JPH08320559A - Photosensitive composition and photosensitive planographic printing plate - Google Patents

Abstract

PURPOSE: To improve chemical resistance, printing resistance, development latitude, suitability to writing with a ball point pen and suitability to the adhesion of a cellophane adhesive tape without deteriorating developability by using a specified polymer as an alkali-soluble resin. CONSTITUTION: In a positive type photosensitive compsn. contg. an o- quinonediazide compd. and an alkali-soluble resin, a polymer contg. at least one structural unit represented by formula I is used as the alkali-soluble resin. In the formula I each of R1 -R3 is H, alkyl or phenyl and X is a group represented by formula II, III, etc. In the formula II, R4 is 1-5C alkylene and each of R5 and R6 is H, alkyl or phenyl. In the formula III, R7 is 1-5C alkylene and each of R8 and R9 is H or an alkyl-contg. aliphatic or arom. group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive composition and a photosensitive lithographic printing plate, and in particular, chemical resistance, printing durability, suitability for suitable developing conditions, suitability for ballpoint pen, cellophane adhesive tape without degrading developability. The present invention relates to a positive photosensitive composition and a photosensitive lithographic printing plate which have high suitability.

[0002]

BACKGROUND OF THE INVENTION Conventionally, as an alkali-soluble resin in a photosensitive composition used for a printing plate, a novolac resin or a vinyl polymer having a phenolic hydroxyl group, JP-A-55 is used.
Condensation resins of polyhydric phenols and aldehydes or ketones described in Japanese Patent No. 57841 are used. Generally, vinyl monomers include unsaturated carboxylic acids such as acrylic acid, esters such as methyl acrylate, phenolic hydroxyl group-containing monomers such as hydroxyphenylacrylamide, and vinyl cyanide compounds such as acrylonitrile. It is used.

In general, a positive-working photosensitive lithographic printing plate using an o-quinonediazide compound has a high sensitivity, excellent chemical resistance and printing durability, and a range of conditions under which suitable development can be carried out. There is a demand for a wide variety. Further, as the support, an aluminum plate or the like is generally used from the viewpoints of hydrophilicity, water retention, adhesion to the photosensitive layer and the like. Here, the chemical resistance refers to various chemicals used at the time of printing, such as isopropyl alcohol, printing ink, surface-adjusting liquid, and plate cleaner. In addition, when performing so-called multi-sided printing in which a plurality of original films are printed one after another at different positions on the photosensitive lithographic printing plate, the positions of the originals may be marked on the photosensitive layer for alignment between the original films. Although an oil-based ballpoint pen is usually used as a writing tool for marking, there is a problem that the solvent of the oil-based ballpoint pen ink is eroded and the photosensitive layer is dissolved. In particular, when the marked portion is the image portion, if the development processing is performed as it is, the photosensitive layer of the mark portion of the image portion is removed, and the mark mark is reproduced on the printed matter at the time of printing, which causes a failure.

Further, for the purpose of fixing the original film during exposure or exposing it in an overlapping manner, it is often the case that a cellophane adhesive tape is directly stuck on the printing plate. These cellophane adhesive tapes are peeled off after baking the original film, but the glue of the cellophane adhesive tapes peeled off during plate making remains on the printing plate, causing poor development and causing a problem of plate surface stains during printing.

In order to obtain such properties as chemical resistance, printing durability, suitability for suitable developing conditions, suitability for ballpoint pens, etc., an o-quinonediazide sulfonic acid ester of a polymer polycondensation resin and a polymer binder have been conventionally used in the photosensitive layer. Techniques such as inclusion have been used, but the alkali solubility decreases as the film strength increases, and problems such as reduced sensitivity and deteriorated developability occur.

Conventionally, a fluorinated surfactant or a nonionic surfactant is added to the photosensitive layer, or an acrylate or methacrylate having a fluoroaliphatic group is added.
It is known that the inclusion of a copolymer with acrylate or methacrylate improves ballpoint pen suitability and cellophane adhesive tape suitability, but these surfactants and the like are used in large amounts to improve ballpoint pen suitability and cellophane adhesive tape suitability. When it is added to, the problem that the sensitivity of the photosensitive lithographic printing plate is lowered or the developability is deteriorated occurs.

