JPH0572723A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain excellent sensitivity during exposure and enough hardness even for a short exposure time by incorporating surface-modified silica fine particles the surfaces of which are coupled with a specified functional group by chemical bonding. CONSTITUTION:This negative-type photosensitive compsn. contains a diazonium compd. and a polymer compd. and further contains surface-modified silica fine particles the surfaces of which are coupled with functional groups expressed by formula I by chemical bonding. In formula I, R is a bivalent connecting group consisting of two or more atoms selected from C, H, N, O, S and Si, and Y is -SO3H, -SO2NH-Q<1>, -A<1>-Q<1>, -CO-A<1>-H, etc., wherein A<1> us O or S and Q<1> is H or hydrocarbon group of 1-15 carbon number which may have substituents.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive composition suitable for use in the production of lithographic printing plates, IC circuits and photomasks. More specifically, the present invention relates to a negative photosensitive composition containing a diazonium compound, a polymer compound, and surface-modified silica fine particles and having excellent sensitivity and abrasion resistance during exposure.

[0002]

2. Description of the Related Art The majority of those used as photosensitive substances in negative acting systems are diazonium compounds, and the most commonly used one is formaldehyde condensation of p-diazodiphenylamine. There are diazo resins typified by products. The composition of the photosensitive layer of a photosensitive lithographic printing plate using a diazo resin may be, for example, a diazo resin alone as described in U.S. Pat.No. 2,714,066, that is, a binder-free composition. As described in JP-A-50-30604, it can be classified into a mixture of a binder and a diazo resin. In recent years, most of photosensitive lithographic printing plates using a diazonium compound have been used. It is composed of a diazonium compound and a polymer that serves as a binder to provide high printing durability.

As such a photosensitive layer, JP-A-50-1 is used.
As described in Japanese Patent No. 18802, a so-called alkali development type in which an unexposed portion is removed (developed) by an aqueous alkaline developer and a so-called solvent development type in which an unexposed portion is removed by an organic solvent-based developer are known. However, from the viewpoint of occupational safety and health, the alkali development type has attracted attention, and this is mainly determined by the properties of the binder. As a method for imparting alkali developability to the binder, a carboxylic acid-containing monomer is copolymerized as described in JP-A-50-118802, or a method described in U.S. Pat. No. 2861058. As described above, there is a method of introducing a carboxylic acid into a polymer by reacting a hydroxyl group of polyvinyl alcohol with a cyclic acid anhydride such as phthalic anhydride.

However, none of the photosensitive compositions has sufficient sensitivity, and a short exposure time makes it impossible to obtain a sufficient image. Further, the photosensitive lithographic printing plate obtained from such a photosensitive composition has a drawback that only a lithographic printing plate having a low printing durability can be obtained. Further, a photosensitive composition containing silica particles, a polymer having a quaternary nitrogen atom, and a photosensitive diazo compound described in JP-A-57-197537, and JP-A-57-1416.
A water-development type in which development is performed only with water, such as a photosensitive composition containing a silica particle and a water-insoluble photosensitive resin described in JP-A-39, is also known, and both are usually used as a filler. The silica fine particles or the hydrophobic silica fine particles are used, but they still have the drawbacks of low sensitivity and low printing durability.

Further, JP-A No. 62-52548 discloses an ethylenically unsaturated addition polymer, an alkali-soluble polymer capable of forming a film, a photopolymerization initiator, and fine particles having a hydrophobic surface (silane coupling agent). , Including modified silica fine particles). However, this is still insufficient in sensitivity and printing durability.

Accordingly, an object of the present invention is to provide a negative photosensitive composition which can form a sufficient image even in a short exposure time, has a strong film strength in the image area and is excellent in abrasion resistance.

[0007]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned objects, the inventors have found that these objects can be achieved by using a novel photosensitive composition, Reached That is, the present invention relates to a negative photosensitive composition containing a diazonium compound and a polymer compound, and further surface modification in which at least one functional group represented by the following general formula (I) is linked to the surface of the particle by a chemical bond. The present invention relates to a photosensitive composition containing silica fine particles.

[0008]

[Chemical 3]

In the formula, R represents a divalent linking group consisting of two or more kinds of atoms selected from C, H, N, O, S and Si, and Y
Is

[0010]

[Chemical 4]

And A ¹ , A ² each represent O or S, and Q ¹ , Q ³ , Q ⁴ each represent H or a C ₁ -C ₁₅ hydrocarbon group which may have a substituent. , Q ²
Represents a C _{1 to} C ₁₅ hydrocarbon group which may have a substituent.

The present invention will be described in detail below. Surface-Modified Silica Particles Surface-modified silica fine particles used in the present invention, in which at least one kind of functional group represented by the above general formula (I) is linked to the particle surface by a chemical bond, preferably have the following general formula (II): ) To (V) is used to surface-modify the silica fine particles with the silane coupling agent, or the silane coupling agent-modified silica fine particles obtained above are further added with an inorganic acid such as HNO ₃ and an alcohol. It can be obtained by treating with carboxylic acid or the like.

[0013]

[Chemical 5]

In the formula, R ¹ , R ² and R ³ are C,
A divalent linking group consisting of two or more kinds of atoms selected from H, N, O, S and Si is shown, and Y ¹ , Y ² and Y ³ are respectively

[0015]

[Chemical 6]

A¹, A²Are O or S respectively
Then M¹Represents a halogen atom, M²Is H or metal or
C which may have a substituent₁~ C₁₅Shows the hydrocarbon group of
And Q¹, Q³, Q^FourAre hydrogen atoms or substituents
C which may have₁~ C ₁₅Represents a hydrocarbon group of²
Is C which may have a substituent₁~ C₁₅The hydrocarbon group of
Show.

X ¹ , X ² and X ³ are each a hydrogen atom,
Halogen ^{atom, -OQ 5, -O-CO-} Q 5, -N (Q 6) (Q 7),
—OSO ₂ CF ₃ and Q ⁵ may have a C ₁ to
Represents a C ₁₅ hydrocarbon group, Q ⁶ represents a hydrogen atom or a C ₁ -C ₁₅ hydrocarbon group which may have a substituent, and Q ⁷ represents
Also contain Si represents a hydrocarbon group which may C ₁ -C _15.

Among these, as a silane coupling agent which can be particularly preferably used, X ¹ , X ² and X ³ are each a halogen atom or --OQ ⁵ (Q ⁵ may have a substituent, C _{1 to} C ₁₅ hydrocarbon groups are shown). Examples of the silane coupling agent preferably used in the present invention include

[0019]

[Chemical 7]

[0020]

[Chemical 8]

[0021]

[Chemical 9]

[0022]

[Chemical 10]

[0023]

[Chemical 11]

And the like. The silica fine particles used for the above-mentioned modification are particles containing silicic acid anhydride (SiO ₂ ) as a main component, and various commercially available products can be used. The particle size of the silica particles is preferably in the range of about 1 nm to 500 nm. More preferably, it is 100 nm or less.

[0025] Specifically, Snowtex OL (manufactured by Nissan Chemical Industries, Ltd.) (particle size 45 nm, silica 20% colloidal aqueous solution), Nippon Aerosil Co., Ltd. AEROSIL130
(Particle size 16 nm silica), Mizusuka Chemical Co., Ltd. Mizukasil P-527U (particle size 60 nm silica) and the like. Further, the surface-modified silica fine particles using the above-mentioned silane coupling agent can be produced by a conventionally known surface modification method.

Specifically, Noboru Suzuki, Nobuko Yuzawa, Atsushi Endo,
Hiroshi Utsuki “(Coloring Material)” 57 , 429 (1984), Hiroshi Yoshioka, Masayuki Ikeno “Surface” 21 , 33 (1983), Hiroshi Utsuki “Surface” 16 , 525 (1978), K. Tanaka, et.
al., Bull. Chem. Soc. Jpn., 53 , 1242 (198)
0), ML Hair, W. Hertl. J. Phys. Chem., 77 ,
1965 (1973), Ya. Davydov et. Al., Chromat.
ographia, 14 , 13 (1981), K. Unger et al.
Colloid polym. Sci., 252 , 317 (1974), R.
Burwell, O. Leal. J. Chem. Soc. Chem. Commun., 3
42 (1974), W. Stoeber, Kolloid-Z. 149 , 3
9 (1956), Franz.Pat. 1368765DAS 1163784
Can be synthesized according to the methods described in the above-mentioned review and references, patents, etc. cited therein.

Further, the modified silica fine particles obtained by these methods are further treated with an inorganic acid such as HNO ₃ and alcohol, carboxylic acid, etc.
The following reactions may be mentioned.

