JPH11327129A - Photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adequate photosensitive composition exhibiting contrasty image forming property and less development blurring, excellent in white light safety, with wide development latitude. SOLUTION: In this photosensitive composition containing a fluorine surface active agent, the fluorine surface active agent is a synthetic resin (I) having: a fluoroaliphatic group (a); a 4C or more aliphatic group or aromatic group having (b); and a substituent having an acidic hydrogen atom (c). Preferably the synthetic resin (I) is a condensation polymerization resin or a polyaddition resin. That is, if the synthetic resin (I) is the condensation polymerization resin or the polyaddition resin, there exist no deviation of composition due to succession of identical monomers in a polymer chain as is the case of radical polymerization system resins, especially there is no part rich in a fluorine component, and hence a problem such as crawling, etc., hardly occurs when being prepared in embrocation.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive composition containing a novel fluorine-based surfactant (also referred to as a fluorine-based polymer), and more particularly to a photosensitive composition useful for a lithographic printing plate. The present invention relates to a photosensitive composition that provides a hard image forming property in a lithographic printing plate.

[0002]

2. Description of the Related Art A lithographic printing plate comprising a photosensitive composition coated on a substrate is usually exposed to light, and then exposed or unexposed portions are removed by alkali development to obtain an image. Next, the image remaining in the printing process acts as an ink receiving portion, and the substrate that appears after elution acts as a water receiving portion to obtain a printed product. At this time, in order to obtain a good printed matter, an image obtained after exposure and development regardless of a negative lithographic printing plate or a positive lithographic printing plate has as high a discrimination of an image part and a non-image part as possible, that is, a high gradation. (High contrast) is preferable in terms of image reproducibility and scratch resistance, and high sensitivity is required.

[0003] The o-typical lithographic printing plate,
A photosensitive composition containing a quinonediazide compound,
It has been industrially used as a lithographic printing plate as a very excellent positive photosensitive composition and as a photoresist. Conventionally, various proposals have been made on a method for increasing the sensitivity of the o-quinonediazide-based positive photosensitive composition,
Shows high-contrast image forming properties without reducing sensitivity,
Further, there is no product which satisfies burning, white light safety and development tolerance.

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

[0005] The white light safety indicates the stability of image sensitivity when the printing plate is exposed to a white light such as a fluorescent light, and the higher the image quality, the lower the white light safety. good. This is due to the fact that quinonediazide is partially decomposed by white light, and the image with high contrast is similar to that when quinonediazide is decomposed in a small amount, the image does not elute and it was not exposed under white light. It becomes an image. The step wedge is a strip-shaped film in which the density changes by 0.15 for each step, and is used to obtain the relationship between the exposure amount and the remaining amount of the photosensitive layer after development after exposure. The clear sensitivity means the sensitivity at which an image starts to be formed after exposure and development. The development tolerance refers to how much the image sensitivity after exposure and development changes when the concentration of the developer changes, and the smaller the change in sensitivity, the better the development tolerance. .

Further, a photopolymerization printing plate containing a photopolymerization initiator represented by a negative type lithographic printing plate and a monomer having a polymerizable double bond, particularly a laser direct plate having high sensitivity to a laser beam in the visible light region. In the case of the exposure type printing plate, when the image is exposed with an inner drum type laser plate setter that fixes the printing plate and rotates and exposes the mirror at high speed, the fog due to scattered light and reflected light occurs because the gradation is conventionally soft. It was easy. Exposure with high energy is desired to increase the printing durability of the printing plate. However, fogging due to scattered light and reflected light is getting worse, so that the exposure amount cannot be increased to increase the printing durability. In order to increase the printing durability, it is necessary to prevent fog due to scattered light and reflected light even at a high exposure amount. This can be solved by making the gradation hard. This is because image exposure with a laser exposes for about 1 microsecond per dot, but fog due to scattered or reflected light is exposed to extremely weak light for a few minutes on the order of several minutes, and the photosensitive layer is exposed. Light curing.

Therefore, when the gradation of the photosensitive material becomes high, the photosensitive material is hardly photocured with weak light, and is removed by development without fogging. In the case of a heat-sensitive lithographic printing plate that draws using an infrared laser, etc., discrimination between the image part and the non-image part is low, that is, the gradation is low (soft tone), so that an image may be missing in the part touched with bare hands. In addition, there has been a problem that stability against trauma is poor. JP-A-62-226143 and JP-A-3-172849 describe a fluorine-containing polymer having a fluoroaliphatic group and a polyoxyalkylene group as a surfactant. Even with these polymers, no effect was obtained with respect to burning and white light safety.

[0008] JP-A-8-15858 describes a fluoropolymer having a fluoroaliphatic group, a polyoxyalkylene group, and an acidic hydrogen atom group as a surfactant. However, even if a polymer described as a specific example in the publication is used, no effect is obtained with respect to burning and self-light safety.

[0009]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, shows a high-contrast image forming property without lowering the sensitivity, and provides a burn-out, white-light safety,
It is intended to provide a satisfactory photosensitive composition having a wide development tolerance.

[0010]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above object can be achieved by adding a specific fluorine-containing polymer to a photosensitive composition. That is, when the following copolymer is added to the photosensitive composition as a fluorine-containing polymer, the present invention shows high image forming properties without lowering the sensitivity, and shows burn-out, white light safety, and development. It has been found that a positive photosensitive composition having a wide tolerance is obtained. This method is particularly effective for enhancing the contrast of a positive photosensitive composition which has been enhanced in sensitivity by a conventionally known method. The addition of the fluorine-containing polymer according to the present invention enhances the contrast of a soft image and increases the print quality. It has been found that blur, white light safety, and development tolerance are improved.

The addition of the fluoropolymer of the present invention increases the gradation in a negative type lithographic printing plate. In particular, a laser-sensitive photopolymerized printing plate has high sensitivity to laser light and high scattering light and reflection. It was found that a printing plate having good fogging property by light and high printing durability was obtained.
Further, it has been found that a heat-sensitive lithographic printing plate has a large discrimination and a high image strength, so that a plate which does not cause image omission at a portion touched by bare hands and has improved stability against trauma can be obtained. The fluoropolymer according to the present invention is a kind of surfactant, which is a fluoroaliphatic group (a), an aliphatic or aromatic group having 4 or more carbon atoms (b), a substituted group having an acidic hydrogen atom. It is a synthetic resin (I) having a group (c), and more preferably, the synthetic resin (I) is a polycondensation or polyaddition resin. If the synthetic resin (I) is a polycondensation or polyaddition resin, there is no component bias due to the continuation of the same monomer in the polymer chain such as a radical polymerization resin, and there is no particularly fluorine-rich part. This has the advantage that problems such as cissing are unlikely to occur.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The fluorine polymer which characterizes the present invention will be described below. The fluorine-based polymer used in the present invention is a polymer containing a structural unit having the above groups a, b, and c. As the form, a styryl resin, a polyester resin, a polyurea resin, a polycarbonate resin, a polyamide resin, a polyacetal resin, or the like is used. be able to. Among them, polycondensation and polyaddition resins are useful, and polyamide resins, polyester resins, polyurea resins, and polycarbonate resins are particularly useful. The polyamide resin, polyester resin, polyurea resin, and polycarbonate resin will be described in detail.

The polyamide resin can be produced by a known and commonly used method. For example, it can be obtained by polycondensation of a diamine compound and a dicarboxylic acid compound. Specific examples of the diamine compound having a fluoroaliphatic group (a) used in the present invention include the following.

[0014]

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[0015]

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[0016]

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The amount of these fluoroaliphatic group-containing diamine compounds used in the fluorine-containing polyamide resin used in the present invention is 3% based on the weight of the polyamide resin.
To 80% by weight, preferably 7 to 60% by weight.

Specific examples of the diamine compound having an aliphatic group or an aromatic group (b) having 4 or more carbon atoms include the following diamines. 1,3
-Diaminopropane, 1,4-diaminobutane, 1,5
-Diaminopentane, hexamethylenediamine, 1,8
-Diaminooctane, 1,12-diaminododecane, trimethyl-1,6-hexanediamine, 2,2′-dimethyl-1,3-propanediamine, DYTEKA amine, 1,9-diaminononane, DYTEK EP amine, 1, 7-diaminoheptane, 1,10-diaminodecane, 2-butyl-2-ethyl-1,5-pentanediamine, SPERMINE, SPERMINE, bis (hexamethylene) triamine, 5-amino-2,
2,4-trimethyl-1-cyclopentamethylamine,
1,2-diaminocyclohexane, 4,4'-methylenebis (2-methylcyclohexylamine), 1,3-cyclohexanebis (methylamine), 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), 4,9-dioxa-1,12-dodecanediamine, 2,2'-ethylenedianiline, 2-aminophenyldisulfide, 4,4'-ethylenedianiline,

4,4'-diaminostilbene, 3,3 '
-Methylenedianiline, 4,4'-methylenedianiline, 4,4'-methylenebis (3-chloro-2,6-diethylamine), 4,4'-oxydianiline, 4-aminophenyldisulfide, 4 ", 4 "'-(hexafluoroisopropylidene) bis (4-phenoxyaniline), 4,4'-thiodianiline, 2,3-diaminophenol, 4,4'-ethylenedi-M-toluidine, o
-Tolidine, 5,5 '-(hexafluoroisopropylidene) -di-o-toluidine, 4,4'-methylenebis (2,6-dimethylaniline), 4,4'-methylenebis (2,6-diethylaniline) , 4,4'-methylenebis (2,6-diisopropylaniline), 3,3 ',
5,5'-tetramethylbenzidine, 2,3-diaminotoluene, 4-chloro-1,2-phenylenediamine,
4,5-dichloro-1,2-phenylenediamine, 4-
Methoxy-1,3-phenylenediamine, 1,4-phenylenediamine, 1,2-phenylenediamine, 1,3
-Diaminotoluene, 4-methoxy-1,2-phenylenediamine, 2,6-diaminotoluene,

2,4-diaminophenol, 4,5-dimethyl-1,2-phenylenediamine, 1,3-phenylenediamine, 2,4-diaminotoluene, 4- (2-
(Hydroxythio) -1,3-phenylenediamine, 2,
4,6-trimethyl-1,3-phenylenediamine,
2,5-diaminotoluidine, 2,5-dichloro-1,
4-phenylenediamine, 2-methoxy-1,4-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, 2-chloro-1,4-phenylenediamine, 3,3 '-(hexafluoropropylidene ) Dianiline, 3,3'-dimethoxybenzidine, 4,4'-diaminodiphenylamine, 3,3'-dimethylnaphthidine, 2,2'-dithiobis (1-naphthylamine),
1,5-diaminonaphthalene, 1,1'-binaphthyl-
2,2'-diamine, 2,7-diaminofluorene,
1,8-diaminonaphthalene, 9,10-diaminophenanthrene

The amount of the aliphatic or aromatic group-containing diamine compound having 4 or more carbon atoms used in the fluorine-containing polyamide resin used in the present invention is 5 to 5 based on the weight of the polyamide resin. It is 80% by weight, preferably 10 to 60% by weight.