[0007]

It is an object of the present invention to provide a photosensitive composition capable of improving chemical resistance, printing durability, acceptability of suitable developing conditions, suitability for ballpoint pen, and suitability for cellophane adhesive tape without deteriorating developability. And a second object is to provide a photosensitive lithographic printing plate capable of achieving the above object.

[0008]

The above-mentioned problems of the present invention are as follows. A positive photosensitive composition containing an o-quinonediazide compound and an alkali-soluble resin, wherein the alkali-soluble resin is a polymer containing at least one structural unit represented by the following general formula [I]. Sex composition,

[0009]

[Chemical 6] R ₁ , R ₂ , and R ₃ represent hydrogen, an alkyl group, or a phenyl group, and X represents any of the following (1) to (7).

[0010]

[Chemical 7] R ₄ represents an alkylene group having 1 to 5 C, and R ₅ and R ₆ represent hydrogen, an alkyl group or a phenyl group.

[0011]

Embedded image R ₇ is an alkylene group having a C number of 1 to 5, and R ₈ and R ₉ are hydrogen or an aliphatic or aromatic group containing an alkyl group, which may be the same or different.

[0012]

[Chemical 9]

2. In a positive photosensitive composition containing an o-quinonediazide compound and an alkali-soluble resin, the alkali-soluble resin comprises a structural unit containing a phenolic hydroxyl group and structural units represented by the following general formulas [II] and [III]. A photosensitive composition which is a copolymer containing at least one;

[0014]

[Chemical 10] R _{1 to} R ₉ represent hydrogen, an alkyl group, or a phenyl group.

3. A photosensitive lithographic printing plate characterized in that a photosensitive layer containing the photosensitive composition according to 1 or 2 above is provided on an aluminum support that has been subjected to graining treatment and anodizing treatment. It

[0016]

According to the present invention, in a positive photosensitive composition containing an o-quinonediazide compound and an alkali-soluble resin, the alkali-soluble resin contains at least one structural unit represented by the general formula [I]. By having a constitution that it is a united structure or a copolymer containing a structural unit having a phenolic hydroxyl group and at least one structural unit represented by the general formulas [II] and [III], the developability is improved. It is possible to improve chemical resistance, printing durability, suitability for suitable developing conditions, suitability for ballpoint pen, and suitability for cellophane adhesive tape without dropping.

[0017]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in more detail below. (Support) The aluminum support used in the present invention includes a support made of pure aluminum and an aluminum alloy. Various aluminum alloys can be used, for example, an alloy of aluminum with a metal such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, or nickel.

(Degreasing Treatment) The aluminum support is preferably subjected to a degreasing treatment in order to remove rolling oil on the aluminum surface prior to roughening. As degreasing treatment,
Degreasing treatment using a solvent such as trichlene and thinner, emulsion degreasing treatment using an emulsion of kesilon and triethanol and the like are used. Also, for degreasing treatment,
It is also possible to use an aqueous solution of alkali such as caustic soda. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, it is possible to remove stains and oxide films which cannot be removed only by the above degreasing treatment.

(Graining treatment) As a graining treatment method performed for improving the adhesion to the photosensitive layer and improving the water retention property, a so-called mechanical rough surface is used in which the surface is mechanically roughened. And a so-called electrochemical surface roughening method in which the surface is electrochemically roughened. Mechanical surface roughening methods include, for example, ball polishing, brush polishing, blast polishing,
There are methods such as buffing. The electrochemical surface roughening method includes, for example, a method of electrolytically treating the support with an alternating current or a direct current in an electrolytic solution containing hydrochloric acid, nitric acid, or the like. The support can be grained by using any one of them or a combination of two or more thereof. Since smut is formed on the surface of the support obtained by the graining treatment as described above, it is generally preferable to appropriately perform washing with water or alkali etching in order to remove the smut. Examples of such a treatment include the alkaline etching method described in Japanese Patent Publication No. 48-28123 and Japanese Patent Laid-Open No. 53-1273.
Examples thereof include a treatment method such as a sulfuric acid desmutting method described in JP-A-9.