[0028]

[Chemical formula 12]

However, Z and Z ¹ each represent a C _{1 to} C ₃₀ hydrocarbon group which may contain N and O, respectively. The amount of the modified silica fine particles used in the present invention is 0.1 to 60% by weight, preferably 0.1 to 60% by weight, based on the total weight of the photosensitive composition containing the diazonium compound, the polymer compound and the modified silica particles.
It is 0.5 to 25% by weight. If the addition amount is less than 0.1% by weight, the effect of the modified silica fine particles is hardly recognized, and if the addition amount is more than 60% by weight, the film strength is lowered. Diazonium Compound The diazonium compound used in the present invention is, for example, a reaction product of a condensate of p-diazodiphenylamine and formaldehyde or acetaldehyde with a hexafluorophosphate or tetrafluoroborate soluble in an organic solvent. Diazo resin inorganic salt, also US Pat. No. 3,300,30
As described in No. 9, the condensate and sulfonic acids such as paratoluenesulfonic acid or salts thereof, phosphinic acids such as benzenephosphinic acid or salts thereof, hydroxyl group-containing compounds such as 2,4-
Reaction products with dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid or a salt thereof, and further, JP-A-58-209733, 62-175731, 63-26264.
Japanese Patent Publication No. 49-48001, an organic solvent-soluble diazo resin which is a reaction product with a sulfonic acid having a long-chain alkyl group, and a co-condensation diazo resin with an aromatic compound described in JP-B-49-48001. Etc. are preferably used.

Furthermore, a diazo resin synthesized by a ring-opening polymerization reaction with an epoxy resin disclosed in Japanese Patent Application Nos. 3-110293 and 3-120380, and JP-A-58-58.
You may use the diazo resin synthesize | combined by the reaction by the olefinic unsaturated compound described in 187925. In the present invention, another diazo resin that can be preferably used is an aromatic compound having at least one organic group of a carboxyl group, a sulfonic acid group, a sulfinic acid group, an oxygen acid group of phosphorus, and a hydroxyl group, It is a cocondensate containing a diazonium compound, preferably an aromatic diazonium compound, as a structural unit.

The aromatic compound having at least one of the above-mentioned carboxyl group, sulfonic acid group, sulfinic acid group, phosphorus oxygen acid group, and hydroxyl group (hereinafter, these groups are also referred to as “acid group”) is In the molecule, an aromatic ring substituted with at least one acid group is contained, and in this case, two or more of the above acid groups may be substituted with the same aromatic ring.

The above aromatic ring is preferably a phenyl group or a naphthyl group. The above-mentioned acid group may be directly bonded to the aromatic ring or may be bonded via a linking group. Examples of the linking group include groups having 1 or more carbon atoms containing an ether bond.

Specific examples of the aromatic compound containing at least one of the above-mentioned carboxyl group, sulfonic acid group, sulfinic acid group, phosphorus oxyacid group, and hydroxyl group include benzoic acid and o-chlorobenzoic acid. Acid, m-chlorobenzoic acid, p-chlorobenzoic acid, phthalic acid, terephthalic acid, diphenylacetic acid, phenoxyacetic acid, p-methoxyphenylacetic acid, p-methoxybenzoic acid, 2,4-dimethoxybenzoic acid, 2,4- Dimethylbenzoic acid, p-phenoxybenzoic acid, 4-anilinobenzoic acid, 4- (m-methoxyanilino) benzoic acid, 4- (p-methoxybenzoyl) benzoic acid, 4- (p-methylanilino) benzoic acid,
4-phenylsulfonylbenzoic acid, phenol, (o,
m, p) -cresol, xylenol, resorcin, 2
-Methylresorcin, (o, m, p) -methoxyphenol, m-ethoxyphenol, catechol, phloroglucin, p-hydroxyethylphenol, naphthol, pyrogallol, hydroquinone, p-hydroxybenzyl alcohol, 4-chlororesorcin, biphenyl 4, 4'-diol, 1,2,4-benzenetriol, bisphenol A, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone,
p-hydroxyacetophenone, 4,4-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylamine, 4,4'-dihydroxydiphenylsulfide cumylphenol, (o, m, p) -chlorophenol, (o, m, p) -Bromophenol, salicylic acid,
4-methylsalicylic acid, 6-methylsalicylic acid, 4-ethylsalicylic acid, 6-propylsalicylic acid, 6-laurylsalicylic acid, 6-stearylsalicylic acid, 4,6-dimethylsalicylic acid, p-hydroxybenzoic acid, 2-methyl-4-hydroxy Benzoic acid, 6-methyl-4-hydroxybenzoic acid, 2,6-dimethyl-4-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,4-dihydroxy-6-methylbenzoic acid, 2,6-dihydroxy Benzoic acid, 2,6-dihydroxy-4-methylbenzoic acid,
4-chloro-2,6-dihydroxybenzoic acid, 4-methoxy-2,6-dioxybenzoic acid, gallic acid, phloroglucin carboxylic acid, 2,4,5-trihydroxybenzoic acid, m-galloyl gallic acid, Tannic acid, m-benzoyl gallic acid, m- (p-toluyl) gallic acid, protocatechuyl-gallic acid, 4,6-dihydroxyphthalic acid, (2,4-dihydroxyphenyl) acetic acid, (2,6
-Dihydroxyphenyl) acetic acid, (3,4,5-trihydroxyphenyl) acetic acid, p-hydroxymethylbenzoic acid, p-hydroxyethylbenzoic acid, 4- (p-hydroxyphenyl) methylbenzoic acid, 4- (o- Hydroxybenzoyl) benzoic acid, 4- (2,4-dihydroxybenzoyl) benzoic acid, 4- (p-hydroxyphenoxy) benzoic acid, 4- (p-hydroxyanilino) benzoic acid, bis (3-carboxy-4-) Hydroxyphenyl)
Amine, 4- (p-hydroxyphenylsulfonyl) benzoic acid, 4- (p-hydroxyphenylthio) benzoic acid, benzenesulfonic acid, p-toluenesulfonic acid, benzenesulfinic acid, p-toluenesulfinic acid, aniline-2- Sulfonic acid, 4-amino-m-toluenesulfonic acid, 2,5-diaminobenzenesulfonic acid, 1-naphthalenesulfonic acid, 1-amino-2-naphthalenesulfonic acid, 5-amino-2-naphthalenesulfonic acid, 7-
Amino-1,3-naphthalenedisulfonic acid, 2-amino-1,5-naphthalenedisulfonic acid, 2-sulfobenzoic acid, (these sulfonic acids or sulfinic acids may be free sulfonic acids or sulfinic acids. However, it may be a metal salt such as sodium, potassium, lithium, cesium, calcium, barium, magnesium, aluminum, zinc, or an unsubstituted or substituted aluminum salt), phenylphosphoric acid, phenylphosphorous acid,
Phenylphosphonic acid, phenylphosphonous acid, phenylphosphinic acid, phenylphosphinic acid, benzylphosphoric acid, benzylphosphonic acid, benzylphosphonic acid, benzylphosphonous acid, benzylphosphinic acid, benzylphosphinic acid, 2-phenylethylphosphorus Acid, 2-phenylethyl phosphorous acid, 1-naphthyl phosphoric acid, 1-naphthyl phosphorous acid, 1-naphthylphosphonic acid, 1-naphthylphosphonous acid, 1-naphthylphosphinic acid, 1-naphthylphosphinic acid, 2- Examples thereof include naphthyl phosphoric acid.

Of these, particularly preferred are 4-methoxybenzoic acid, 3-chlorobenzoic acid, 2,4-dimethoxybenzoic acid, p-phenoxybenzoic acid, 4-anilinobenzoic acid, phenoxyacetic acid, phenylacetic acid, p-acetic acid. -Hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, benzenesulfonic acid, p-toluenesulfinic acid, 1-naphthalenesulfonic acid, phenylphosphoric acid, phenylphosphonic acid.

The aromatic diazonium compound forming the constitutional unit of the above-mentioned co-condensed diazo resin is, for example, Japanese Patent Publication No. 49-4.
Although diazonium salts such as those listed in Japanese Patent No. 8001 can be used, in particular diphenylamine-4.
-Diazonium salts are preferred. Diphenylamine-4
-Diazonium salts are derived from 4-amino-diphenylamines, and such 4-amino-diphenylamines include 4-amino-diphenylamine,
4-amino-3-methoxy-diphenylamine, 4-amino-2-methoxy-diphenylamine, 4'-amino-2-methoxy-diphenylamine, 4'-amino-4
-Methoxy-diphenylamine, 4-amino-3-methyldiphenylamine, 4-amino-3-ethoxy-diphenylamine, 4-amino-3-β-hydroxyethoxydiphenylamine, 4-amino-diphenylamine-
2-sulfonic acid, 4-amino-diphenylamine-2-
Carboxylic acid, 4-amino-diphenylamine-2'-carboxylic acid and the like can be mentioned, and particularly preferred are 3-methoxy-4-amino-4-diphenylamine and 4-amino-diphenylamine.

The above-mentioned co-condensed diazo resin can be obtained by a known method, for example, Photographic Science and Engineering (Photo. Sci., Eng.) Vol. 17, page 33 (1973), US Pat. No. 2,063, 631, Ibid. 2,679,498
According to the method described in each specification, a diazonium salt, an aromatic compound having an acid group and aldehydes such as paraformaldehyde, acetaldehyde, benzaldehyde or ketones such as acetone and acetophenone are subjected to a heavy bond in sulfuric acid, phosphoric acid or hydrochloric acid. It is obtained by It can also be synthesized by using the method described in JP-B-49-45322 and JP-B-49-45323.

The charged molar ratio of the aromatic compound having at least one of the acid groups and the aromatic diazo compound is 1: 0.
1 to 0.1: 1, preferably 1: 0.5 to 0.2: 1, more preferably 1: 1 to 0.2: 1. In this case, the molar ratio of the total amount of the aromatic compound having at least one of the acid groups and the aromatic diazo compound to the aldehyde or ketone is usually 1: 0.5 to 2.0, preferably 1: 0. 7-1.5
Then, the co-condensed diazo resin is obtained by reacting at low temperature for a short time, for example, for about 3 hours.