The diamine compound having a substituent (c) having an acidic hydrogen atom includes, for example, compounds represented by the following general formulas [1] to [4].

[0023]

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In the formula, R ¹ represents a hydrogen atom, an alkyl, an aryl, an alkoxy or an aryloxy group, preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and a carbon atom having 6 to 15 carbon atoms.
Aryl groups. R ^{2 to} R ⁴ may be the same or different, and may have a single bond, a divalent alkyl group or an aryl group which may have a substituent such as an alkyl group, an aryl group, an alkoxy group, or a halogen atom. Is shown.
Preferably an alkylene group having 1 to 20 carbon atoms, 6 carbon atoms
~ 15 arylene groups, more preferably 1 to 1 carbon atoms
8 alkylene groups. Ar represents a trivalent aryl group.

R ⁵ may have a substituent such as an alkyl group, an aryl group, an alkoxy group and a halogen atom.
A valent alkyl group or an aryl group; Preferred are an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 15 carbon atoms. Q represents an N-sulfonamide group (—CO—N
H-SO ₂ -), sulfonamide group (-SO ₂ NH-),
N-sulfonyluureido group (-NH-CO-NH-SO
_2- ), N-aminosulfonylamide group (-CO-NH
—SO ₂ —NH—), a sulfonyluethane group (—O—C
_{O-NH-SO 2 -)} , an imido group (-CO-NH-CO
-), a sulfonimide group (-SO ₂ NHSO ₂ - shows a). Specific examples of the diamine compound having a substituent (c) having an acidic hydrogen atom include the following.

[0026]

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[0027]

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[0028]

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[0029]

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The amount of the substituent-containing diamine compound having an acidic hydrogen atom used in the fluorine-containing polyamide resin used in the present invention is 5 to 80% by weight based on the weight of the polyamide resin, and is preferably It is 10 to 70% by weight.

As the diamine component used in the present invention, known amine compounds can be used in addition to the diamine compounds represented by the components (a), (b) and (c) of the present invention. . For example, ethylenediamine,
1,3-diaminopropane, 1,2-diaminopropane, N- (3-aminopropyl) -1,3-propanediamine, diethylenetriamine, N- (2-aminoethyl) 1,3-propanediamine, N-1 -Isopropyldiethylenetriamine, 3,3'-diamino-N-methyldipropylamine, triethyleneetheramine,
1,4,7,11-tetraazaundecane, tetraethylenepentamine, N, N′-bis (3-aminopropyl) ethylenediamine, pentaethylenehexamine,
4- (aminomethyl) -1,8-octanediamine,
4,7,10-trioxa-1,13-tridecanediamine, 2,2'-oxybis (ethylamine), 2,
2 '-(ethylenedioxy) bis (ethylamine) and the like.

The fluoroaliphatic group (a) used in the present invention
Specific examples of the dicarboxylic acid compound having the following are, for example, the following.

[0033]

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The amount of these fluoroaliphatic group-containing dicarboxylic acid compounds used in the fluorinated polyamide resin used in the present invention is 3 to 80% by weight, preferably 7 to 80% by weight, based on the weight of the polyamide resin. 60% by weight.

Further, specific examples of the dicarboxylic acid compound having an aliphatic group or an aromatic group (b) having four or more carbon atoms include the following dicarboxylic acids.

Phthalic acid, isophthalic acid, 3,6-endomethylenetetrahydrophthalic acid, tetrahydrophthalic acid, adipic acid, sebacic acid, diethylmaleic acid,
2,3-dimethylsuccinic acid, 2,2-dimethylsuccinic acid, butylmaleic acid, 2-ethyl-2-methylsuccinic acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethyl Glutaric acid, 3-methyladipic acid, azelaic acid, 1,10-decanedicarboxylic acid, tetracosanedicarboxylic acid, 3,3-dimethylglutaric acid, 3-t-butyladipic acid, 1,12-dodecanedicarboxylic acid , 1,11-undecanedicarboxylic acid, hexadecanedicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,3-adamantanediacetic acid, 3,3-
Tetramethylene glutaric acid, 1,1-cyclohexanediacetic acid, 1,4-cyclohexanedicarboxylic acid,

Phenylsuccinic acid, 1,2-phenylenedioxydiacetic acid, 3-phenylglutaric acid, 1,3-
Phenylenediacetic acid, 1,4-phenylenediacetic acid, 2,5
Dihydroxy-1,4-benzenediacetic acid, 2-carboxybenzenepropanoic acid, 4,4 '-(hexafluoroisopropylidene) bisbenzoic acid, 4,
4'-oxybis (benzoic acid), 2,2 '
-Iminodibenzoic acid, 2-methoxyphthalic acid, 4,4'-bis (3-carboxy-4-chloroaniline) trityl chloride, diphenyl acid, 4,4'-
Biphenyldicarboxylic acid, 2,2'-dithioortholic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid,
2,7-di-t-butyl-9,9-dimethyl-4,5-
Xanthene dicarboxylic acid.

The amount of the aliphatic or aromatic group-containing dicarboxylic acid compound having 4 or more carbon atoms used in the fluorine-containing polyamide resin used in the present invention is 5 parts by weight based on the weight of the polyamide resin. ~ 80% by weight
And preferably 10 to 60% by weight.

Further, specific examples of the dicarboxylic acid compound having the substituent (c) having an acidic hydrogen atom include the following.

[0040]

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The amount of the dicarboxylic acid compound having a substituent having an acidic hydrogen atom used in the fluorine-containing polyamide resin used in the present invention is preferably 5 to 80% by weight based on the weight of the polyamide resin. Is 10-7
0% by weight.

As the dicarboxylic acid component used in the present invention, a known dicarboxylic acid compound is used in addition to the dicarboxylic acid compounds represented by the components (a), (b) and (c) of the present invention. be able to. For example, maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, chlorinated maleic acid, thiodiglycolic acid, methylmaleic acid, methylsuccinic acid, ethylmaleic acid, glutaric acid, dimethylmaleic acid and the like can be mentioned.

The polyester resin can be produced by a known and commonly used method. For example, it can be obtained by polycondensation of a diol compound and a dicarboxylic acid compound.

(A) represented as a component having a group,
Examples of a diol component having a fluoroaliphatic group in which a hydrogen atom is substituted by a fluorine atom include JP-A-8-158.
No. 58, diol compounds can be used. The amount of these fluoroaliphatic group-containing diol compounds used in the fluorine-containing polyester resin used in the present invention is 3 to 8 based on the weight of the polyester resin.
0% by weight, preferably in the range of 7 to 60% by weight.

Also, a diol having a linear or branched alkyl or alkylene group having 4 or more carbon atoms or an aryl group which may or may not be substituted, represented as the component having the group (b). For example, 4
Alkyl groups having up to 30, preferably 9 to 25 carbon atoms can be used. The aryl group in the aryl group which may be substituted or unsubstituted has 6 to 6 carbon atoms.
A divalent aromatic diol component having 20, preferably 6 to 14 carbon atoms can be used.

For example, tetraethylene glycol, neopentyl glycol, 1,3-butylene glycol,
1,6-hexanediol, 2-butyl-1,4-diol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-bis-β-hydroxyethoxycyclohexane, cyclohexanedimethanol, tricyclo Decane dimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A,
Bisphenol F ethylene oxide adduct, bisphenol F propylene oxide adduct, hydrogenated bisphenol A ethylene oxide adduct, hydrogenated bisphenol A propylene oxide adduct, hydroquinone dihydroxyethyl ether p-xylylene glycol, dihydroxyethyl sulfone, Bis (2-hydroxyethyl) -2,4-tolylene dicarbamate, 2,4
-Tolylene-bis (2-hydroxyethylcarbamide), bis (2-hydroxyethyl) -m-xylylenedicarbamate, bis (2-hydroxyethyl) isophthalate and the like.

Particularly preferred examples include 1,10-decanediol, 1,12-dodecanediol, 1,14-
Tetradecanediol, t-butylbenzenediol,
Examples thereof include n-octylbenzenediol. The amount of the diol compound having an alkyl or alkylene group having 4 or more carbon atoms or an aryl group which may or may not be substituted, which is used in the fluorine-containing polyester resin used in the present invention, is the amount of the polyester resin. It is between 5 and 80% by weight, preferably between 10 and 60% by weight, based on the weight.

As examples of the diol component having an acidic hydrogen atom, which is shown as the component having the group (c), compounds represented by the following general formulas [5] to [8] can be used.

[0049]

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In the formula, R ¹ represents a hydrogen atom, an alkyl, aryl, alkoxy, or aryloxy group, preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and a carbon atom having 6 to 15 carbon atoms.
Aryl groups. R ^{2 to} R ⁴ may be the same or different, and may have a single bond, a divalent alkyl group or an aryl group which may have a substituent such as an alkyl group, an aryl group, an alkoxy group, or a halogen atom. Is shown.
Preferably an alkylene group having 1 to 20 carbon atoms, 6 carbon atoms
~ 15 arylene groups, more preferably 1 to 1 carbon atoms
8 alkylene groups. Ar represents a trivalent aryl group. R ⁵ represents a monovalent alkyl group or an aryl group which may have a substituent such as an alkyl group, an aryl group, an alkoxy group and a halogen atom. Preferred are an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 15 carbon atoms.

