylene oxide addition compounds may be used alone or in combination of two or more. The addition amount of these water-soluble ethylene oxide addition compounds is from 0.001 to 5
% Is suitable, more preferably 0.001-2% by weight.

The above-mentioned various surfactants and organic solvents can be further added to the developer, if necessary, for the purpose of accelerating the developability, dispersing the developing residue and increasing the ink affinity of the printing plate image area. .

The PS developed with the developer having such a composition
The plate is subjected to post-treatment with washing water, a rinsing solution containing a surfactant or the like, a finisher containing a gum arabic or a starch derivative, or a protective gum solution. These treatments can be used in various combinations for the post-treatment of the PS plate of the present invention.

In recent years, automatic developing machines for PS plates have been widely used in the plate and printing industries 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 PS plate, each processing solution tank and a spray device, and pumps the exposed PS plate horizontally while pumping it. Each processing liquid is sprayed from a spray nozzle to perform development and post-processing. Recently, a PS plate is immersed and transported by a submerged guide roll or the like in a processing solution tank filled with a processing solution to carry out development processing, or a fixed amount of small amount of washing water is supplied to the plate surface after development for washing. A method is also known in which the waste water is reused as dilution water of a developer undiluted solution.

In such automatic processing, processing can be performed while replenishing each processing solution with a replenisher in accordance with the processing amount, operating time, and the like. Further, a so-called disposable processing method in which processing is performed with a substantially unused processing liquid can also be applied. The lithographic printing plate obtained by such a process is set on an offset printing machine and used for printing a large number of sheets.

[0167]

The present invention will be described in more detail with reference to Synthesis Examples and Examples below, but of course the scope of the present invention is not limited by these.

Synthesis Example 1 The following compound (A) 16.8 parts by weight, the following compound (B) 1
0.9 parts by weight and 7.6 parts by weight of lauryl methacrylate were dissolved in 65.7 parts by weight of methyl cellosolve, and heated to 65 ° C. under a nitrogen stream. Next, 0.82 parts by weight of azobisisobutyronitrile (AIBN) was added, and the mixture was stirred for 4 hours, further stirred at 75 ° C. for 1 hour, diluted with 100 parts by weight of methyl ethyl ketone, and then poured into 3000 parts by weight of water. Thus, a polymer was precipitated. The precipitated polymer was filtered and dried to obtain P-5 shown in the specific examples of the polymer of the present invention.
(Weight average molecular weight, M _w = 23,000) was obtained. The numbers in the structural formulas of the specific examples of the polymer all indicate the molar ratio of each monomer component.

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Synthesis Examples 2 and 3 and Comparative Synthesis Example The polymers shown in Table 1 were synthesized in the same manner as in Synthesis Example 1. Further, as a polymer used in a comparative example, a copolymer shown in Synthesis Example 9 of JP-A-8-15858 described below was also synthesized by the same method. The weight average molecular weight of the obtained polymer was determined by GPC (Gel Permeatio).
nChromatography (abbreviation for nChromatography) and measured in terms of standard polystyrene, and are shown in Table 1.

[0171]

[Table 1]

[0172]

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Examples 1 to 3 and Comparative Example 1 All percentages in this example are by weight unless otherwise specified. JIS A 0.24mm thick
Nylon brush and 40
After graining using an aqueous suspension of 0 mesh pumistone, it was washed well with water. 70% in 10% sodium hydroxide
After immersion at 60 ° C. for 60 seconds for etching, the substrate was washed with running water, then neutralized with 20% HNO ₃ , and washed with water. This is expressed as 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 charge of 160 coulomb / dm ² . When the surface roughness was measured, it was 0.6 μm ( _Ra display). Continued 3
After desmutting 2 minutes immersed 55 ° C. in a 0% aqueous H ₂ SO _4, the current density 14A in 20% H ₂ SO ₄ aqueous solution /
After anodic oxidation and rinsing with water so that dm ² and the amount of anodic oxide film correspond to 2.5 g / m ² , sodium silicate was then added.
The substrate was treated with a 5 wt% aqueous solution at 30 ° C. for 20 seconds and washed with water to form a substrate.

The undercoat liquid (I) having the following composition was applied to the surface of the substrate thus treated, and dried at 70 ° C. for 10 seconds.
Substrate [A] was prepared. The coating amount after drying was 5 mg / m ² . Undercoat liquid (I) Compound of structural formula (A) 0.3 g Compound of structural formula (B) 0.013 g Methanol 100 g Pure water 1 g

[0175]

Embedded image

Then, the photosensitive solution shown in Table 2 was applied on the substrate [A] by rod coating at 12 ml / m ² ,
For 1 minute to obtain a positive photosensitive lithographic printing plate. The coating amount after drying was 1.15 g / m ² .