Further, as a diazo resin other than the co-condensation diazo resin with an aromatic compound having the above acid group, Japanese Patent Application No.
A diazo resin condensed with an aldehyde containing an acid group or an acetal compound thereof disclosed in JP-A-130493, JP-A-1-303705 and JP-A-2-53101 can also be preferably used. Next, the counter anion of the diazo resin will be described.

The counter anion includes an anion that stably forms a salt with the diazo resin and makes the resin soluble in an organic solvent. These include organic carboxylic acids such as decanoic acid and benzoic acid, organic phosphoric acids such as phenylphosphoric acid and sulfonic acids, and typical examples thereof include fluoroalkanesulfonic acids such as methanesulfonic acid and trifluoromethanesulfonic acid. , Laurylsulfonic acid, dioctylsulfosuccinic acid, dicyclohexylsulfosuccinic acid, camphorsulfonic acid, tolyloxy-3-propanesulfonic acid, nonylphenoxy-3-propanesulfonic acid, nonylphenoxy-4-butanesulfonic acid, dibutylphenoxy-3
-Propanesulfonic acid, diamylphenoxy-3-propanesulfonic acid, dinonylphenoxy-3-propanesulfonic acid, dibutylphenoxy-4-butanesulfonic acid, dinonylphenoxy-4-butanesulfonic acid, benzenesulfonic acid, toluenesulfone Acid, mesitylene sulfonic acid, p-chlorobenzene sulfonic acid, 2,5-dichlorobenzene sulfonic acid, sulfosalicylic acid, 2,5-
Dimethylbenzenesulfonic acid, p-acetylbenzenesulfonic acid, 5-nitro-o-toluenesulfonic acid, 2-
Nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-chloro-5
-Nitrobenzenesulfonic acid, butylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, butoxybenzenesulfonic acid, dodecyloxybenzenesulfonic acid, 2
-Hydroxy-4-methoxybenzophenone-5-sulfonic acid, isopropylnaphthalenesulfonic acid, butylnaphthalenesulfonic acid, hexylnaphthalenesulfonic acid,
Octylnaphthalenesulfonic acid, butoxynaphthalenesulfonic acid, dodecyloxynaphthalenesulfonic acid, dibutylnaphthalenesulfonic acid, dioctylnaphthalenesulfonic acid, triisopropylnaphthalenesulfonic acid, tributylnaphthalenesulfonic acid, 1-naphthol-5-sulfonic acid, naphthalene-1- Sulfonic acid, naphthalene-
2-sulfonic acid, 1,8-dinitro-naphthalene-3,
Aliphatic and aromatic sulfonic acids such as 6-disulfonic acid and dimethyl-5-sulfoisophthalate, 2,2 ', 4
4'-tetrahydroxybenzophenone, 1,2,3-
Aromatic compounds containing hydroxyl groups such as trihydroxybenzophenone and 2,2 ′, 4-trihydroxybenzophenone
Examples thereof include halogenated Lewis acids such as hexafluorophosphoric acid and tetrafluoroboric acid, perhalogen acids such as CIO ₄ and IO _{4, and the} like, but are not limited thereto. Of these, particularly preferred are butylnaphthalenesulfonic acid, dibutylnaphthalenesulfonic acid, hexafluorophosphoric acid,
2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and dodecylbenzenesulfonic acid.

The diazo resin used in the present invention can have any desired molecular weight by varying the molar ratio of each monomer and the condensation conditions, but it is effective for the intended purpose of the present invention. The molecular weight is about 400
To 100,000, preferably about 800 to 8,000
A value of 0 is suitable. The above diazo resins may be used alone or in a mixture of two or more kinds.

The total amount of diazo resin contained in the photosensitive layer is preferably 1 to 70% by weight, more preferably 3 to 60% by weight. Polymer Compound The polymer compound preferably used in the present invention includes a copolymer having one or more of the monomers shown in the following (1) to (15) as its structural unit. (1) Acrylamides, methacrylamides, acrylic esters, methacrylic esters and hydroxystyrenes having aromatic hydroxyl groups, such as N- (4-hydroxyphenyl) acrylamide or N- (4-hydroxyphenyl) methacrylamide , O-, m-, p-hydroxystyrene, o-, m-, p-hydroxyphenyl-
Acrylate or methacrylate, (2) acrylic acid ester having an aliphatic hydroxyl group, and methacrylic acid ester, such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, (3) acrylic acid, methacrylic acid Unsaturated carboxylic acids such as maleic anhydride and itaconic acid, (4) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate,
Hexyl acrylate, cyclohexyl acrylate, octyl acrylate, benzyl acrylate, acrylate-2
-(Substituted) alkyl acrylates such as chloroethyl, glycidyl acrylate and N-dimethylaminoethyl acrylate, (5) methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, glycidyl methacrylate, N-dimethyl (Substituted) alkyl methacrylate such as aminoethyl methacrylate, (6) acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N-ethyl acrylamide, N-hexyl methacrylamide, N-cyclohexyl acrylamide, N-hydroxyethyl Acrylamide, N-phenyl acrylamide, N-nitrophenyl acrylamide, Acrylamide or methacrylamide such as -ethyl-N-phenylacrylamide, (7) Vinyl ether such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether or phenyl vinyl ether, (8) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate, (9) styrenes such as styrene, α-methyl styrene and chloromethyl styrene, (10) methyl vinyl ketone, ethyl vinyl ketone, propyl Vinyl ketone,
Vinyl ketones such as phenyl vinyl ketone, (11) olefins such as ethylene, propylene, isobutylene, butadiene and isoprene, (12) N-vinylpyrrolidone,
N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile, etc. (13) Maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide,
Unsaturated imides such as N- (p-chlorobenzoyl) methacrylamide, (14) N- (o-aminosulfonylphenyl) methacrylamide, N- (m-aminosulfonylphenyl) methacrylamide, N- (p-amino) Sulfonylphenyl methacrylamide, N- (1- (3-aminosulfonyl) naphthyl) methacrylamide, N- (2
Methacrylic acid amides such as -aminosulfonylethyl) methacrylamide, and acrylamides having the same substituents as described above, o-aminosulfonylphenyl methacrylate, m-aminosulfonylphenyl methacrylate, p-aminosulfonylphenyl methacrylate, 1 Methacrylic acid esters such as-(3-aminosulfonylnaphthyl) methacrylate, and unsaturated sulfonamides such as acrylic acid esters having the same substituents as above.

Further, a monomer copolymerizable with the above-mentioned monomer may be copolymerized. For example, the copolymer obtained by copolymerizing the above-mentioned monomers may be modified with glycidyl methacrylate, glycidyl acrylate, etc., but is not limited thereto. Further, the above-mentioned copolymer preferably contains the unsaturated carboxylic acid listed in (3), and the preferable carboxylic acid value of the copolymer is 0 to 4 meq / g, more preferably 0.5. ~ 3.5 meq
/ G.

Further, among the monomers shown in (1) to (15), the monomers listed in (2) and (12) above, particularly 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate or acrylonitrile,
Further, copolymers containing the monomers listed in (4) and (5) above, particularly ethyl acrylate, butyl acrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate or benzyl methacrylate, are preferred. ..

Further, as preferable polymer compounds other than the above, polyurethane having an alkali-soluble group as described in JP-A-62-123452 and JP-A-62-62452 are described.
The polyvinyl acetal resin which has an alkali-soluble group as described in 169154 publication is mentioned.
The weight average molecular weight of the polymer compound is from 0.5000 to 300,000, more preferably from 10,000 to 200,000.

The above polymer compounds may be used alone or in combination of two or more. If necessary, polyvinyl butyral resin, polyurethane resin, polyamide resin, epoxy resin, novolac resin, natural resin or the like may be added to the polymer compound. Other Additives The polymer compound used in the present invention is usually contained in the solid content of the photosensitive composition in an amount of 40 to 99% by weight, preferably 50 to 95% by weight. The photosensitive diazo resin used in the present invention is usually contained in an amount of 1 to 60% by weight, preferably 3 to 40% by weight.

A dye may be further used in the photosensitive composition of the present invention. The dye is used for the purpose of obtaining a visible image by exposure (exposed visible image) and a visible image after development. As the dye, those that "change color tone" by reacting with free radicals or acids can be preferably used. Here, "the color tone changes" includes both a change from colorless to a color tone and a change from a colored to a colorless or a different color tone. Preferred dyes are those which form a salt with an acid to change the color tone.

For example, Victoria Pure Blue BOH
[Hodogaya Chemical], Oil Blue # 603 [Orient Chemical], Patent Pure Blue [Sumitomo Mikuni Chemical], Crystal Violet, Brilliant Green, Ethyl Violet, Methyl Violet, Methyl Green, Erythrosine B, Basic Fuchsin, Malachite Green, oil red, m-cresol purple, rhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, cyano-p-diethylaminophenylacetanilide, and other triphenylmethanes, diphenylmethanes, oxazines, xanthenes, The iminonaphthoquinone-based, azomethine-based, or anthraquinone-based dyes are examples of the discoloring agent that changes from a colored color to a colorless or different colored color tone.