Q represents an N-sulfonamide group (—CO—NH
—SO ₂ —), a sulfonamide group (—SO ₂ NH—), N
- sulfonyl ureido group (-NH-CO-NH-SO 2
-), N-aminosulfonylamide group (-CO-NH-
SO ₂ —NH—), a sulfonyluethane group (—O—CO
-NH-SO ₂ -), an imido group (-CO-NH-CO
-), a sulfonimide group (-SO ₂ NHSO ₂ - shows a). The amount of the diol component having an acidic hydrogen atom used in the fluorine-containing polyester resin used in the present invention is 5 to 80 based on the weight of the polyester resin.
%, Preferably in the range of 10 to 70% by weight. Hereinafter, examples of the diol component having an acidic hydrogen atom will be described.

[0052]

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[0053]

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[0054]

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[0055]

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Other known diol compounds can be used as components other than the components having the groups (a), (b) and (c). Examples of this include ethylene glycol, diethylene glycol, triethylene glycol and the like. In addition to these diols, diol compounds having a polyoxyalkylene group described in JP-A-8-15858 can be used. In addition,
Specific examples of the dicarboxylic acids having groups (a), (b) and (c) include those described above.

The polyurea resin can be produced by a known and commonly used method. For example, it can be obtained by polyaddition of a diamine compound and a diisocyanate compound. Specific examples of the diamine having the groups (a), (b) and (c) used in the present invention include those described above. Specific examples of the diisocyanate compound used in the present invention include, for example, the following diisocyanate compounds having an aliphatic group or an aromatic group (b) having 4 or more carbon atoms.

For example, 2,4-tolylene diisocyanate, a dimer of 2,4-tolylene diisocyanate, 2,2
6-tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,
Aromatic diisocyanate compounds such as 4'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate: hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer Aliphatic diisocyanate compounds such as acid diisocyanate: isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4
(Or 2,6) alicyclic diisocyanate compound such as diisocyanate, 1,3- (isocyanatomethyl) cyclohexane and the like: diol and diisocyanate such as adduct of 1 mol of 1,3-butylene glycol and 2 mol of tolylene diisocyanate And a diisocyanate compound which is a reaction product with the above.

The polycarbonate can be produced by a known and commonly used method. For example, the following reactions are known. 1) Transesterification of carbonic acid diester obtained from monofunctional aromatic or aliphatic oxy compound with diol compound 2) Transesterification of diol compound with bisalkyl or bisaryl carbonate of itself or other diol compound 3) Reaction of a diol compound with phosgene in the presence of an acid binder 4) Dichloro compound and bischlorocarbonate of the diol compound (bischloroformate) in the presence of an acid binder
Specific examples of the diol compounds having the groups (a), (b) and (c) used in the present invention include those described above.

The synthetic resin can have other linking groups in the main chain in addition to the linking groups. For example, a polycarbonate having an ester bond and a polycarbonate having a urethane bond can be given. Hereinafter, specific examples of the structure of the fluoropolymer according to the present invention will be described. The numbers in the formula indicate the molar ratio of each monomer component.

[0061]

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[0062]

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[0063]

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[0064]

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The range of the molecular weight of the fluoropolymer used in the present invention is from 3,000 to 200,000 as an average molecular weight.
0, more preferably 6,000-100,
000. The range of the addition amount of the fluoropolymer in the photosensitive composition of the present invention is preferably 0.001 to 10% by weight based on the total composition except for the solvent, and is preferably 0.01 to 10% by weight.
-5% by weight is more preferred.

Next, other components required for preparing the positive photosensitive composition according to the present invention will be described.
As the positive photosensitive composition, any one can be used as long as its solubility or swelling property with respect to a developer changes before and after exposure, and an o-quinonediazide compound is preferable. 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 that increase are preferred.

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

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

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 by an acid-decomposable group and a photoacid generator can be used. Known photoacid generators can be used in the chemical amplification system.

For example, SISchlesinger, Photogr.Sci.E
ng., 18,387 (1974), TSBal etal, Polymer, 21,423 (198
0) etc., U.S. Pat.No.4,069,055
No. 4,069,056, ammonium salts described in JP-A-3-140,140, etc., DCNecker et al., Macromolecules, 17,2468
(1984), CSwen et al, Teh, Proc.Conf.Rad.Curing ASI
A, p478 Tokyo, Oct (1988), U.S. Pat.No. 4,069,055,
4,069,056, etc., phosphonium salts, JVCrivello
etal, Macromorecules, 10 (6), 1307 (1977), Chem. & Eng.Ne
ws, Nov. 28, p31 (1988), European Patent No. 104,143, U.S. Patent No. 339,049, No. 410,201, JP-A-2-150,848, JP-A-2-296,514, etc.
llo etal, Polymer J. 17, 73 (1985), JVCrivello eta
lJOrg.Chem., 43, 3055 (1978), WRWatt et al., J. Polym
er Sci., Polymer Chem. Ed., 22, 1789 (1984), JVCrivel
lo etal, Polymer Bull., 14,279 (1985), JVCrivello e
tal, Macromorecules, 14 (5), 1141 (1981), JVCrivello
etal, J. Polymer Sci., Polymer Chem. Ed., 17, 2877 (1979)
, EP 370,693, U.S. Patent 3,902,114, EP 233,567, 297,443, 297,442, U.S. Pat.
No. 60,013, 4,734,444, 2,833,827, Dokoku Patent No.
2,904,626, 3,604,580, 3,604,581, etc., sulfonium salts, JVCrivello etal, Macromorecule
s, 10 (6), 1307 (1977), JVCrivello etal, J. Polymer Sc
Selenonium salts described in i., Polymer Chem. Ed., 17, 1047 (1979), etc., CSWen et al., Teh, Proc. Conf.
ASIA, p478 Tokyo, Oct (1988), etc., onium salts such as arsonium salts, U.S. Pat.No. 3,905,815, JP-B-46-46
05, JP-A-48-36281, JP-A-55-32070, JP-A-60
-239736, JP-A-61-169835, JP-A-61-169837,
JP-A-62-58241, JP-A-62-212401, JP-A-63-7024
No. 3, organic halogen compounds described in JP-A-63-298339, K. Meier et al., J. Rad.Curing, 13 (4), 26 (1986), TP
Gill et al., Inorg.Chem., 19, 3007 (1980), D. Astruc, Ac
c. Chem. Res., 19 (12), 377 (1896), organometallics / organic halides described in JP-A-2-14145, etc., S. Hayase et al.
J. Polymer Sci., 25, 753 (1987), E. Reichmanis et al., J. Ph
olymer Sci., Polymer Chem. Ed., 23, 1 (1985), QQZhu et.
al, J. Photochem., 36, 85, 39, 317 (1987), B. Amit et al, Tet
rahedron Lett., (24) 2205 (1973), DHR Bartonetal, JC
hem Soc., 3571 (1965), PM Collins et al., J. Chem. SoC., P
erkin I, 1695 (1975), M. Rudinstein et al., Tetrah edron Lett., (17), 1445 (1975), JWWalker et al. J. Am. C
hem. Soc., 110, 7170 (1988), SCBusman et al., J. Imaging
Technol., 11 (4), 191 (1985), HM Houlihan et al, Macormo
lecules, 21, 2001 (1988), PM Collins et al., J. Chem. So
c., Chem.Commun., 532 (1972), S.Hayase et al, Macromole
cules, 18, 1799 (1985), E. Reichmanis et al., J. Electroche
m.Soc., Solid State Sci.Technol., 130 (6), FMHouliha
n etal, Macromolcules, 21, 2001 (1988), European Patent 029
0,750, 046,083, 156,535, 271,851,
0,388,343, U.S. Pat.Nos. 3,901,710, 4,181,531
JP-A-60-198538, JP-A-53-133022 and the like, a photoacid generator having an o-nitrobenzyl-type protecting group, M.TU
NOOK etal, Polymer Preprints Japan, 35 (8), G. Berner
etal, J.Rad.Curing, 13 (4), WJMijs etal, Coating Tech
nol., 55 (697), 45 (1983), Akzo, H. Adachi et al, Polymer
Preprints, Japan, 37 (3), European Patent Nos. 0199,672, 845
No. 15, No. 199,672, No. 044,115, No. 0101,122, U.S. Pat.Nos. 4,618,564, 4,371,605, 4,431,774,
JP-A-64-18143, JP-A-2-245756, Japanese Patent Application No. 3-14010
Compounds which generate sulfonic acid upon photodecomposition, such as iminosulfonate described in JP-A No. 9-16654.
Disulfone compounds described in No. 4, etc. can be exemplified.

The amount of the compound that decomposes upon irradiation with actinic rays or radiation to generate an acid is usually 0.02% 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
A compound having a bond, and the following examples can be given. a) comprising at least one group of orthocarboxylic acid esters and / or carboxylic acid amide acetals, wherein the compounds can be polymerizable, said groups occurring as crosslinking elements in the main chain or as lateral substituents B) an oligomeric or polymeric compound containing a repeating acetal and / or ketal group in the main chain; c) a compound containing at least one enol ester or N-acylaminocarbonate group; d) a β-keto ester Or a cyclic acetal or ketal of β-keto amide,

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

Compounds of the type (a) which can be cleaved by acids as components of the radiation-sensitive mixture are described in 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 with the acid-decomposable group is usually 1 to 60% by weight, more preferably 5 to 40% by weight, based on the total solid content of the photosensitive composition.