(Anodic oxidation treatment) An oxide film is formed on the support by anodic oxidation in order to improve abrasion resistance, chemical resistance and water retention. In this anodic oxidation, generally, a method of electrolyzing with an aqueous solution containing sulfuric acid and / or phosphoric acid or the like at a concentration of 10 to 50% at a current density of 1 to 10 A / dm ² is preferably used. A method of electrolyzing in sulfuric acid at a high current density as described in Japanese Patent No. 1,412,768 and US Pat. No. 3,511,6
61, there is a method of electrolyzing using phosphoric acid.

(Sealing treatment) The support may be subjected to sealing treatment after the anodizing treatment. Examples of the sealing treatment include boiling water treatment, steam treatment, sodium silicate treatment, dichromate aqueous solution treatment, nitrite treatment, and ammonium acetate treatment.

(Hydrophilic treatment) Further, it is preferable that the support is subjected to an anodizing treatment (further after the pore-sealing treatment) and then a hydrophilic treatment, that is, a hydrophilic layer is provided.
Examples of the hydrophilic layer include alkali metal silicates described in US Pat. No. 3,181,461 and US Pat.
Hydrophilic cellulose described in JP-A No. 0,426, amino acids and salts thereof described in JP-A-60-149491 and 63-165183, JP-A-60-2329.
No. 98, hydroxyl group-containing amines and salts thereof, JP-A-62-19494, phosphate salts, and polymer containing a sulfo group-containing monomer unit, described in JP-A-59-101651. A compound etc. are mentioned.

Further, in order to prevent scratches on the photosensitive layer when the photosensitive lithographic printing plates are superposed, and to prevent elution of the aluminum component into the developing solution at the time of development, JP-A-50-50
-151136, 57-63293, 60-7.
No. 3538, No. 61-67863, JP-A-6-351.
The treatment of providing a protective layer on the back surface of the support described in No. 74 etc. can be performed.

(Photosensitive layer) Next, a photosensitive layer containing the following photosensitive composition of the present invention (claim 1 or 2) is coated on the surface-treated aluminum support and dried. As a result, the photosensitive lithographic printing plate of the present invention (claim 3) is obtained. The photosensitive substance used in this photosensitive layer is not particularly limited, and various substances usually used in photosensitive lithographic printing plates can be used. Hereinafter, this point will be described.

(Photosensitive Composition Containing o-Quinonediazide Compound) o Used in the positive-type photosensitive composition layer of the present invention.
-The quinonediazide compound is a compound having an o-quinonediazide compound in the molecule, and the o-quinonediazide compound that can be used in the present invention is not particularly limited, and examples thereof include a compound having an o-quinonediazide group. Examples thereof include an ester compound of a condensation resin, for example, o-naphthoquinonediazide sulfonic acid and a polycondensation resin of phenols and aldehydes or ketones.

Examples of the above-mentioned phenols include monohydric phenols such as phenol, o-cresol, m-cresol, p-cresol, 3,5-xylenol, carvacrol and thymol, and dihydric compounds such as catechol, resorcinol and hydroquinone. Examples include trihydric phenols such as phenol, pyrogallol, and phloroglucin. Examples of the aldehyde include formaldehyde, benzaldehyde, acetaldehyde, crotonaldehyde, and furfural. Preferred of these are formaldehyde and benzaldehyde. Examples of the ketone include acetone and methyl ethyl ketone.

Specific examples of the polycondensation resin include phenol / formaldehyde resin, m-cresol / formaldehyde resin, m- and p-mixed cresol / formaldehyde resin, resorcin / benzaldehyde resin, pyrogallol / acetone resin and the like. To be

The condensation rate of o-naphthoquinonediazide sulfonic acid with respect to the OH group of the phenol of the o-naphthoquinonediazide compound (reaction rate for one OH group) is
15 to 80% is preferable, and 20 to 45 is more preferable.
%.