On the other hand, examples of the discoloring agent that changes from colorless to colored include leuco dyes and, for example, triphenylamine, diphenylamine, o-chloroaniline, 1,2,3-triphenylguanidine, naphthylamine, diaminodiphenylmethane, p, p. ′ -Bis-dimethylaminodiphenylamine, 1,2-dianilinoethylene, p, p ′,
p ″ -tris-dimethylaminotriphenylmethane,
p, p'-bis-dimethylaminodiphenylmethylimine, p, p ', p "-triamino-o-methyltriphenylmethane, p, p'-bis-dimethylaminodiphenyl-4-anilinonaphthylmethane, p, Examples thereof include primary or secondary arylamine dyes represented by p ′, p ″ -triaminotriphenylmethane. Particularly preferably, triphenylmethane-based and diphenylmethane-based dyes are effectively used, more preferably triphenylmethane-based dyes, and particularly Victoria Pure Blue BOH.

The above dye is usually contained in the photosensitive composition in an amount of about 0.5.
To about 10% by weight, more preferably about 1 to 5% by weight. Various additives can be further added to the photosensitive composition of the present invention. For example, alkyl ethers (such as ethyl cellulose and methyl cellulose) for improving coating properties, fluorosurfactants and nonionic surfactants (particularly preferred are fluorosurfactants), flexibility of coating film, resistance to coating. A plasticizer for imparting abrasion resistance (for example, butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate,
Trioctyl phosphate, tetrahydrofurfuryl oleate, oligomers and polymers of acrylic acid or methacrylic acid, of which tricresyl phosphate is particularly preferred), and an oil sensitizer for improving the oil sensitivity of the image area (for example, JP-A No. 55-527, half-esterified products of styrene-maleic anhydride copolymer with alcohol, novolak resins such as pt-butylphenol-formaldehyde resin, and 50 of p-hydroxystyrene.
% Fatty acid ester, etc.), stabilizer (eg phosphoric acid, phosphorous acid, organic acid (citric acid, oxalic acid, dipicolinic acid, benzenesulfonic acid, naphthalenesulfonic acid, sulfosalicylic acid, 4-methoxy-2-hydroxybenzophenone- 5-sulfonic acid, tartaric acid, etc.), a development accelerator (eg higher alcohol, acid anhydride, etc.) and the like are preferably used.

The amount of these additives to be added depends on the intended use,
Depending on the purpose, it is generally 0.0
It is 1 to 30% by weight. Photosensitive lithographic printing plate using the photosensitive composition of the present invention To provide the photosensitive composition on the support, a photosensitive diazo resin, a polymer compound, modified silica fine particles of the present invention,
And, if necessary, a predetermined amount of various additives is added to a suitable solvent (methyl cellosolve, ethyl cellosolve, dimethoxyethane, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, 1-methoxy-2.
-Propanol, methyl cellosolve acetate, acetone, methyl ethyl ketone, methanol, dimethylformamide, dimethylacetamide, cyclohexanone, dioxane, tetrahydrofuran, methyl lactate, ethyl lactate, ethylene dichloride, dimethylsulfoxide, water or a mixture thereof) A coating solution of the photosensitive composition may be prepared, coated on a support, and dried.

The solvent used may be a single solvent, but it is more preferable to use a mixture of a high boiling point solvent such as methyl cellosolve, 1-methoxy-2-propanol and methyl lactate and a low boiling point solvent such as methanol and methyl ethyl ketone. The solid concentration of the photosensitive composition at the time of coating is 1 to
It is desirable to set it in the range of 50% by weight. In this case, the coating amount of the photosensitive composition is about 0.2 to 10 g / m 2.
^It may be about ² (dry weight), and more preferably,
It is preferable to set it to 0.5 to 3 g / m ² .

Such a photosensitive composition is coated on a suitable support to obtain a photosensitive lithographic printing plate. Examples of such a support include paper, plastic (for example, polyethylene, polypropylene, polystyrene, etc.) laminated paper,
Aluminum (including aluminum alloys), metal plates such as zinc and copper, cellulose diacetate, cellulose triacetate, cellulose propionate, polyethylene terephthalate, polyethylene-polypropylene, polycarbonate, polyvinyl acetal and other plastic films, Examples thereof include paper or plastic films laminated or vapor-deposited with the metals as described above, copper plates plated with aluminum or chrome, and of these, aluminum and aluminum-coated composite supports are particularly preferable.

The thickness of the aluminum plate preferably used is 0.1 mm to 0.6 mm. The photosensitive lithographic printing plate of the present invention may be used on only one side or may be used on both sides by the same treatment. The following will be described only for the case of one side, but in the case of producing a photosensitive lithographic printing plate which can be used for both sides, the same treatment may be applied to both sides.

The surface of the aluminum material enhances water retention,
Surface treatment is desirable for the purpose of improving the adhesion to the photosensitive layer. For example, as a roughening method, generally known brush polishing method, ball polishing method, electrolytic etching,
Methods such as chemical etching, liquid honing, sand blasting and the like and combinations thereof may be mentioned, preferably brush polishing, electrolytic etching, chemical etching and liquid honing may be mentioned, among which the use of electrolytic etching is particularly preferred. Roughening methods including are preferred. Further, as described in JP-A-54-63902, a method of brush-polishing and then electrolytic etching is also preferable.

As the electrolytic bath used for electrolytic etching, an aqueous solution containing an acid, an alkali or a salt thereof, or an aqueous solution containing an organic solvent is used. Of these, hydrochloric acid, nitric acid or their solutions is used. Electrolytes containing salts are preferred. Further, the surface-roughened aluminum plate is desmutted with an acid or alkali aqueous solution, if necessary.

The aluminum plate thus obtained is preferably subjected to anodizing treatment, and particularly preferably, a method of treating with a bath containing sulfuric acid or phosphoric acid can be mentioned. Further, if necessary, the silicate treatment (sodium silicate, sodium silicate) described in US Pat. No. 2,714,066 and US Pat. No. 3,181,461 and US Pat. No. 2,946,638 are described. Potassium Fluorozirconate Treatment, Phosphomolybdate Treatment Described in U.S. Pat. No. 3,201,247, British Patent No. 1,
Alkyl titanate treatment described in No. 108,559,
Polyacrylic acid treatment described in German Patent No. 1,091,433, polyvinyl phosphonic acid treatment described in German Patent No. 1,134,093 and British Patent No. 1,230,447, Japanese Patent Publication No. 44-6409 Phosphonic acid treatment described in the publication, phytic acid treatment described in U.S. Pat.No. 3,307,951 and further described in JP-A-58-16893 and JP-A-58-18291 Those treated with a salt of a lipophilic organic polymer compound and a divalent metal are particularly preferable.

As another hydrophilic treatment method, silicate electrodeposition described in US Pat. No. 3,658,662 can also be mentioned. It is also preferable that after the graining treatment and the anodic oxidation, the sealing treatment is performed. Such sealing treatment is performed by immersion in hot water and a hot aqueous solution containing an inorganic salt or an organic salt, a steam bath, or the like.

More specifically, the support suitable for use in the present invention is as follows: 0.1 to 0.5% iron and silicon.
1S aluminum plate containing 0.03 to 0.3%, 0.001 to 0.03% of copper, and 0.002 to 0.1% of titanium, alkali, preferably 1 to 30% of sodium hydroxide, To an aqueous solution of potassium hydroxide, sodium carbonate, sodium silicate, etc.,
Immerse at a temperature of 20 to 80 ° C. for 5 seconds to 250 seconds to perform etching. Aluminum may be added to the etching bath at about 1/5 of the alkali. Then, it is immersed in a 10 to 30% nitric acid or sulfuric acid aqueous solution at a temperature of 20 to 70 ° C. for 5 seconds to 250 seconds to carry out neutralization and smut removal after alkali etching.

After cleaning the surface of this aluminum alloy plate,
The roughening process described below is performed. As the roughening treatment, brush polishing and / or electrolytic etching treatment is suitable. For the brush polishing, it is preferable to use a pumicetone-water suspension and a nylon brush, and the average surface roughness is 0.25.
˜0.9 μm is preferred.

The electrolytic solution used in the electrolytic etching treatment is an aqueous solution of hydrochloric acid or nitric acid, and the concentration is preferably in the range of 0.01 to 3% by weight, and 0.05 to 2.5% by weight. It is more preferable if it exists. In addition, nitrates, chlorides, monoamines, diamines, and
Aldehydes, phosphoric acid, chromic acid, boric acid, corrosion inhibitors (or stabilizers) such as ammonium oxalate, and a grain leveling agent can be added. Further, the electrolytic solution may contain an appropriate amount (1 to 10 g / l) of aluminum ions.

The temperature of the electrolytic solution is usually 10 to 60 ° C. As the alternating current used at this time, any of rectangular wave, trapezoidal wave, and sine wave can be used as long as positive and negative polarities are exchanged alternately. Phase alternating current can be used. Further, the current density is 5 to 100 A / dm ² , and it is desirable to perform the treatment for 10 to 300 seconds.