Examples of the water-insoluble synthetic resin soluble in an alkaline aqueous solution (hereinafter referred to as an alkali-soluble resin) include phenol-formaldehyde resin, cresol-formaldehyde resin, phenol-cresol-formaldehyde co-condensation resin, phenol-modified xylene resin,
In addition to polyhydroxystyrene, polyhalogenated hydroxystyrene, a copolymer of N- (4-hydroxyphenyl) methacrylamide, a copolymer of hydroquinone monomethacrylate, a sulfonylimide polymer described in JP-A-7-28244, And carboxyl group-containing polymers described in JP-A-7-36184. Other acrylic resins containing a phenolic hydroxyl group as disclosed in JP-A-51-34711, acrylic resins having a sulfonamide group described in JP-A-2-866, and urethane-based resins. Various alkali-soluble polymer compounds can also be used. These alkali-soluble polymer compounds have a weight average molecular weight of 50.
0 to 20,000 and number average molecular weight of 200 to 60,00
0 is preferred. 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 cyclic acid anhydrides, phenols and organic acids in order to increase the sensitivity. The cyclic acid anhydride U.S. Pat phthalic anhydride as described in 4,115,128 Pat, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-oxy - [delta ⁴ -
Examples include tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, and pyromellitic anhydride. As phenols, bisphenol A, p-nitrophenol, p-ethoxyphenol,
2,3,4-trihydroxybenzophenone, 4-hydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 4,4 ', 4 "-trihydroxy-triphenylmethane, 4,4', 3", 4 "-Tetrahydroxy-3,5,3 ', 5'-tetramethyltriphenylmethane.

As the organic acids, JP-A-60-8894
2, sulfonic acids, sulfinic acids, alkyl sulfates, phosphonic acids, phosphinic acids, phosphoric esters, carboxylic acids, and the like described in JP-A No. 2-96755 and JP-A-2-96755. p-toluenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethyl sulfate, phenylphosphonic acid,
Phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, adipic acid, p-toluic acid, 3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, 1,4-cyclohexene-2,2- Examples thereof include dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, and ascorbic acid. The above cyclic acid anhydrides,
The proportion of phenols and organic acids in the photosensitive composition is preferably from 0.05 to 15% by weight, more preferably from 0.1 to 5% by weight.

Next, the photosensitive composition of the present invention when used as a photosensitive layer of a photopolymerizable printing plate will be described. When the photosensitive composition of the present invention is a photopolymerizable photosensitive composition, the main components thereof include, in addition to the fluorine-based polymer, a compound containing an addition-polymerizable ethylenic double bond, And a compound such as a thermal polymerization inhibitor, if necessary.

The compound containing a double bond capable of addition polymerization is
It can be arbitrarily selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds. For example, those having a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof. Examples of monomers and copolymers thereof include esters of unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) with aliphatic polyhydric alcohol compounds, and unsaturated esters. Examples include amides of carboxylic acids and aliphatic polyamine compounds.

Specific examples of the ester monomer of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include acrylates such as ethylene glycol diacrylate, triethylene glycol diacrylate, and 1,3.
-Butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol pentaacrylate
G, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer and the like.

Examples of the methacrylate include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol. Dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentamethacrylate, sorbitol tri Methacrylate, sorbitol tetramethacrylate , Bis [p- (3--methacryloxy-2-hydroxypropoxy) phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

Examples of itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate,
There are 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetritaconate and the like.

The crotonates include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate,
Sorbitol tetradicrotonate and the like. Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. The maleic acid ester includes ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetramaleate and the like. Furthermore, a mixture of the above-mentioned ester monomers can also be mentioned.

Specific examples of the amide monomer of the aliphatic polyamine compound and the unsaturated carboxylic acid include methylenebis-acrylamide, methylenebis-methacrylamide, 1,6-hexamethylenebis-acrylamide, 1,6- Hexamethylene bis-methacrylamide,
Examples include diethylenetriaminetrisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide, and the like. Another example is JP-B-48-417.
08 polyisocyanate compound having two or more isocyanate groups in one molecule described in
A vinyl urethane compound containing two or more polymerizable vinyl groups in one molecule to which a hydroxyl group-containing vinyl monomer represented by the following general formula (A) is added is exemplified. CH ₂ ＣC (R ₅ ) COOCH ₂ CH (R ₆ ) OH (A) (where R ₅ and R ₆ represent H or CH ₃ )

Further, urethane acrylates described in JP-A-51-37193,
64183, JP-B-49-43191, JP-B-52
And polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid as described in JP-A-30490. In addition, Journal of the Adhesion Society of Japan vol. 20, No. 7, 300-30
Those introduced as photocurable monomers and oligomers on page 8 (1984) can also be used. In addition, the amount of these used is 5-70 with respect to all components.
% By weight (hereinafter abbreviated as%), preferably 10 to 50
%.

As the photopolymerization initiator contained in the photopolymerizable photosensitive composition used in the present invention, various photopolymerization initiators known in patents and literatures, or 2 A combination system of two or more photopolymerization initiators (photopolymerization initiation system) can be appropriately selected and used. For example, when light near 400 nm is used as a light source, benzyl, benzoin ether, Michler's ketone, anthraquinone, thioxanthone, acridine, phenazine, benzophenone, and the like are widely used.

In addition, visible light of 400 nm or more, an Ar laser, a second harmonic of a semiconductor laser, SHG-YAG
Even when a laser is used as a light source, various photopolymerization initiation systems have been proposed, for example, US Pat. No. 2,850,44.
Certain photoreducing dyes described in No. 5, such as rosbengal, eosin, erythrosine, and the like, or a system based on a combination of a dye and a photopolymerization initiator, for example, a complex initiation system of a dye and an amine (Japanese Patent Publication No. Sho 44) -20189), a combination system of hexaarylbiimidazole, a radical generator and a dye (JP-B-45-37377), and a system of hexaarylbiimidazole and p-dialkylaminobenzylidene ketone (JP-B-47-2528; 54-1 Kaisho
55292), a system of a cyclic cis-α-dicarbonyl compound and a dye (JP-A-48-84183), a system of a cyclic triazine and a merocyanine dye (JP-A-54-151024).
No.), a system of 3-ketocoumarin and an activator (JP-A-52-1)
No. 12681, JP-A-58-15503), a system of biimidazole, a styrene derivative and a thiol (JP-A-59-15503).
140203), a system of an organic peroxide and a dye (JP-A-5
9-1504, JP-A-59-140203, JP-A-59-189340, JP-A-62-174203,
JP-B-62-1641, U.S. Pat. No. 4,766,055
No.), a system of a dye and an active halogen compound (JP-A-63-2
58903, JP-A-2-63054, etc.),

A system comprising a dye and a borate compound (JP-A-62-2
No. 143044, JP-A-62-150242, JP-A-64-13140, JP-A-64-13141, JP-A-64-13142, JP-A-64-13143, JP-A-64-13144 JP-A-64-17048,
JP-A-1-229003, JP-A-1-298348
And a system comprising a dye having a rhodanine ring and a radical generator (Japanese Patent Laid-Open No. 2-1796).
No. 43, JP-A-2-244050), titanocene and 3
-Ketocoumarin dye system (JP-A-63-221110)
), A system in which a titanocene and a xanthene dye are further combined with an ethylenically unsaturated compound capable of addition polymerization containing an amino group or a urethane group (JP-A-4-221958,
JP-A-4-219756), a system of titanocene and a specific merocyanine dye (JP-A-6-295061), and a system of titanocene and a dye having a benzopyran ring (JP-A-8-295).
No. 334897). The amount of these photopolymerization initiators used is 100 ethylenically unsaturated compounds.
It can be used in an amount of 0.05 to 100 parts by weight, preferably 0.1 to 70 parts by weight, more preferably 0.2 to 50 parts by weight based on parts by weight.

Further, in the photopolymerizable photosensitive composition of the present invention, in addition to the above basic components, unnecessary thermal polymerization of an ethylenically unsaturated compound which can be polymerized during the production or storage of the photosensitive composition. It is desirable to add a small amount of a thermal polymerization inhibitor in order to prevent the polymerization. Suitable thermal polymerization inhibitors include haloid quinone, p-methoxyphenol, di-t
-Butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-
Methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol),
N-nitrosophenylhydroxylamine cerium salt, N-nitrosophenylhydroxylamine aluminum salt and the like can be mentioned. The addition amount of the thermal polymerization inhibitor is preferably from about 0.01% to about 5% based on the weight of the whole composition.
If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition by oxygen, and may be unevenly distributed on the surface of the photosensitive layer in a drying process after coating. . The addition amount of the higher fatty acid derivative is preferably about 0.5% to about 10% of the whole composition.

A lithographic printing plate having a photosensitive layer using the photosensitive composition of the present invention as a photosensitive layer is provided on the photosensitive layer in order to prevent polymerization inhibition by oxygen. A protective layer may be provided. Examples of the water-soluble vinyl polymer contained in the oxygen-blocking protective layer include polyvinyl alcohol, and its partial esters, ethers, and acetal, or a substantial amount of unsubstituted vinyl alcohol units that have the necessary water solubility. And copolymers thereof. Polyvinyl alcohol is hydrolyzed by 71 to 100% and has a polymerization degree of 30.
Those having a range of 0 to 2400 are exemplified.

Specifically, PVA-10 manufactured by Kuraray Co., Ltd.
5, PVA-110, PVA-117, PVA-117
H, PVA-120, PVA-124, PVA-124
H, PVA-CS, PVA-CST, PVA-HC, P
VA-203, PVA-204, PVA-205, PV
A-210, PVA-217, PVA-220, PVA
-224, PVA-217EE, PVA-217E, P
VA-220E, PVA-224E, PVA-405,
PVA-420, PVA-613, L-8 and the like. Examples of the copolymer include 88-100% hydrolyzed polyvinyl acetate chloroacetate or propionate, polyvinyl formal and polyvinyl acetal, and copolymers thereof. Other useful polymers include polyvinylpyrrolidone, gelatin and gum arabic, which may be used alone or in combination.

The solvent used for coating the oxygen barrier protective layer of the present invention is preferably pure water, but alcohols such as methanol and ethanol, and ketones such as acetone and methyl ethyl ketone may be mixed with pure water. . The concentration of the solid content in the coating solution is suitably from 1 to 20% by weight. Known additives such as a surfactant for improving coating properties and a water-soluble plasticizer for improving physical properties of the film may be added to the oxygen-barrier protective layer of the present invention. Examples of the water-soluble plasticizer include propionamide, cyclohexanediol, glycerin, and sorbitol. Further, a water-soluble (meth) acrylic polymer or the like may be added. The coating amount of the oxygen-barrier protective layer is suitably in the range of about 0.1 / m ² to about 15 / m ² by weight after drying. More preferably, it is 1.0 / m ² to about 5.0 / m ² .