Further, as the o-quinonediazide compound used in the present invention, the following compounds described in JP-A-58-43451 can also be used. That is, for example, 1, 2
-Benzoquinone diazide sulfonate, 1,2-
Known 1,2-naphthoquinone diazide sulfonic acid ester, 1,2-benzoquinone diazide sulfonic acid amide, 1,2-naphthoquinone diazide sulfonic acid amide, etc.
Quinone diazide compounds, more specifically J. Kosar "Light-Sensitive Systems" (Light-Sensitive System)
ems) pp. 339-352 (1965), John.
Willie & Sons (John Willey &
Sons, Inc. (New York) and W. S. De Forest, "Photoresist", Volume 50 (1975), McGraw H
ill) (New York) 1,2-
Benzoquinonediazide-4-sulfonic acid phenyl ester, 1,2,1 ', 2'-di- (benzoquinonediazide-4-sulfonyl) -dihydroxybiphenyl, 1,2
-Benzoquinonediazide-4- (N-ethyl-M-β-
Naphthyl) -sulfonamide, 1,2-naphthoquinonediazide-5-sulfonic acid cyclohexyl ester, 1-
(1,2-naphthoquinonediazide-5-sulfonyl)-
3,5-Dimethylpyrazole, 1,2-naphthoquinonediazide-5-sulfone-4'-hydroxydiphenyl-
4'-azo-β-naphthol-ester, N, N-di-
(1,2-naphthoquinonediazide-5-sulfonyl)-
Aniline, 2 '-(1,2-naphthoquinonediazide-5
-Sulfonyloxy) -1-hydroxy-anthraquinone, 1,2-naphthoquinonediazide-5-sulfone-
2,4-dihydroxybenzophenone ester, 1,2
-Naphthoquinonodiazide-5-sulfonic acid-2,3,4
-Trihydroxybenzophenone ester, a condensate of 2 mol of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 1 mol of 4,4'-diaminobenzophenone,
Condensate of 2 mol of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 1 mol of 4,4′-dihydroxy-1,1′-diphenylsulfone, 1 mol of 1,2-naphthoquinonediazide-5-sulfonic acid chloride Examples thereof include a 1,2-quinonediazide compound such as a condensate of 1 mol of purpurogallin and 1,2-naphthoquinonediazide-5- (N-dihydroabietyl) -sulfonamide. In addition, Japanese Examined Patent Publications No. 37-1953 and 37-3627
Nos. 37-13109, 40-26126, 40-3801, 45-5604, 45-27.
No. 345, No. 51-13013, JP-A-48-965.
The 1,2-quinonediazide compounds described in JP-A No. 75, 48-63802 and 48-63803 can also be mentioned.

Of the above o-quinonediazide compounds,
An o-quinone diazide ester compound obtained by reacting 1,2-benzoquinone diazide sulfonyl chloride or 1,2-naphthoquinone diazide sulfonyl chloride with pyrogallol-acetone condensation resin or 2,3,4-trihydroxybenzophenone is particularly preferable. As the o-quinonediazide compound used in the present invention, the above compounds may be used alone or in combination of two or more kinds. The proportion of the o-quinonediazide compound in the photosensitive composition is preferably 6 to 60% by weight, and particularly preferably 10 to 50% by weight.

(Alkali-Soluble Resin) The alkali-soluble resin used in the photosensitive composition of the present invention is a polymer containing at least one structural unit represented by the general formula [I] in the present invention shown in claim 1. The present invention according to claim 2 is a copolymer comprising a structural unit having a phenolic hydroxyl group and at least one structural unit represented by the general formulas [II] and [III]. Incidentally, other alkali-soluble resins as the third component, for example, novolac resins, condensation resins of polyhydric phenols and aldehydes or ketones described in JP-A-55-57841, as long as the effects of the present invention are not impaired. Etc. may be included.

Specific examples of the monomer having the structural unit represented by the general formula [I] include (1) N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, N, N- Diethylaminoethyl acrylate, N, N-diethylaminoethyl methacrylate, etc. (2) R ₇ is preferably ethylene,
For example, EO-modified phenoxyphosphoric acid acrylate, EO
Modified phenoxy phosphate acrylate, EO modified phosphate methacrylate, EO modified phosphate dimethacrylate, E
O-modified phosphoric acid diacrylate, EO-modified phosphoric acid triacrylate, EO, BuOH-modified phosphoric acid acrylate, E
O, BuOH modified methacrylate, EO, octanol modified phosphate acrylate, EO, octanol phosphate methacrylate, etc. (3) Dicyclopentanyl acrylate, dicyclopentanyl methacrylate, etc. (4) Dicyclopentenyl acrylate, dicyclopentenyl methacrylate , EO-modified dicyclopentenyl acrylate, EO-modified dicyclopentenyl methacrylate, etc.,
(5) Glycidyl acrylate, glycidyl methacrylate, etc., (6) Isobornyl acrylate, isobornyl methacrylate, etc., (7) Tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, caprolactone-modified tetrahydrofurfuryl acrylate,
Examples thereof include caprolactone-modified tetrahydrofurfuryl methacrylate.