The surface roughness of the aluminum alloy support in the present invention is adjusted to 0.2 to 0.8 μm by adjusting the amount of electricity. Aluminum alloy grained like this,
It is preferable to remove smut adhering to the surface with 10 to 50% hot sulfuric acid (40 to 60 ° C.) or a dilute alkali (sodium hydroxide or the like). When removed with an alkali, it is subsequently immersed in an acid (nitric acid or sulfuric acid) for neutralization for cleaning.

After removing the surface smut, an anodic oxide film is provided. As the anodizing method, a conventionally well-known method can be used, but sulfuric acid is used as the most useful electrolytic solution. Next to that, phosphoric acid is also a useful electrolyte. Further, the mixed acid of sulfuric acid and phosphoric acid disclosed in JP-A-55-28400 is also useful.

In the sulfuric acid method, the treatment is usually performed with a direct current, but it is also possible to use an alternating current. The concentration of sulfuric acid is 5
Used at 30%, 5 to 25 in the temperature range of 20 to 60 ° C
Electrolytic treatment is carried out for 0 seconds, and an oxide film of 1 to 10 g / m ² is provided on the surface. The electrolytic solution preferably contains aluminum ions. Further, the current density at this time is preferably 1 to 20 A / dm ² .

In the case of the phosphoric acid method, a concentration of 5 to 50%,
1 to 15 A for 10 to 300 seconds at a temperature of 30 to 60 ° C
Processed at a current density of / dm ² . Aluminum substrates treated in this manner are further described in US Pat.
It is desirable to carry out a surface treatment with silicates as described in the specification No. 066.

On the back surface of the support of the photosensitive lithographic printing plate used in the present invention, there is an organic layer for suppressing the elution of the aluminum anodic oxide film during development and for preventing the photosensitive layer from being scratched when stacked. A coating layer made of a molecular compound (hereinafter, this coating layer will be referred to as a backcoat layer) may be provided.
As a material for the back coat, Japanese Patent Application No. Hei 2-327111
An organic polymer compound which is insoluble in an alkaline developing solution as disclosed in Japanese Patent No. 3,839,049 is used. The thickness of the back coat layer basically needs to be a thickness capable of suppressing elution of the anodized film of aluminum during development, and is preferably in the range of 0.01 to 50 μm, more preferably 0.05 to 10 μm. .. Although various methods can be applied as a method for coating the back surface of the aluminum support with the back coat layer, the most preferable method for securing the above-mentioned coating amount is a method in which the solution is coated and dried.

Further, it is also preferable to undercoat the following compounds on the surface of the support. Examples of the compound used for the undercoat include phosphonic acids having an amino group such as carboxymethyl cellulose, dextrin, gum arabic, and 2-aminoethylphosphonic acid, phenylphosphonic acid which may have a substituent, naphthylphosphonic acid, and alkylphosphone. Acid, organic phosphonic acid such as glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid, phenylphosphoric acid which may have a substituent, naphthylphosphoric acid, organic phosphoric acid such as alkylphosphoric acid and glycerophosphoric acid, a substituent Phenylphosphinic acid, which may have
Organic phosphinic acids such as naphthylphosphinic acid, alkylphosphinic acids and glycerophosphinic acids, amino acids such as glycine and β-alanine, and amine hydrochlorides having a hydroxyl group such as triethanolamine hydrochloride. A water-soluble polymer having a sulfonic acid group described in JP-A-101651 and an acid dye described in JP-A-60-64352 are preferably used.

This undercoat layer can be provided by dissolving the above compound in water, methanol, ethanol, methyl ethyl ketone, or the like or a mixed solvent thereof, coating on a support and drying. Further, a yellow dye may be added to improve the tone reproducibility of the photosensitive lithographic printing plate. The coating amount of the undercoat layer after drying is suitably ² to 200 mg / m ² , and preferably 5 to 100 mg / m ² .

Further, it is preferable that a mat layer composed of protrusions provided independently of each other is provided on the coated photosensitive layer. The purpose of the matte layer is to improve the vacuum adhesion between the negative image film and the photosensitive lithographic printing plate during contact exposure, thereby shortening the vacuuming time and preventing the collapse of fine halftone dots during exposure due to poor adhesion. That is.

A method for applying the matte layer is described in JP-A-55.
No. 12974, there is a method of heat-sealing powdered solid powder, and another method of spraying polymer-containing water described in JP-A-58-182636 and drying, and any method may be used. However, it is desirable that the matte layer itself be dissolved in an aqueous alkaline developer containing substantially no organic solvent or be removable by this.

The photosensitive composition of the present invention coated on a support is exposed through a transparent original image having a line image, a halftone image or the like, and then developed with an aqueous alkaline developing solution,
A negative relief image is given to the original picture. Any known developer may be used for the developing treatment of the photosensitive printing plate using the composition of the present invention, but the following are preferable.

For example, the developing solution contains at least one kind of alkaline agent and water as essential components. As the alkaline agent contained as an essential component in the developer, sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium, potassium, or ammonium salt of secondary or tertiary phosphate, meta, Inorganic alkali agents such as sodium silicate, sodium carbonate, sodium hydrogen carbonate, potassium carbonate and ammonia, mono-, di- or trimethylamine, mono-, di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di- or triethanolamine, Examples thereof include organic amine compounds such as mono-, di- or triisopropanolamine, ethyleneimine and ethylenediimine.
The alkaline agents may be used alone or in combination of two or more.

The content of these alkaline agents in the developing solution is 0.05 to 10% by weight, preferably 0.5 to 5% by weight. If it is less than 0.05% by weight, the development will be poor, and if it exceeds 10% by weight, the printing performance as a lithographic printing plate will be adversely affected. In addition to the above-mentioned essential components, anionic surfactants, amphoteric surfactants such as those described in JP-A-50-51324, JP-A-59-75255 and JP-A-60-75255 are also contained in the developer. At least one nonionic surfactant as described in JP-A-111246, or JP-A-55-95946.
By incorporating the polymer electrolyte as described in JP-A-56-142528, the wettability to the photosensitive composition can be enhanced and the gradation can be further enhanced. Among the above, an anion activator is preferable.

The amount of such a surfactant or polymer electrolyte to be added is not particularly limited, but is preferably 0.003 to 5% by weight, and particularly preferably 0.006 to 1% by weight. Also,
The developing solution for developing a photosensitive printing plate using the composition of the present invention may contain a water-soluble sulfite, if necessary. As such a water-soluble sulfite, an alkali or alkaline earth metal salt of sulfite is preferable, and examples thereof include sodium sulfite, potassium sulfite, lithium sulfite and magnesium sulfite. The content of these sulfites in the developer composition is 0 to 4% by weight, and preferably 0.
It is 1 to 1% by weight.

Instead of the water-soluble sulfite, an alkali-soluble pyrazolone compound, an alkali-soluble thiol compound, or a hydroxy aromatic compound such as methylresorcin may be contained. Of course, water-soluble sulfites of these compounds can be used together. Further, if necessary, additives such as a defoaming agent and a water softener can be contained. The antifoaming agent is preferably a silicone type, and examples of the water softening agent include polyphosphates and aminopolycarboxylic acids.
The optimum amount of such a water softener varies depending on the hardness of the hard water used and the amount used, but if the general amount is shown, it is 0.01 to 5% by weight in the developer at the time of use. , And more preferably in the range of 0.01 to 0.5% by weight.

The developer for developing the photosensitive printing plate using the composition of the present invention may contain a specific organic solvent, if necessary. The organic solvent can dissolve, swell, or disperse the non-exposed area (non-image area) of the above-mentioned photosensitive composition layer when contained in a developing solution, and has a solubility in water of 10% by weight at room temperature. The following organic solvents are preferred. Examples of such an organic solvent include the following. For example, carboxylic acid esters such as ethyl acetate, butyl acetate, benzyl acetate, ethylene glycol monobutyl acetate, butyl lactate and butyl levulinate; ketones such as methyl isobutyl ketone and cyclohexanone; ethylene glycol monobutyl ether,
Alcohols such as ethylene glycol benzyl ether, ethylene glycol monophenyl ether, benzyl alcohol, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol; alkyl substituted aromatic hydrocarbons, halogenated hydrocarbons and the like. You may use it in combination of 2 or more types of these organic solvents. Among the above organic solvents, ethylene glycol monophenyl ether and benzyl alcohol are particularly effective. Further, the content of these organic solvents in the developer is 0 to 20% by weight, and particularly preferable results are obtained when the content is 2 to 10% by weight.

Further, a certain solubilizing agent may be contained in order to assist the dissolution of the above-mentioned organic solvent in water. As such a solubilizing agent, it is preferable to use a low molecular weight alcohol or ketone which is more soluble in water than the organic solvent used.
Moreover, an anion activator, an amphoteric activator, etc. can also be used. As the activator, for example, sodium isopropylnaphthalene sulfonate, sodium N-methyl-N-pentadecylaminoacetate, sodium lauryl sulfate and the like are preferable.

However, when an organic solvent or the like is contained, there are problems in hygiene such as toxicity during work, odor and the like, safety problems such as fire and gas explosion, workability problems such as generation of bubbles, pollution due to waste liquid, etc. Therefore, those containing substantially no organic solvent are more preferable. The term "substantially free of organic solvent" means that the organic solvent is not contained to the extent of causing inconvenience in terms of environmental hygiene, safety, workability, etc., and in the present invention. The proportion of the substance in the composition is 2% by weight or less, preferably 1% by weight or less.