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.

The photosensitive compound which releases an acid upon exposure includes, for example, o-naphthoquinonediazide-4-sulfonic acid halogenide described in JP-A-50-36,209; No. 223, trihalomethyl-2-pyrone and trihalomethyl-s-triazine; various o-naphthoquinonediazide compounds described in JP-A-55-62,444; 77, 742, 2-trihalomethyl-5-aryl-1,3,4-oxadiazole compounds; diazonium salts and the like. These compounds can be used alone or as a mixture, and the amount added is based on the total weight of the composition.
A range from 0.3 to 15% by weight is preferred.

In the photosensitive composition according to the present invention, at least one or more organic dyes that change the color tone by interacting with the photolysis product of a compound that 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 [Orient Chemical Industry Co., Ltd.], Oil Red 5B [Orient Chemical Industry Co., Ltd.], Oil Scarlet # 308 [Orient Chemical Industry Co., Ltd.], Oil Red OG [Orient Chemical Co., Ltd.] Industrial Co., Ltd.), Oil Red RR (Orient Chemical Co., Ltd.), Oil Green # 502 (Orient Chemical Co., Ltd.), Spiron Red BEH Special (Hodogaya Chemical Co., Ltd.), Victoria Pure Blue BOH (made by Hodogaya Chemical Industry Co., Ltd.),

Patent Pure-Blue (manufactured by Sumitomo Sangoku Chemical 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-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2 -Carbostearylamino-4-p-dihydroxyethyl-amino-phenyliminonaphthoquinone, p-methoxybenzoyl-p'-diethylamino-
o'-methylphenyliminoacetanilide, cyano-
p-diethylaminophenyliminoacetanilide, 1
-Phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, 1-β-naphthyl-4-
p-diethylaminophenylimino-5-pyrazolone and the like.

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

Others 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.

In the photosensitive composition of the present invention, Japanese Patent Application Laid-Open No.
Non-ionic surfactants described in JP-A-251740 and JP-A-4-68355;
An amphoteric surfactant as described in JP-A-9-121044 and JP-A-4-13149 can be added. Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, monoglyceride stearate, polyoxyethylene sorbitan monooleate, polyoxyethylene nonyl phenyl ether, and the like. Specific examples of the activator include alkyl di (aminoethyl) glycine, alkyl polyaminoethyl glycine hydrochloride, Amogen K (trade name, manufactured by Dai-ichi 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.

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

In the photosensitive composition according to the present invention, a yellow dye, preferably having an absorbance at 417 nm and an absorbance at 436 nm, is used.
More than 70% of yellow dyes can be added. The present invention relates to a positive type using the above quinonediazide or a compound having an alkali-soluble group protected by an acid-decomposable group.
In addition to PS plates and negative PS plates using a photopolymerization system, the following types of lithographic printing plate materials can be similarly used. (1) Negative lithographic printing plate material using diazo resin (2) Negative lithographic printing plate material using photocrosslinkable resin (3) Alkali-soluble binder, acid generator, acid (heat) crosslinkable compound Negative-type laser direct-drawing lithographic printing material including (4) an alkali-soluble binder, a positive-type laser further containing a substance that is thermally decomposable and substantially reduces the solubility of the alkali-soluble binder when not decomposed. Direct-drawing lithographic printing materials

Hereinafter, the materials used in each example will be described in detail. As the diazo resin used in (1), for example, there is a diazo resin represented by a salt of a condensate of a diazodiarylamine and an active carbonyl compound, and a photosensitive, water-insoluble and organic solvent-soluble resin is preferable. Particularly preferred diazo resins include, for example, 4-diazodiphenylamine, 4-diazo-3-methyldiphenylamine, 4-diazo-4'-
Methyldiphenylamine, 4-diazo-3'-methyldiphenylamine, 4-diazo-4'-methoxydiphenylamine, 4-diazo-3-methyl-4'-ethoxydiphenylamine, 4-diazo-3-methoxydiphenylamine and the like and formaldehyde, para Formaldehyde,
An organic acid salt or an inorganic acid salt of a condensate with acetaldehyde, benzaldehyde, 4,4'-bis-methoxymethyldiphenyl ether or the like.

Examples of the organic acid at this time include methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid,
Xylenesulfonic acid, mesitylenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, propylnaphthalenesulfonic acid, 1-naphthol-5-sulfonic acid, 2-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 2-hydroxy-4-methoxy Benzophenone-5-sulfonic acid and the like are mentioned, and inorganic acids include hexafluorophosphoric acid, tetrafluoroboric acid, thiocyanic acid and the like. Further, JP-A-54-30,
No. 121, a diazo resin whose main chain is a polyester group; a reaction between a polymer having a carboxylic anhydride residue described in JP-A-61-273538 and a diazo compound having a hydroxyl group. A diazo resin obtained by reacting a polyisocyanate compound with a diazo compound having a hydroxyl group can also be used.

The use amount of these diazo resins is preferably in the range of 0 to 40% by weight based on the solid content of the composition, and if necessary, two or more diazo resins may be used in combination. In preparing the negative photosensitive composition, an organic polymer binder is usually used in combination. As such an organic polymer binder, for example, acrylic resin, polyamide resin,
Examples include polyester resin, epoxy resin, polyacetal resin, polystyrene resin, and novolak resin. Furthermore, in order to improve performance, known additives, for example,
Thermal polymerization inhibitors, dyes, pigments, plasticizers, stability improvers and the like can be added.

Suitable dyes include, for example, crystal violet, maracay green, Victoria blue,
Basic oil-soluble dyes such as methylene blue, ethyl violet, and rhodamine B are included. Examples of commercially available products include “Victoria Pure Blue BOH” (manufactured by Hodogaya Chemical Industry Co., Ltd.) and “Oil Blue # 603”.
(Manufactured by Orient Chemical Industry Co., Ltd.). Examples of the pigment include phthalocyanine blue, phthalocyanine green, dioxazine violet, quinacridone red, and the like.

Examples of the plasticizer include diethyl phthalate, dibutyl phthalate, dioctyl phthalate, tributyl phosphate, trioctyl phosphate, tricresyl phosphate, tri (2-chloroethyl) phosphate, tributyl citrate and the like. Further, as known stability improvers, for example, phosphoric acid, phosphorous acid, oxalic acid, tartaric acid, malic acid, citric acid, dipicolinic acid, polyacrylic acid, benzenesulfonic acid, toluenesulfonic acid and the like can be used in combination. The amount of these various additives varies depending on the purpose, but generally, the amount of the solid content of the photosensitive composition is 0 to 0.
A range of 30% by weight is preferred.

As the photocrosslinkable resin used in (2), a photocrosslinkable resin having an affinity for an aqueous alkaline developer is preferable. For example, a cinnamic acid group described in JP-B-54-15711 can be used. Copolymer having a carboxyl group; phenylenediacrylic acid residue described in JP-A-60-165646 and polyester resin having a carboxyl group; phenylenediacrylic acid residue described in JP-A-60-203630 Polyester resin having a phenolic hydroxyl group; polyester resin having a phenylenediacrylic acid residue and a sodium iminodisulfonyl group described in JP-B-57-42858;
Polymers having an azide group and a carboxyl group in the side chain described in JP-A-7-295212, and polymers having a maleimide group in the side chain described in JP-A-7-295212 can be used.

An alkali-soluble binder used in (3),
As the acid generator, the same materials as those described above for the positive PS plate using quinonediazide or a compound having an alkali-soluble group protected by an acid-decomposable group can be used. The acid (thermal) crosslinkable compound refers to a compound that crosslinks in the presence of an acid, and includes, for example, aromatic compounds and heterocyclic compounds that are polysubstituted with a hydroxymethyl group, an acetoxymethyl group, or an alkoxymethyl group. Among them, preferred examples include compounds obtained by condensing phenols and aldehydes under basic conditions. Preferred among the above compounds are, for example, compounds obtained by condensing phenol and formaldehyde under basic conditions as described above, similarly, compounds obtained from m-cresol and formaldehyde, and compounds obtained from bisphenol A and formaldehyde. Compound,
Compounds obtained from 4,4'-bisphenol and formaldehyde, and other compounds disclosed as resol resins in GB 2,082,339 are exemplified.

These acid-crosslinkable compounds have a weight average molecular weight of 500 to 100,000 and a number average molecular weight of 200 to 100.
50,000 are preferred. Other preferred examples include aromatic compounds substituted with an alkoxymethyl or oxiranylmethyl group disclosed in EP-A-0,212,482, EP-A-0,133,216, and D-A.
EA 3,634,671, DE 3,711,2
Monomer and oligomer melamine-formaldehyde condensate and urea-formaldehyde condensate disclosed in No. 64, and alkoxy-substituted compounds disclosed in EP-A-0,212,482. Still other preferred examples are, for example, melamine-formaldehyde derivatives having at least two free N-hydroxymethyl, N-alkoxymethyl or N-acyloxymethyl groups.
Of these, N-alkoxymethyl derivatives are particularly preferred.

Also, low molecular weight or oligomeric silanols can be used as silicon-containing crosslinkers. Examples of these are dimethyl- and diphenyl-silanediols and oligomers which have already been precondensed and contain these units, for example those disclosed in EP-A 0,377,155. Among aromatic compounds and heterocyclic compounds poly-substituted with an alkoxymethyl group, compounds having an alkoxymethyl group at a position adjacent to the hydroxyl group, and the alkoxy group of the alkoxymethyl group having 18 or less carbon atoms are preferable. Specific examples include the following general formulas (3) to (3).
The compound of (6) can be mentioned.