[0177]

[Table 2]

[0178]

Embedded image

A mat layer-forming resin solution was sprayed on the surface of the photosensitive layer prepared as described above to form a mat layer. However, in order to measure the contact angle on the surface of the photosensitive layer later, a part was cut out before the mat layer was provided.
As a resin solution for forming a mat layer, methyl methacrylate / ethyl acrylate / acrylic acid (charged weight ratio: 65: 2)
0:15) A 12% aqueous solution containing a part of the copolymer as a sodium salt (potassium salt or ammonium salt depending on the case) was prepared, and the number of rotations of the atomizing head was 25,000 rpm by a rotary atomizing electrostatic coating machine. , The amount of resin solution sent is 40 ml /
Min, the voltage applied to the atomizing head was -90 kV, the ambient temperature at the time of application was 25 ° C., and the relative humidity was 50%. 2.5 seconds after application, steam was sprayed on the application surface and wetted, and then wetted After 3 seconds, hot air having a temperature of 60 ° C and a humidity of 10% was blown for 5 seconds to dry. The application amount of this mat layer is 150 mg / m ²
Met.

The photosensitive lithographic printing plate thus prepared was evaluated by the following method. The contact angle was determined using a contact angle meter (CA-S150 type) manufactured by Kyowa Interface Science Co., Ltd. on a photosensitive lithographic printing plate that had been cut out before the mat layer was formed, using a droplet method with pure water. Was measured. The height of the mat is measured by using a photosensitive lithographic printing plate provided with a mat layer up to Kosaka Laboratory Co., Ltd.
And a three-dimensional roughness analyzer MODEL SE-3FK and a three-dimensional roughness analyzer SPA-11.

For the vacuum contact time, the photosensitive lithographic printing plate provided up to the mat layer is set in a baking frame (type YHP) manufactured by Kitamura Photographic Materials Co., Ltd., and a 175 L 50% halftone original is further set. Thereafter, the vacuum pump is started, and the number of seconds in which the photosensitive lithographic printing plate and the original film adhere to each other is visually evaluated. The shorter the time, the better the vacuum adhesion.
The presence or absence of sludge is determined by sensitizing the photosensitive lithographic printing plate provided up to the mat layer to 100 cc of the aqueous solution shown in Table 3, backing the entire surface of the prepared photosensitive lithographic printing plate 1 m ² , developing, and adding fluorine to the processing solution. It was evaluated whether sludge caused by the polymer occurred. The exposure is performed on a photosensitive lithographic printing plate provided up to the mat layer using a manuscript composed of solid and halftone dots, and an automatic developing machine 900VR manufactured by Fuji Photo Film Co., Ltd. [Developer is manufactured by Fuji Photo Film Co., Ltd.] DP-7 (1: 8) and finisher using FP-2W (1: 1)]
The printing machine was used to evaluate the number of prints required to obtain a printed material having no problem of ink deposition on the image area. The smaller the number, the better the inking property. Table 4 shows the results.

[0182]

[Table 3]

[0183]

[Table 4]

As can be seen from Table 4, Examples 1 to 3 were used.
Has a high contact angle value, so that the inking property is good, the mat height is high, and the vacuum adhesion is also good.

Examples 4 to 6 and Comparative Example 2 In the same manner as in Examples 1 to 3 and Comparative Example 1, the photosensitive solution shown in Table 5 was applied to the substrate [A] on which the coating of the undercoating solution was performed by rod coating at 12 ml / m 2. ^{2 was} applied and dried at 100 ° C. for 1 minute to obtain a positive photosensitive lithographic printing plate. The coating amount after drying is 1.
It was 15 g / m ² .

[0186]

[Table 5]

The photosensitive lithographic printing plate thus prepared was evaluated in the same manner as in Examples 1 to 3 and Comparative Example 1. Table 7 shows the results.

[0188]

[Table 6]

[0189]

[Table 7]

As can be seen from Table 7, when the amount of the fluorine-containing polymer added was increased, Examples 4 to 6 exhibited better inking property and vacuum adhesion, and showed no sludge generation. is there. On the other hand, the polymer of the comparative example improves the vacuum adhesion to some extent, but increases the generation of sludge and cannot be used at all.

[0191]

According to the present invention, it is possible to obtain a photosensitive lithographic printing plate which shows a high contrast image forming property without lowering the sensitivity and has a good inking property. Furthermore, an excellent photosensitive lithographic printing plate can be obtained in which the vacuum deposition time is shortened due to the high mat forming ability and baking does not occur.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08F 220/20 C08F 220/20 220/58 220/58 220/60 220/60 C08L 101/02 C08L 101/02 101/12 101 / 12 G03F 7/00 503 G03F 7/00 503 7/022 7/022 7/115 7/115 (72) Inventor Kazuo Fujita 4000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture Inside Fujisha Shin Film Co., Ltd.

Claims (2)

[Claims] Claims: 1. A support comprising, on one or both surfaces of a support, an addition-polymerizable monomer (1) having a fluoroaliphatic group in which a hydrogen atom is substituted by a fluorine atom in a side chain, and an acidic hydrogen atom. At least one selected from addition-polymerizable monomers having an acidic group in which a hydrogen atom is bonded to a nitrogen atom, addition-polymerizable monomers having a phenolic hydroxyl group, and addition-polymerizable monomers having a -COOH group
A photosensitive lithographic printing plate having a positive photosensitive layer containing a polymer compound containing seed (2) as a copolymer component, and having a surface contact angle value of 105 ° or more. . 2. The photosensitive lithographic printing plate according to claim 1, further comprising a mat layer formed by spraying an aqueous liquid in which a mat forming agent is dissolved or dispersed on the photosensitive layer.