As such an aqueous alkaline developer containing substantially no organic solvent, for example, JP-A-59-8424 is known.
1, JP-A-57-192952 and JP-A-62-2.
It is possible to use the developer composition described in JP-A No. 4263, etc., which is used when the positive type lithographic printing plate is imagewise exposed and then developed. Photosensitive lithographic printing plates using the photosensitive composition of the present invention are disclosed in JP-A-54-8002 and 55-55.
The plate-making process may be carried out by the methods described in JP-A-115045 and JP-A-59-58431. That is, after the development treatment, it may be washed with water and then subjected to a desensitizing treatment, or as it is, a desensitizing treatment, or a treatment with an aqueous solution containing an acid, or a treatment with an aqueous solution containing an acid, followed by a desensitizing treatment.

Further, in the developing process of this type of photosensitive lithographic printing plate, the alkaline aqueous solution is consumed depending on the processing amount to reduce the alkaline concentration, or the alkaline concentration is reduced by air due to long-term operation of the automatic developing solution. As a result, the processing capacity is reduced.
A replenisher may be used to restore throughput as described in US Pat. In this case, it is preferable to supplement by the method described in US Pat. No. 4,882,246.

Further, the plate making process as described above is described in Japanese Patent Laid-Open No. Hei 2
It is preferably carried out by an automatic developing machine as described in JP-A-7054 and JP-A-2-32357. Desensitizing gums optionally applied in the final step of the plate making process are Japanese Patent Publication Nos. 62-16834, 62-25118, 63-52600, and JP-A 62-7595, 62.
Those described in JP-A-11693 and JP-A-62-83194 are preferable.

After the development processing, if necessary, the unnecessary portion of the image area can be erased with a commercially available negative erasing liquid or rubbed with a stone stick. Further, examples of the light source used for the exposure include a carbon arc lamp, a mercury lamp, a xenon lamp, a metal halide lamp, a strobe, an ultraviolet ray and a laser beam.

[0083]

INDUSTRIAL APPLICABILITY The photosensitive composition of the present invention has excellent sensitivity at the time of exposure, sufficient curing can be obtained even in a short exposure time, and when used in a photosensitive lithographic printing plate, the image area obtained after exposure and development can be improved. The film strength is high and the abrasion resistance is excellent.
Therefore, the work efficiency, cost, etc. of lithographic printing plate production are significantly improved.

[0084]

EXAMPLES The present invention will be described in more detail with reference to synthesis examples and examples, but the contents of the present invention are not limited thereto. Synthesis Example of Silica Coupling Agent Modified Silica Fine Particles 1: M
G1 high - speed stirrer was charged with 10 g of silica fine particles (Mizucasil P-527U manufactured by Mizusawa Chemical Industry Co., Ltd.), 5 g of 3-cyanopropyltrimethoxysilane, 5 g of 25% aqueous ammonia, and 200 ml of toluene, and stirred at 18000 rpm for 1 hour.
Mixed. This mixture was placed in a flask equipped with a stirrer, a cooling tube, and a dehydration trap, and heated and stirred at a toluene reflux temperature for 2 hours.

After stirring, the contents of the flask were separated into a toluene solution and a deposit by a centrifuge at 7,000 rpm for 30 minutes. This deposit was dispersed in 400 ml of acetone using an ultrasonic disperser, and after dispersion, it was separated again by a centrifuge. The operation of washing with acetone was further repeated twice, and the resulting deposit was naturally dried to obtain 12 g of a white powder.

The carbon content measured by elemental analysis was C (%): 6.25, and the particle size was 60 nm when observed by an electron microscope. Synthesis Example 2 of Silica Coupling Agent Modified Silica Fine Particles: M
G-2 high - speed stirrer, 10 g of silica fine particles (Mizukasil P-527U manufactured by Mizusawa Chemical Industry Co., Ltd.), 8 g of 2- (4-chlorosulfonylphenyl) ethyltrichlorosilane, 5 g of water,
200 ml of toluene was added and mixed with stirring at 18000 rpm for 1 hour.

This mixture was placed in a flask equipped with a stirrer, a cooling tube equipped with a trap containing an alkali, and a dehydration trap, and heated and stirred at a toluene reflux temperature for 2 hours. After stirring, centrifuge the contents of the flask to 70
Separation into a toluene solution and a deposit was carried out at 00 rpm for 30 minutes. Acetone 400 was applied to this deposit using an ultrasonic disperser.
It was dispersed in ml, and after dispersion, it was separated again by a centrifuge. This operation of washing with acetone was repeated twice more, and the resulting deposit was naturally dried to obtain 14 g of a white powder.

The carbon content measured by elemental analysis was C (%): 11.1, and the particle size was 60 nm when observed by an electron microscope. Synthesis Example 3 of Silica Coupling Agent Modified Silica Fine Particles: M
G-3 High - speed stirrer, 10 g of silica fine particles (Mizukasil P-527U manufactured by Mizusawa Chemical Industry Co., Ltd.), 2.5 g of 3-cyanopropyltrimethoxysilane, 3 g of benzoxailepine dimethyl ester, 5 g of 25% ammonia solution, and 200 ml of toluene. Was added, and the mixture was stirred and mixed at 18000 rpm for 1 hour.

This mixture was placed in a flask equipped with a stirrer, a condenser and a dehydration trap, and heated and stirred at the reflux temperature of toluene for 2 hours. After stirring, the content of the flask was separated into a toluene solution and a deposit by a centrifuge at 7,000 rpm for 30 minutes. 400 ml of acetone for this deposit
The mixture was dispersed by using an ultrasonic disperser, and after the dispersion, the mixture was again separated by a centrifuge. This operation of washing with acetone was repeated twice more, and the resulting deposit was naturally dried to obtain 12.5 g of a white powder.

The carbon content measured by elemental analysis was C (%): 9.65, and the particle size was 60 nm as observed by an electron microscope. Synthesis Example 4 of Silica Coupling Agent Modified Silica Fine Particles: M
G-4 high speed stirrer contained 10 g of silica fine particles (Mizukasil P-527U manufactured by Mizusawa Chemical Industry Co., Ltd.), 4 g of 2- (4-chlorosulfonylphenyl) ethyltrichlorosilane, 5 g of water,
200 ml of toluene was added, and the mixture was stirred and mixed at 18000 rpm for 1 hour.

This mixture was placed in a flask equipped with a stirrer, a cooling tube equipped with a trap containing an alkali, and a dehydration trap, and heated and stirred at a toluene reflux temperature for 2 hours. After stirring, centrifuge the contents of the flask for 7 minutes.
The toluene solution and the precipitate were separated in 30 minutes at 000 rpm. This deposit was dispersed in 400 ml of acetone using an ultrasonic disperser, and after dispersion, it was separated again by a centrifuge. The operation of washing with acetone was further repeated twice, and the resulting deposit was naturally dried to obtain 12 g of a white powder. The carbon content measured by elemental analysis was C (%): 6.53.

12 g of this white powder was put into a high speed stirrer,
Further, 5.5 g of 25% aqueous ammonia solution and 200 ml of toluene were added thereto, and the mixture was stirred at 18000 rpm for 1 minute, subsequently 2.5 g of 3-cyanopropyltrimethoxysilane was added, and the mixture was stirred at 18000 rpm for 1 hour and mixed. .. This mixture was placed in a flask equipped with a stirrer, a cooling tube, and a dehydration trap, and heated and stirred at a toluene reflux temperature for 2 hours.

After stirring, the contents of the flask were separated into a toluene solution and a deposit by a centrifugal separator at 7,000 rpm for 30 minutes. This deposit was dispersed in 400 ml of acetone using an ultrasonic disperser, and after dispersion, it was separated again by a centrifuge. This operation of washing with acetone was repeated twice more, and the resulting deposit was naturally dried to obtain 13.1 g of a white powder.

The carbon content measured by elemental analysis was C (%): 9.13, and the particle size was 60 nm when observed by an electron microscope. Synthesis example 5 of silica particles modified with silane coupling agent,
6: Silica fine particles (Mizukasil P-527U manufactured by Mizusawa Chemical Industry Co., Ltd.) 10 g, 3-glycidoxypropyltrimethoxysilane 5 g, 25% aqueous ammonia solution 5 in a MG-5 and MG-6 high - speed stirrer
g and 200 ml of toluene were added, and the mixture was stirred and mixed at 18,000 rpm for 1 hour.

This mixture was placed in a flask equipped with a stirrer, a condenser and a dehydration trap, and heated and stirred at the reflux temperature of toluene for 2 hours. After stirring, the content of the flask was separated into a toluene solution and a deposit by a centrifuge at 7,000 rpm for 30 minutes. Acetone 400 with this deposit
The mixture was dispersed in ml using an ultrasonic disperser, and after dispersion, it was separated again by a centrifuge. This operation of washing with acetone was repeated twice more, and the resulting deposit was naturally dried to obtain 12.8 g of white powder (MG-5).