[0116]

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[0117]

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In the formula, L _{1 to} L ₈ may be the same or different and represent an alkoxymethyl group substituted with an alkoxy group having 18 or less carbon atoms, such as methoxymethyl, ethoxymethyl and the like. These are preferred because they have high crosslinking efficiency and can improve printing durability. The above compounds that are crosslinked by heat may be used alone,
Two or more types may be used in combination. The acid-crosslinkable compound used in the present invention is used in an amount of 5 to 80% by weight, preferably 10 to 75% by weight, particularly preferably 20 to 70% by weight, based on the total solid content of the lithographic printing plate material. .
If the amount of the acid-crosslinkable compound is less than 5% by weight, the durability of the photosensitive layer of the lithographic printing plate material obtained is deteriorated.
Exceeding 0% by weight is not preferred in terms of stability during storage.

As the alkali-soluble binder used in (4), the same materials as those used in the positive PS plate using quinonediazide described above can be used. As a substance that is thermally decomposable and does not decompose substantially, it substantially reduces the solubility of the alkali-soluble binder, and various onium salts, quinonediazide compounds, etc. are excellent in lowering the solubility of the alkali-soluble binder. And is preferably used. Examples of the onium salts include diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, arsonium salts, and the like.

Suitable onium salts used in the present invention include, for example, S. I. Schle
singer, Photogr. Sci. Eng. , 1
8, 387 (1974); S. Bal et a
l. , Polymer, 21, 423 (1980); JP-A-5-158230; diazonium salts described in U.S. Pat.
No. 056, JP-A-3-140140, etc .; C. Necker et al. , Ma
cromolecules, 17, 2468 (198
4), C.I. S. Wen et al. , Teh, Pr
oc. Conf. Rad. Curing ASIA, p
478, Tokyo, Oct (1988), U.S. Patent Nos. 4,069,055 and 4,069,056, and the like. V. Crivello et
al. , Macromolecules, 10
(6), 1307 (1977), Chem. & En
g. News, Nov .; 28, p31 (1988), EP 104,143, US Patent 339,049.
No. 410,201, JP-A-2-150848, JP-A-Hei.
Iodonium salts described in 2-296514, JVCrivello e
t al., Polymer J. 17, 73 (1985), JVCrivello et a
l., J. Org.Chem., 43, 3055 (1978), WRWatt et al.,
J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (198
4), JVCrivello et al., Polymer Bull., 14,279 (198
5), JVCrivello et al., Macromolecules, 14 (5), 11
41 (1981), JVCrivello et al., J. Polymer Sci., Pol
ymer Chem.Ed., 17,2877 (1979), EP 370,693
No. 3,902,114; European Patent No. 233,567;
Nos. 297,443 and 297,442; U.S. Patent No. 4,933,377
Nos. 410,201, 339,049, 4,760,013,
4,734,444, 2,833,827, German Patent 2,904,626
Nos. 3,604,580 and 3,604,581, JVCrivello et al., Macromolecules, 10
(6), 1307 (1977), JVCrivello et al., J. Polymer Sc
i., Polymer Chem. Ed., 17, 1047 (1979) and the like, CSWen et al., Teh, Proc. Conf. Ra.
d. Curing ASIA, p478, Tokyo, Oct (1988) and the like.

In the present invention, among these, diazonium salts are particularly preferred. Particularly preferred diazonium salts include those described in JP-A-5-158230. Suitable quinonediazide compounds include o-quinonediazide compounds.

The o-quinonediazide compound used in the present invention is a compound having at least one o-quinonediazide group, which increases alkali solubility by thermal decomposition, and can be a compound having various structures. In other words, o-quinonediazide helps the solubility of the light-sensitive material system by both the effect of losing the ability to suppress the dissolution of the alkali-soluble binder due to thermal decomposition and the effect of converting o-quinonediazide itself into an alkali-soluble substance. Examples of the o-quinonediazide compound used in the present invention include, for example, J
. Writer "Light-Sensitive Systems"
(John Wiley & Sons. Inc.) The compounds described on pages 339 to 352 can be used, but in particular sulfonic esters or sulfonic acids of o-quinonediazide reacted with various aromatic polyhydroxy compounds or aromatic amino compounds. Amides are preferred. In addition, Japanese Patent Publication No. 43-2840
No. 3 benzoquinone- (1,1)
2) Esters of -diazidosulfonic acid chloride or naphthoquinone- (1,2) -diazide-5-sulfonic acid chloride with pyrogallol-acetone resin, benzoquinone described in U.S. Pat. Nos. 3,046,120 and 3,188,210 -(1,2) -diazidosulfonic acid chloride or naphthoquinone- (1,2) -diazide-
Esters of 5-sulfonic acid chloride with phenol-formaldehyde resin are also suitably used.

Further, esters of naphthoquinone- (1,2) -diazide-4-sulfonic acid chloride with phenol-formaldehyde resin or cresol-formaldehyde resin, naphthoquinone- (1,2) -diazide-4-sulfonic acid chloride and pyrogallol Esters with acetone resins are likewise preferably used. Other useful o-quinonediazide compounds are reported and known in numerous patent-related documents. For example, JP 47-5303, JP 48-63802, JP 48-63803,
JP-A-48-96575, JP-A-49-38701, JP-A-48-13354
No., JP-B-41-11222, JP-B-45-9610, JP-B-49-1
No. 7481, U.S. Pat.Nos. 2,797,213 and 3,454,400,
No. 3,554,323, No. 3,573,917, No. 3,674,495
No. 3,785,825; British Patent No. 1,277,602;
Nos. 1,251,345, 1,267,005, 1,329,888,
Documents such as 1,330,932 and German Patent No. 854,890
(Specification).

The amount of the o-quinonediazide compound used in the present invention is preferably from 1 to 50% by weight, more preferably from 5 to 30% by weight, particularly preferably from 10 to 50% by weight, based on the total solids of the lithographic printing plate material. -30% by weight.
These compounds can be used alone or as a mixture of several types. If the amount of the o-quinonediazide compound is less than 1% by weight, the recording properties of the image will be deteriorated, while if it exceeds 50% by weight, the durability of the image portion will be deteriorated and the sensitivity will be lowered.

The counter ions of the onium salt include tetrafluoroboric acid, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, 5-nitro-o-toluenesulfonic acid,
-Sulfosalicylic acid, 2,5-dimethylbenzenesulfonic acid, 2,4,6-trimethylbenzenesulfonic acid, 2
-Nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-fluorocaprylnaphthalenesulfonic acid, dodecylbenzenesulfonic acid, 1-naphthol-5-sulfonic acid, 2-methoxy-4-hydroxy-5- Benzoyl-benzenesulfonic acid, paratoluenesulfonic acid and the like can be mentioned. Among them, alkyl aromatic sulfonic acids such as hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid and 2,5-dimethylbenzenesulfonic acid are particularly preferable. The amount of the above compound other than the o-quinonediazide compound is preferably 1 to 50% by weight, more preferably 5 to 30% by weight, particularly preferably 10 to 30% by weight, based on the total solid content of the lithographic printing plate material. Range.

When a lithographic printing plate photosensitive material is obtained from the photosensitive composition containing a fluorine-containing surfactant of the present invention, it is first provided on a suitable support. The photosensitive composition containing the fluorinated surfactant of the present invention is dissolved or dispersed in the following organic solvents alone or as a mixture, applied to a support, and dried. As the organic solvent, any known organic solvents can be used.
C, in particular in the range from 60 C to 160 C, are selected for their advantages in drying. Of course, it is better to select one in which the surfactant of the present invention dissolves.

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

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

The drying of the photosensitive composition applied on the support is usually performed with heated air. Heating is 30
C. to 200.degree. C., particularly preferably 40 to 140.degree. In addition to a method in which the drying temperature is kept constant during the drying, a method in which the temperature is gradually increased may be performed. Good results may be obtained by dehumidifying the drying air. The heated air is applied at 0.1 m / sec to 30 m /
It is preferable to supply at a rate of second, especially 0.5 m / sec to 20 m / sec.

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

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

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

Further, silicate electrodeposition as described in US Pat. No. 3,658,662 is also 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 aluminum plate thus grained is washed with water and chemically etched as required.

The etching solution is usually selected from aqueous solutions of bases or acids 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. When the concentration of the etchant and the temperature of the etchant are set, the dissolution rate of the aluminum or alloy to be used is determined by the immersion time.
Most preferably, it is carried out at a rate of from 0.3 g to 40 g / m ² per minute, but it may be higher or lower.

The etching is performed by immersing the aluminum plate in the above-mentioned etching solution, or by applying an 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, borofluoric acid and the like are used. The etched aluminum plate is optionally washed with water and anodized. The anodic oxidation can be performed by a method conventionally used in this field. Specifically, when direct current or alternating current is passed through aluminum in an aqueous solution or a non-aqueous solution of sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, or a combination of two or more thereof, aluminum An anodized film can be formed on the surface of the support.

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

Organic undercoat layer: It is preferable to provide an organic undercoat layer before coating the photosensitive layer on the photosensitive lithographic printing plate of the present invention in order to reduce the remaining photosensitive layer in the non-image area. Examples of the organic compound used in the organic undercoat layer include carboxymethyl cellulose, dextrin, gum arabic,
-Phosphonic acids having an amino group such as -aminoethylphosphonic acid, phenylphosphonic acid which may have a substituent,
Organic phosphonic acids such as naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid; phenylphosphoric acid which may have a substituent; naphthylphosphoric acid; Organic phosphoric acid, optionally substituted phenylphosphinic acid, naphthylphosphinic acid, organic phosphinic acid such as alkylphosphinic acid and glycerophosphinic acid, amino acids such as glycine and β-alanine, and hydrochloride of triethanolamine And the like, but may be used in combination of two or more.

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

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In the general formula [IV], R₁Is hydrogen field
Represents a hydrogen atom, a halogen atom or an alkyl group, but is preferably
Is a hydrogen atom, a chlorine atom, or an alkyl having 1 to 4 carbon atoms.
Represents a kill group. Particularly preferably, a hydrogen atom or a methyl group
Represents R_TwoAnd R_ThreeAre each independently a hydrogen atom, a hydroxyl group,
Halogen atom, alkyl group, substituted alkyl group, aromatic
Group, substituted aromatic group, -OR_Four, -COOR_Five, -CONH
R ₆, -COR₇Or -CN, or R_TwoWhen
R_ThreeMay combine to form a ring. Where R_Four~ R₇Is
Each represents an alkyl group or an aromatic group. More preferred R
_TwoAnd R_ThreeAre each independently a hydrogen atom, a hydroxyl group, a chlorine atom
, A C1-C4 alkyl group, a phenyl group, -OR
_Four, -COOR_Five, -CONHR₆, -COR₇, -CN
Yes, where R_Four~ R₇Is an alkyl group having 1 to 4 carbon atoms.
Or a phenyl group. Particularly preferred R_TwoAnd R_ThreeAre each
Independently, hydrogen, hydroxyl, methyl or methoxy
Group.