The carbon content measured by elemental analysis was C (%): 9.00, and the particle size was 60 nm when observed by an electron microscope. This white powder (MG-
5) 12.8 g was placed in a flask equipped with a stirrer and a cooling tube, 5 g of p-cyanobenzyl alcohol, 0.2 g of concentrated sulfuric acid and 200 ml of toluene were added, and the mixture was heated and stirred at a toluene reflux temperature for 3 hours. .. After stirring, the content in the flask was separated into a toluene solution and a deposit in a centrifugal separator at 7,000 rpm for 30 minutes.

This precipitate was dispersed in 400 ml of methanol by using an ultrasonic disperser, and after dispersion, it was separated again by a centrifuge. Next, the same washing operation was repeated twice with 400 ml of acetone, and the resulting deposit was naturally dried to obtain 14.5 g of white powder (MG-6). When the carbon content was measured by elemental analysis, C (%):
16.6, and a particle size of 6 when observed with an electron microscope.
It was 0 nm. Synthesis Examples 7 to 3 of Silica Coupling Agent Modified Silica Fine Particles
2: MG-7 to 32 modified silica fine particles Synthesis In the same manner as in Examples 1 to 6, modified silica fine particles MG-7 to MG-32 were synthesized using the silane coupling agent and alcohol shown in Table 1. Observation by an electron microscope showed that the particle size was 60 nm in all cases.

[0098]

[Table 1]

[0099]

[Table 2]

[0100]

[Table 3]

[0101]

[Table 4]

[0102]

[Table 5]

[0103]

[Table 6]

[0104]

[Table 7]

[0105]

[Table 8]

[0106]

[Table 9]

Example 1 99.5% aluminum, 0.01% copper, and 0.00 titanium.
JIS A1 containing 3%, 0.3% iron and 0.1% silicon
050 aluminum material thickness 0.24mm rolled plate 400
A 20 wt% aqueous suspension of mesh pumicetone (manufactured by Kyoritsu Nigyo Co., Ltd.) and a rotating nylon brush (6-10 nylon) were used to grain the surface of the suspension, followed by thorough washing with water.

This was immersed in a 15% by weight sodium hydroxide aqueous solution (containing 5% by weight of aluminum) for etching so that the amount of aluminum dissolved was 5 g / m ² , and then washed with running water. Further, it is neutralized with 1% by weight nitric acid, and then neutralized.
7% by weight nitric acid in water (containing 0.5% by weight of aluminum)
Among them, a rectangular wave alternating waveform voltage (current ratio r = 0.90, Japanese Patent Publication 58) with a voltage of 10.5 volts at the anode and a voltage of 9.3 volts at the cathode.
Electrolytic surface-roughening treatment was performed by using the current waveform described in the example of JP-A-5796) with an electric quantity at the time of anodic of 160 clones / dm ² . After washing with water, immersing in a 10 wt% sodium hydroxide aqueous solution at 40 ° C to dissolve aluminum in an amount of 1 g
After being etched so as to be / m ² , it was washed with water.

Next, in a 30% by weight sulfuric acid aqueous solution at 50 ° C.
It was dipped, desmutted and washed with water. Furthermore, sulfur of 35 ℃
Directly in 20% by weight aqueous acid solution (containing 0.8% aluminum)
A porous anodic oxide film formation treatment was performed using a flowing current.
That is, the current density is 13 A / dm ²Electrolyze for electrolysis time
The weight of anodic oxide film is 2.0g / m²And Washing with water
Then, add 30% to a 3 wt% aqueous solution of sodium silicate at 70 ° C.
It was soaked for 2 seconds, washed with water and dried.

The aluminum support thus obtained had a reflection density of 0.28 as measured by a Macbeth RD920 reflection densitometer and a center line average roughness of 0.54 μm. The following photosensitive liquids [M] -1 to [M] -32 were applied on the thus prepared substrate using a wheeler,
It was dried at 80 ° C. for 2 minutes. The dry weight was 1 g / m ² . Table 2 shows the polymer compounds of the present invention used in the photosensitive liquids [M] -1 to [M] -32. Further, the following copolymer (P-1) was used as the polymer compound.

P-1

[0112]

[Chemical 13]

Photosensitive liquid [M] : Silica coupling agent-modified silica fine particles of the present invention (Table 2)
0.2 g 4-n-dodecylbenzenesulfonate of a condensate of 4-diazodiphenylamine and formaldehyde 0.5 g Polymer compound (P-1) 4.8 g Victoria Pure Blue BOH (Dye manufactured by Hodogaya Chemical Co., Ltd.) 0.1 g Megafac F-177 (manufactured by Dainippon Ink and Chemicals, Inc., fluorine-based nonionic surfactant) 0.02 g 1-methoxy-2-propanol 100 g The modified silica fine particles of the present invention are 1 An ultrasonic dispersion in -methoxy-2-propanol was used.

Next, as a comparative example, a photosensitive solution [N] -using unmodified silica particles and hydrophobic silica particles, which are usually used as a filler in place of the modified silica particles of the present invention in the above-mentioned photosensitive solution. 1, [N] -2 and a photosensitive solution [L] -1 containing no filler (polymerization reduction amount of 0.2 g due to no addition of filler was increased to 5.0 g of polymer compound (P-1)). It was supplemented by the above).

Table 2 shows comparative unmodified silica fine particles and hydrophobic silica fine particles used for the photosensitive liquids [N] -1 and [N] -2. Each photosensitive lithographic printing plate [M] -1 to [M] -1 to [M] -32 and each of the photosensitive lithographic printing plates obtained using [N] -1, [N] -2 and [L] -1. Fuji step film P manufactured by Fuji Photo Film Co., Ltd. is overlaid on M] -32 and [N] -1, [N] -2, [L] -1, and PS light manufactured by Fuji Photo Film Co., Ltd. is used for 1 m. After exposure for 1 minute from the distance of 1 minute and immersion for 1 minute in the developer [A] shown below, the surface was lightly rubbed with a brush to remove the unexposed portion.

Developer [A] Sodium sulfite 5 g Benzyl alcohol 30 g Sodium carbonate 5 g Sodium isopropylnaphthalene sulfonate 12 g Triethanolamine 20 g Water 1000 g The sensitivity of the lithographic printing plate thus obtained to the exposure amount was visually determined. I read it as the number of steps. The results are shown in Table 2. Further, each of these printing plates was applied to a printing machine SOR-M manufactured by Heidelberg. Graph N manufactured by Dainippon Ink Co., Ltd. was used as the ink, and dampening water was printed on coated paper using 10% isopropanol added with 1% EU-3 manufactured by Fuji Photo Film Co., Ltd.

Table 2 also shows the results of examining the printing durability of each printing plate based on the final number of printed sheets of [L] -1 without addition of a filler and setting this as the printing durability of 100%. Table 2 ─────────────────────────────────── Modified silica fine particles used in photosensitive lithographic printing plate and development Printing durability after (%) Filler Number of steps of solid part ──────────────────────────────────── 〔 M] -1 MG-1 6 150 [M] -2 MG-2 4 120 [M] -3 MG-3 6 140 [M] -4 MG-4 6 140 [M] -5 MG-5 4 115 [ M] -6 MG-6 6 140 [M] -7 MG-7 5 120 [M] -8 MG-8 5 120 [M] -9 MG-9 6.5 155 [M] -10 MG-10 6 .5 150 [M] -11 MG-11 4 115 [M] -12 MG-12 6 140 [M] -13 MG-13 13 115 115 [M] -14 MG-14 6 145 [M] -15 MG- 15 4 115 [M] -16 MG 16 6 150 [M] -17 MG-17 4 120 [M] -18 MG-18 6 150 [M] -19 MG-19 5 150 [M] -20 MG-20 5 150 [M] -21 MG- 21 6 150 [M] -22 MG-22 6 150 [M] -23 MG-23 5 5 145 [M] -24 MG-24 6 155 [M] -25 MG-25 6 155 [M] -26 MG- 26 6 155 [M] -27 MG-27 5 150 [M] -28 MG-28 6 155 [M] -29 MG-29 4 150 [M] -30 MG-30 6 150 [M] -31 MG- 31 4 150 [M] -32 MG-32 6 150 [N] -1 (Comparative Example) Mizukasil P-527U 3 100 (Mizawa Chemical Co., Ltd.) [N] -2 (Comparative Example) Aerosil R972 3 105 (Nippon Aerosil Co., Ltd.) [L] -1 (Comparative example) ─── 3 100 ─────────────────────────── ───────── From Table 2, the silane coupling agent-modified silica fine particles of the present invention are printing plates prepared by adding ordinary fillers [N] -1 and [N] -2 shown in Comparative Examples. And [L] -1, the number of steps in the solid part and the printing durability were excellent as compared with the printing plate with no added filler, and a printing plate having high sensitivity and high printing durability was provided.

Example 2 To 99.5% aluminum, 0.01% of copper and 0.0% of titanium were added.
JIS A1 containing 3%, 0.3% iron and 0.1% silicon
050 aluminum material thickness 0.24mm rolled plate 400
A 20% by weight aqueous suspension of mesh pumice (manufactured by Kyoritsu Nigyo Co., Ltd.) and a rotating nylon brush (6-10 nylon) were used to grain the surface of the suspension, followed by thorough washing with water.

This was immersed in a 15% by weight sodium hydroxide aqueous solution (containing 5% by weight of aluminum) to perform etching so that the amount of aluminum dissolved was 5 g / m ² , and then washed with running water. Further neutralize with 1% by weight nitric acid, then
In a 0.7% by weight aqueous nitric acid solution (containing 0.5% by weight of aluminum), a rectangular wave alternating waveform voltage (current ratio r = 0.90, voltage at anode: 10.5 V, voltage at cathode: 9.3 V) Electrolytic surface roughening treatment was carried out using the current waveform described in the example of JP-B-58-5796) with an electric quantity at the anode of 160 clones / dm ² . After washing with water, it was dipped in a 10% by weight aqueous sodium hydroxide solution at 40 ° C., etched so that the amount of aluminum dissolved was 1 g / m ² , and then washed with water.

Next, it was immersed in a 30% by weight aqueous solution of sulfuric acid at 50 ° C., desmutted, and washed with water. Further, a porous anodic oxide film forming treatment was carried out using a direct current in a 20% by weight sulfuric acid aqueous solution (containing 0.8% by weight of aluminum) at 35 ° C. That is, electrolysis was performed at a current density of 13 A / dm ² , and the anodic oxide film weight was adjusted to 2.0 g / m ² by adjusting the electrolysis time.
After washing with water, it was immersed in a 3% by weight aqueous solution of sodium silicate at 70 ° C. for 30 seconds, washed with water and dried.

The aluminum support thus obtained had a reflection density of 0.28 as measured by a Macbeth RD920 reflection densitometer and a center line average roughness of 0.54 μm. The following photosensitive solutions [V] -1 to [V] -32 were applied on the thus prepared substrate using a wheeler,
It was dried at 80 ° C. for 2 minutes. The dry weight was 1 g / m ² . Table 3 shows the polymer compounds of the present invention used in the photosensitive liquids [V] -1 to [V] -32. Further, the following copolymer (P-2) was used as the polymer compound.

P-2

[0123]

[Chemical 14]

Photosensitive liquid [V] : Silica coupling agent-modified silica fine particles of the present invention (Table 3)
0.2g 4-diazodiphenylamine and 4-n-dodecylbenzene sulfonate of a condensate of phenoxyacetic acid and formaldehyde 0.5g Polymer compound (P-2) 4.8g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) Dye) 0.1 g Megafac F-177 (manufactured by Dainippon Ink and Chemicals, fluorine-based nonionic surfactant) 0.02 g 1-methoxy-2-propanol 100 g The modified silica fine particles of the present invention are preliminarily 1 An ultrasonic dispersion in -methoxy-2-propanol was used.

Next, as a comparative example, a photosensitive solution [W] -using unmodified silica fine particles and hydrophobic silica fine particles, which are usually used as a filler in place of the modified silica fine particles of the present invention in the above-mentioned photosensitive solution. 1, [W] -2 and a photosensitive solution [K] -1 containing no filler (polymerization reduction amount of 0.2 g due to no addition of filler was increased to 5.0 g of the polymer compound (P-2)). It was supplemented by the above).

Table 3 shows comparative unmodified silica fine particles and hydrophobic silica fine particles used for the photosensitive liquids [W] -1 and [W] -2. Each of the photosensitive lithographic printing plates [V] -1 to [V] -1 to [V] -32 and [W] -1, [W] -2 and [K] -1 obtained using the photosensitive liquids [V] -1 to [V] -32. V] -32 and [W] -1, [W] -2, and [K] -1 are overlaid with a gray scale tablet manufactured by Fuji Photo Film Co., Ltd., and PS light manufactured by Fuji Photo Film Co., Ltd. After exposing from a distance for 1 minute and immersing in the following developing solution [B] for 1 minute,
The surface was lightly rubbed with a brush to remove the unexposed portion. still,
The pH of the developer was 13.

Developer [B] SiO ₂ / Na ₂ O Sodium silicate having a molar ratio of about 1.2 g 25 g water 1000 g The sensitivity of the lithographic printing plate thus obtained to the exposure amount was visually evaluated as the number of steps of the solid part. Read The results are shown in Table 3. Further, each of these printing plates was applied to a printing machine SOR-M manufactured by Heidelberg. Graph N manufactured by Dainippon Ink Co., Ltd. was used as the ink, and 1% EU-3 manufactured by Fuji Photo Film Co., Ltd. was added to 10% isopropanol for dampening water.
The addition was used to print on coated paper.

Table 3 also shows the results of examining the printing durability of each printing plate based on the final number of printed sheets of [K] -1 with no added filler as 100% printing durability. Table 3 ──────────────────────────────────── Modified silica fine particles used in photosensitive lithographic printing plate and development Printing durability after (%) Filler Number of steps of solid part ──────────────────────────────────── 〔 V] -1 MG-1 6 150 [V] -2 MG-2 4 120 [V] -3 MG-3 6 140 [V] -4 MG-4 6 140 [V] -5 MG-5 4 120 [ V] -6 MG-6 6 150 [V] -7 MG-7 5 120 [V] -8 MG-8 5 120 [V] -9 MG-9 7 155 [V] -10 MG-10 7 140 [ V] -11 MG-11 4 120 [V] -12 MG-12 6 130 [V] -13 MG-13 4 120 [V] -14 MG-14 6 145 [V] -15 MG-15 4 115 [ V] -16 MG-16 6 150 [V] -17 MG-17 4 120 [V] -18 MG-18 6 155 [V] -19 MG-19 5 155 [V] -20 MG-20 5 155 [V] -21 MG-21 6 155 [V] -22 MG-22 6 150 [V] -23 MG-23 5 140 [V] -24 MG-24 6 155 [V] -25 MG-25 6 155 [V] -26 MG-26 6 155 [V] -27 MG-27 5 150 [V] -28 MG-28 6 155 [V] -29 MG-29 4 150 [V] -30 MG-30 6 150 [V] -31 MG-31 4 150 [V] -32 MG-32 6 150 [W] -1 (comparative example) Mizukasil P-527U 395 (manufactured by Mizusawa Chemical Co., Ltd.) [W] -2 (comparative example) Aerosil R972 3 100 (comparative example) Made by Nippon Aerosil Co., Ltd. [K] -1 (comparative example) ─── 3 100 ───────────────────────────── From Table 3, the silane coupling agent-modified silica fine particles of the present invention are shown in Comparative Examples as [W] -1, [W] -2 printing plates by addition of usual fillers and [K]. As compared with the printing plate of No. 1 without the addition of the filler, both the number of steps of the solid part and the printing durability were excellent, and a printing plate with high sensitivity or printing durability was provided.

Example 3 Photosensitive planographic printing plate [V] -9 obtained from Example 2,
[V] -10 and [W] -1, [W] -2, [K] -1
A gray scale tablet manufactured by Fuji Photo Film Co., Ltd. is overlaid on the above, and exposed with a PS light manufactured by Fuji Photo Film Co., Ltd. for 1 minute from a distance of 1 m.
After soaking for a minute, the surface was lightly rubbed with a brush to remove the unexposed portion. The pH of the developer was 12 or less.

Developer [C] Sodium hydrogencarbonate 10 g Sodium carbonate 20 g Sodium n-butylnaphthalene sulfonate 50 g Water 1000 g The sensitivity of the obtained lithographic printing plate to the exposure amount was visually read as the number of solid steps. The results are shown in Table 4.

Each of these printing plates was placed on a printer SOR-M manufactured by Heidelberg. Graph N manufactured by Dainippon Ink Co., Ltd. was used as the ink, and isopropanol 1 was used as the fountain solution.
Printing was performed on coated paper using 0% of 1% EU-3 manufactured by Fuji Photo Film Co., Ltd. added. Based on the final number of printed sheets of [K] -1 with no filler added, this is the printing durability 1
The results of examining the printing durability of each printing plate as 00% are also shown in Table 4.

From Table 4, photosensitive lithographic printing plate [V] -9 using the silane coupling agent-modified fine particles of the present invention,
[V] -10 has a larger number of stages, higher sensitivity, and excellent printing durability than the photosensitive lithographic printing plates [W] -1, [W] -2, and [K] -1 of Comparative Examples. Was there. Table 4 ──────────────────────────────────── Modified silica fine particles used in photosensitive lithographic printing plate and development Printing durability after (%) Filler Number of steps of solid part ──────────────────────────────────── 〔 V] -9 MG-9 7 155 [V] -10 MG-10 7 150 [W] -1 (comparative example) Mizukasil P-527U 3 105 (manufactured by Mizusawa Chemical Industry Co., Ltd.) [W] -2 (comparative) Example) Aerosil R972 3 110 (manufactured by Nippon Aerosil Co., Ltd.) [K] -1 (comparative example) ─── 3 100 ─────────────────────── ─────────────

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location H01L 21/027

Claims (1)

[Claims] 1. A negative type photosensitive composition containing a diazonium compound and a polymer compound, further comprising surface modification in which at least one functional group represented by the following general formula (I) is linked to the particle surface by a chemical bond. A photosensitive composition comprising fine silica particles. [Chemical 1] (In the formula, R represents a divalent linking group consisting of two or more kinds of atoms selected from C, H, N, O, S and Si, and Y represents And A ¹ and A ² each represent O or S, and Q ¹ , Q ³ and Q ⁴ each represent H or a C _{1 to} C ₁₅ hydrocarbon group which may have a substituent. , Q ² represents a C _{1 to} C ₁₅ hydrocarbon group which may have a substituent. )