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

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 coated on an aluminum plate and dried, and a method in which water or methanol, ethanol, methyl ethyl ketone, or the like is used. An aluminum plate is immersed in a solution in which the above organic compound is dissolved in an organic solvent or a mixed solvent thereof to adsorb the organic compound, and thereafter, washed with water or the like and dried to form an organic undercoat layer. Is the way. In the former method, a solution of the above organic compound having a concentration of 0.005 to 10% by weight can be applied by various methods. For example, any method such as bar coater coating, spin coating, spray coating, and curtain coating may be used. In the latter method, the concentration of the solution is 0.01 to 20% by weight, preferably 0.05 to 20% by weight.
-5% by weight, the immersion temperature is 20-90 ° C., preferably 25-50 ° C., and the immersion time is 0.1 second-20 minutes,
Preferably it is 2 seconds to 1 minute.

The pH of the solution used is adjusted by 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)
Can be added. Formula (1) (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 2 mg / m ² , sufficient printing durability cannot be obtained. The same is true even if it is larger than 100 mg / m ² .

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

The planographic printing plate prepared as described above is usually subjected to image exposure and development processing. As the light source of the actinic ray used for image exposure, for example, a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp,
There are carbon arc lamps and the like. As radiation, electron beam,
X-rays, ion beams, far infrared rays, and the like. G line,
i-line, Deep-UV light, and high-density energy beam (laser beam) are also used. Laser beams include helium / neon laser, argon laser, krypton laser, helium / cadmium laser, KrF
Excimer laser and the like can be mentioned. In the laser direct-writing printing plate, a light source having an emission wavelength in the near infrared to infrared region is preferable, and a solid-state laser and a semiconductor laser are particularly preferable.

Preferred as a developer for a lithographic printing plate using the photosensitive composition of the present invention are those containing (a) at least one saccharide selected from non-reducing sugars and (b) at least one base and having a pH of at least one. The developer is in the range of 9.0 to 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.

It is preferable that the main components of this developer are at least one compound selected from non-reducing sugars and at least one base, and the pH of the solution is 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 reducing property, trehalose-type oligosaccharides in which reducing groups are bonded to each other, glycosides in which a reducing group of a saccharide is bonded to a non-saccharide. 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 developer 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 alkali 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), sulfosalicylic 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).

Of 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,
Nonionic surfactants such as N, 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.

Further 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 and 4-methylcyclohexanol, N-phenylethanolamine, N-phenyldiethanolamine and the like can be mentioned. 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 when the amount of the surfactant is small and the amount of the organic solvent is large, the organic solvent is not completely dissolved, and therefore, it is impossible to expect good developing property.

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.

The developing solution may further contain an organic carboxylic acid. 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 aliphatic and aromatic carboxylic acids are preferably used as a sodium salt, a potassium salt or an ammonium salt in order to increase the 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 its chelation, 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 a developer for a lithographic printing plate using the photosensitive composition of the present invention, a developer described in JP-A-6-282079 can also be used. This is SiO ₂ / M ₂ O
(M represents an alkali metal) molar ratio of 0.5 to 2.0
And a water-soluble ethylene oxide adduct obtained by adding 5 mol or more of ethylene oxide to a sugar alcohol having 4 or more hydroxyl groups. 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
L-sorbit, D, L-mannit, D, L-idit, D, L-talit, dursit, allozulcit, and the like, and also di-, tri-, tetra-, penta-, and hexaglycerin obtained by condensing 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 suitably from 0.001 to 5% by weight, more preferably from 0.001 to 2% by weight, based on the developer (working solution).

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

PS developed with a 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 as a main component, 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 template 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, the operating time, and the like. Further, a so-called disposable processing method in which processing is performed with a substantially unused processing liquid can also be applied. The lithographic printing plate obtained by such a process is set on an offset printing machine and used for printing a large number of sheets.

[0172]

The present invention will be further described below with reference to examples. However, the present invention is not limited by these examples. Synthesis Examples 1 to 5 The components having the groups (a), (b), and (c) were polymerized by a known method to synthesize the polymers shown in Table 1. Further, the compound (polymer) of Comparative Example was synthesized in the same manner.

[0173]

[Table 1]

[Examples 1 to 4, Comparative Examples 1 and 2] All percentages in this example are% by weight unless otherwise specified. The surface of a JIS A1050 aluminum plate having a thickness of 0.24 mm was grained using a nylon brush and an aqueous suspension of 400 mesh pumistone, and then thoroughly washed with water. After immersing in 10% sodium hydroxide at 70 ° C. for 60 seconds for etching, washing with running water and then 20% HN
Washed with O ₃ for neutralization and water. This was subjected to electrolytic surface roughening treatment in a 1% nitric acid aqueous solution at an anode electricity of 160 coulomb / dm ² using a sinusoidal alternating waveform current under the condition of V _A = 12.7 V. When the surface roughness was measured,
m (indicated by _Ra ). Subsequently, the plate 30% H ₂ SO
_{4 After} immersing in an aqueous solution and desmutting at 55 ° C for 2 minutes,
Anodizing was performed in a 20% H ₂ SO ₄ aqueous solution so that the current density was 14 A / dm ² , and the amount of the anodic oxide film was equivalent to 2.5 g / m ^2. The substrate was prepared by treating at 20 ° C. for 20 seconds and washing with water.

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 solution (I) Compound of the following structural formula (A) 0.42 g Compound of the following structural formula (B) 0.013 g Methanol 100 g Pure water 1 g

[0176]

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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 . In order to further shorten the vacuum adhesion time, a mat layer was formed as described in JP-B-61-28986.

[0178]

[Table 2]

The photosensitive lithographic printing plate thus prepared was evaluated by the following method. Sensitivity is a step wedge manufactured by Fuji Photo Film Co., Ltd. (the density difference between each step is 0.15)
Through a 3 kW metal halide lamp from a distance of 1 m for 1 minute, and then using a PS processor 900U manufactured by Fuji Photo Film Co., Ltd. at 30 ° C.
For 12 seconds, the molar ratio of SiO ₂ / K ₂ O is 1.16,
The film was developed with an aqueous solution having an O ₂ concentration of 1.4%, and expressed by the number of clear stages. The higher the number of stages, the higher the sensitivity.
The gradation represents the difference between the number of clear steps and the number of solid steps of the sample for which the sensitivity was evaluated. A lower value indicates a higher contrast. The development tolerance is based on the developer described above.
Exposure and development were performed in the same manner as in the above sensitivity except that a liquid whose pH was increased or decreased by 0.2 was used to show the change in the number of solid plates due to the pH. The smaller this value is, the better the development tolerance is. Table 4 shows the results.

[0180]

[Table 3]

[0181]

[Table 4]

As can be seen from Table 4, Examples 1 to 4
Has a high contrast without deteriorating the sensitivity, and has good development tolerance.

[Examples 5 to 9, Comparative Example 3] Thickness 0.30
An 1 mm aluminum plate of 1 mm was grained using a No. 8 nylon brush and an 800 mesh aqueous suspension of pumicestone, and the surface was grained, and then thoroughly washed with water. After being immersed in 10% sodium hydroxide at 70 ° C. for 60 seconds for etching, washed with running water, washed neutralized with 20% HNO ₃ and washed with water. This was converted to 300 coulombs / d in a 1% aqueous nitric acid solution using a sinusoidal alternating current under the condition of _VA = 12.7V.
Electrolytic surface-roughening treatment was performed with an anode electricity amount of m ² . When the surface roughness was measured, it was 0.45 μm (Ra display). Subsequently, it was immersed in a 30% aqueous solution of H ₂ SO _{4 and} desmutted at 55 ° C. for 2 minutes.
In a H ₂ SO ₄ aqueous solution, a cathode was arranged on the grained surface, and anodized at a current density of 5 A / dm ² for 50 seconds to obtain a thickness of 2.7 g / m ² .

Furthermore, No. 3 sodium silicate (SiO ₂ = 28 to
(2.5% by weight of 30%, Na ₂ O = 9 to 10%, Fe = 0.02% or less), pH = 11.2, 70 ° C. for 13 seconds, and then washed with water. The silicate amount at that time was 10 mg / m ² . For measurement, the amount of Si element was determined by fluorescent X-ray analysis. Next, a liquid composition (sol solution) of the SG method was prepared by the following procedure. The following composition was weighed into a beaker and stirred at 25 ° C. for 20 minutes. Si (OC ₂ H ₅ ) ₄ 38 g 3-methacryloxypropyltrimethoxysilane 13 g 85% phosphoric acid aqueous solution 12 g Deionized water 15 g Methanol 100 g

The solution was transferred to a three-necked flask, fitted with a reflux condenser, and immersed in the oil bath at room temperature. The contents of the three-necked flask were heated to 50 ° C. in 30 minutes while stirring with a magnetic stirrer. While maintaining the bath temperature at 50 ° C, the reaction was further performed for 1 hour to obtain a liquid composition (sol liquid). This sol solution was diluted with methanol / ethylene glycol = 20/1 (weight ratio) so as to be 0.5% by weight, applied with a wheeler to a substrate, and dried at 100 ° C. for 1 minute. The coating amount at that time was 4 mg / m ² . The amount of this coating was also determined by fluorescent X-ray analysis to determine the amount of Si element.
It was taken as the coating amount. A high-sensitivity photopolymerizable composition 1 having the following composition was applied on the aluminum plate treated in this manner so that the dry coating weight was 1.5 g / m ^2, and 100 ° C.
For 1 minute to form a photosensitive layer.

[Photopolymerizable Composition 1] Tetramethylolmethanetetraacrylate 1.5 g Linear organic high molecular polymer (B1) 2.0 g Allyl methacrylate / methacrylic acid copolymer (copolymerization molar ratio 80/20) ) Sensitizer (C1) 0.15 g

[0187]

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(Λ _max THF 479 nm, ε = 6.9 × 10 ⁴ ) 0.2 g of photopolymerization initiator (D1)

[0189]

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IRGACURE907 (E1) (manufactured by Ciba-Geigy) 0.4 g Fluoropolymer (P) shown in Table 5 0.2 g ε-phthalocyanine / (B1) dispersion 0.2 g Fluorine-nonionic interface Activator Megafax F177 0.03 g (manufactured by Dainippon Ink and Chemicals, Inc.) Methyl ethyl ketone 9.0 g Propylene glycol monomethyl ether acetate 7.5 g Toluene 11.0 g

On this photosensitive layer, polyvinyl alcohol (98 mol% saponification, polymerization degree 5
00) of a 3% by weight aqueous solution having a dry coating weight of 2.5 g /
m ² and dried at 120 ° C. for 3 minutes to obtain a photopolymerizable lithographic printing plate. These plates were purchased from Optronics XLP4000 (Ar laser 75mW, 488n).
m) at 4,000 dpi at 0.15 mJ / cm ²
Under the condition of 75 lines / inch, 1% to 99% was exposed in two portions at 1% intervals. Thereafter, a post-heating treatment was performed by exposing to 120 ° C. for 20 seconds.

The development was carried out by dipping in the following developer at 25 ° C. for 30 seconds. (Developer) 1K potassium silicate 30g potassium hydroxide 15g water 1000g

Next, GU-7 (Fuji Photo Film Co., Ltd.)
) Was diluted twice with water to treat the plate surface. 400
Under the conditions of 0 dpi and 175 lines / inch, the plate energy amount reproduced by 1% was obtained as the sensitivity of the sample.
For printing durability measurement, Heidelberg SOR was used as a printing machine.
KZ was used, and Claf G (N) manufactured by Dai Nippon Ink was used as the ink. As a plate cleaner,
An acidic PS plate cleaner CL-2 (manufactured by Fuji Photo Film Co., Ltd.) was used.

Each sample was stored at 60 ° C. for 3 days, exposed and developed in the same manner and printed, and the stain resistance of the non-image area was visually evaluated to evaluate the stability over time. 5000th sheet from printing start
The S plate cleaner CL-2 was impregnated into a printing sponge, and a halftone dot portion was wiped off to wash the ink on the plate surface. After that, PS is repeated for every 10,000 sheets up to the 145,000th sheet.
Wash the ink on the plate surface with the plate cleaner CL-2,
150,000 sheets were printed. Table 5 shows the results obtained by extracting printed matter every 10,000 sheets and evaluating halftone dots obtained by washing the plate surface with PS plate cleaner CL-2 and halftone dots not washed.

The solid printing durability refers to the number of sheets that can be printed normally without any solid printing on the printed portion, and the highlight printing durability indicates that 2% of 175 lines / inch is printed on printed matter. Indicates the number of prints to be reproduced. The gradation represents the difference between the number of clear steps and the number of solid steps of the sample for which the sensitivity was evaluated. A lower value indicates a higher contrast.

[0196]

[Table 5]

From the above results, in the photosensitive lithographic printing plate of the present invention, by using the unique fluoropolymer of the present invention in the photosensitive composition, the printing plate can be maintained while maintaining the printing durability of the printing plate. Could be hardened.

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

[0199]

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

[0201]

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

[Embodiments 10 to 13] The thickness of 0.30 mm
Trichlorethylene for aluminum plate (material 1050)
After washing and degreasing, nylon brush and 400 mesh
Graining the surface with a pumicestone-water suspension of
Washed well with water. This plate is 25% sodium hydroxide at 45 ° C
Immerse in an aqueous solution of lithium for 9 seconds to etch and rinse
Later, another 2% HNO _ThreeFor 20 seconds and washed with water.
At this time, the etching amount of the grained surface is about 3 g / m.^Twoso
there were. Next, this plate is_TwoSO_FourAs an electrolyte
Flow density 15A / dm^Two3g / m^TwoDC anodized film
And then washed with water and dried. Next on this aluminum plate
The following undercoat liquid was applied and dried at 80 ° C. for 30 seconds. Dry
10 mg / m coating amount after drying^TwoMet.

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

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

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

Table 6 shows the fluorinated copolymers and crosslinking agents used in Solutions [G-1] to [G-4]. Further, an acid generator [SH-1] and an infrared absorber [IK-
The structure of 1) is shown below.

[0208]

[Table 6]

[0209]

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The obtained negative type lithographic printing plate material [G-1]
To [G-4] with a bare hand, and then the wavelength of 820
Scanning exposure was performed using a semiconductor laser that emits infrared light of about 850 nm. After exposure, 3 hours at 110 ° C with panel heater
After heat treatment for 0 second, development was carried out with a developing solution DP-4 (1: 8 water dilution) manufactured by Fuji Photo Film Co., Ltd. After the image formation, it was visually determined whether or not the image of the portion touched with bare hands was missing.
In [1] to [G-4], clear image omission did not occur.

Comparative Example 4 Example 1 was repeated except that the polymer compound [R-1] was used in place of the fluorinated copolymer in the solution [G] used in Example 10.
A solution was prepared in the same manner as in Example 1. This solution was applied to the primed aluminum plate used in Example 10 and
After drying at 00 ° C for 1 minute, a negative type lithographic printing plate [Q-
1] was obtained. The weight after drying was 1.5 g / m ² .
An image was formed on the obtained lithographic printing plate material [Q-1] by the same operation as in Example 10. After image formation, it was visually determined whether the image of the part touched with bare hands was missing,
In the negative type lithographic printing plate material [Q-1], clear image omission occurred.

Comparative Example 5 The procedure of Example 1 was repeated except that the polymer compound [R-2] was used in place of the fluorinated copolymer in the solution [G] used in Example 10.
A solution was prepared in the same manner as in Example 1. This solution was applied to the primed aluminum plate used in Example 10 and
After drying at 00 ° C for 1 minute, a negative type lithographic printing plate [Q-
2] was obtained. The weight after drying was 1.5 g / m ² .
An image was formed on the obtained lithographic printing plate material [Q-2] by the same operation as in Example 10. After image formation, it was visually determined whether the image of the part touched with bare hands was missing,
In the negative type lithographic printing plate material [Q-2], clear image omission occurred.

[Preparation of Copolymer 1] A 20 ml three-necked flask equipped with a stirrer, a condenser and a dropping funnel was charged with N-
4.61 g (0.0192 mol) of (p-aminosulfonylphenyl) methacrylamide, 2.94 g (0.0258 mol) of ethyl methacrylate, 0.80 g (0.015 mol) of acrylonitrile and 20 g of N, N-dimethylacetamide , And the mixture was stirred while being heated to 65 ° C. by a hot water bath. "V-65"
0.15 g (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred for 2 hours under a nitrogen stream while maintaining the temperature at 65 ° C. To this reaction mixture, 4.61 g of N- (p-aminosulfonylphenyl) methacrylamide and 2.94 of ethyl methacrylate were further added.
g, 0.80 g of acrylonitrile, N, N-dimethylacetamide and 0.15 g of "V-65" were added dropwise over 2 hours using a dropping funnel. After the addition was completed, the resulting mixture was further stirred at 65 ° C. for 2 hours. After the completion of the reaction, 40 g of methanol was added to the mixture, and the mixture was cooled.
After stirring the mixture for 0 minutes, the precipitate was taken out by filtration and dried to obtain 15 g of a white solid. The weight average molecular weight (polystyrene standard) of this specific copolymer 1 measured by gel permeation chromatography was 53,000.

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

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

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

Undercoat liquid 0.3 g of the following compound 100 g of methanol 1 g of water

[0218]

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Example 14 The following photosensitive solution 1 was prepared. The obtained substrate was coated with 1.8 g of this photosensitive solution 1 in an amount of 1.8 g.
/ M ² to obtain a lithographic printing plate.

Photosensitive solution 1 Fluorine-containing polymer P-8 0.03 g The above copolymer 1 0.75 g m, p-cresol novolak (m, p ratio = 6/4, 0.25 g, weight average molecular weight 3,500, unreacted cresol 0.5% by weight) p-toluenesulfonic acid 0.003 g tetrahydrophthalic anhydride 0.03 g cyanine dye (the following structure) 0.017 g counter ion of Victoria Pure Blue BOH 0.015 g 1-naphthalenesulfonic acid anion Dye Megafac F-177 0.05 g (manufactured by Dainippon Ink and Chemicals, Inc., fluorine-based surfactant) γ-butyl lactone 10 g methyl ethyl ketone 10 g 1-methoxy-2-propanol 1 g

[0221]

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The obtained lithographic printing plate was evaluated for development stability against damage. Table 7 shows the evaluation results.

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

[0224]

[Table 7]

[Examples 15 and 16, Comparative Examples 6 and 7] Except that the fluorine-containing polymer P-10, P-12, R-1, and R-2 were used instead of the fluorine-containing polymer P-8, respectively. A lithographic printing plate was obtained in the same manner as in Example 14. The resulting lithographic printing plate was evaluated for development stability against damage in the same manner as in Example 14. Table 7 shows the evaluation results. From Table 7, it can be seen that the stability against trauma in the state before development is significantly improved by the addition of the specific fluorine-containing polymer.

[0226]

The photosensitive composition of the present invention, by containing a specific fluorine-containing polymer, exhibits a high contrast image forming property without lowering its sensitivity, and exhibits a burn-out,
The white light safety and the development tolerance were broadly satisfactory.

Claims (2)

[Claims] 1. A photosensitive composition containing a fluorinated surfactant, wherein the fluorinated surfactant is a fluoroaliphatic group (a), an aliphatic group having 4 or more carbon atoms or an aromatic group. (B) A photosensitive composition, which is a synthetic resin (I) having a substituent (c) having an acidic hydrogen atom. 2. The photosensitive composition according to claim 1, wherein the synthetic resin (I) is a polycondensation or polyaddition resin.