The monomer having the structural unit shown in the present invention is preferably a copolymer with another vinyl-based monomer, and as the other vinyl-based monomer, those conventionally used can be used. However, unsaturated carboxylic acids such as acrylic acid, esters such as methyl acrylate, phenolic hydroxyl group-containing monomers such as hydroxyphenylacrylamide, and vinyl cyanide compounds such as acrylonitrile are preferable. In the case of a copolymer with another vinyl-based monomer, the proportion of the structural unit represented by the present invention is preferably 2 to 50 mol%. The proportion of the vinyl-based polymer in the photosensitive layer is 0.5. ˜70 wt% is preferred. The molecular weight of the vinyl polymer is preferably Mw.
In the range of 2000 to 300,000, the number average of Mn is 1000 to 2
It is in the range of 50,000. Polydispersity (Mw / Mn) is 1.1-
The range is 10.

Next, the vinyl-based copolymer having a phenolic hydroxyl group used in the present invention as defined in claim 2 is a polymer having a unit having the phenolic hydroxyl group in its molecular structure and has the following general formula: [IV] to [VII
Polymers containing at least one structural unit of I] are preferred.

[0035]

[Chemical 11]

In the above general formulas [IV] to [VIII], R
₁ and R ₂ each represent a hydrogen atom, an alkyl group or a carboxyl group, preferably a hydrogen atom. R ₃ represents a hydrogen atom, a halogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group such as a methyl group or an ethyl group. R ₄ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, preferably a hydrogen atom. A
Represents a alkylene group which may have a substituent, which connects a nitrogen atom or an oxygen atom and an aromatic carbon atom,
m represents an integer of 0 to 10, and B represents a phenylene group which may have a substituent or a naphthylene group which may have a substituent. Specific structural units include, for example, the following (1) to (8).

[0037]

[Chemical 12]

[0038]

[Chemical 13]

Examples of conventionally used vinyl monomers include ethylenically unsaturated olefins such as ethylene, propylene, isobutylene, butadiene and isoprene, such as styrene, α-methylstyrene, p-methylstyrene and p-chlorostyrene. Styrenes such as, acrylic acid, acrylic acids such as methacrylsan, for example, itaconic acid, maleic acid, unsaturated aliphatic dicarboxylic acids such as maleic anhydride, such as methyl acrylate, ethyl acrylate, -n-butyl acrylate, Esters of α-methylene aliphatic monocarboxylic acids such as isobutyl acrylate, dodecyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate and ethyl ethacrylate. , For example Ronitoriru, nitriles methacrylonitrile, etc., such as acrylamide, amides such as methacrylamide, such as acrylic anilide, p
-Chloroacrylanilide, m-nitroacrylanilide, m-methoxyacrylanilide and other anilides such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and other vinyl esters such as methyl vinyl ether, ethyl vinyl ether and isobutyl vinyl ether. , Vinyl ethers such as β-chloroethyl vinyl ether, vinyl chloride, vinylidene chloride, vinylidene cyanide, for example, 1-methyl-1-methoxyethylene, 1,1-dimethoxyethylene, 1,2-dimethoxyethylene, 1,1-dimethoxy. Carbonyl ethylene, 1
Ethylene derivatives such as -methyl-1-nitroethylene,
For example, N-vinylpyrrole, N-vinylcarbazole,
There are N-vinyl type monomers such as N-vinyl indole, N-vinyl pyrrolidene and N-vinyl pyrrolidone. These monomers are present in the polymer compound with a structure in which the unsaturated double bond is cleaved. Among the above monomers, aliphatic monocarboxylic acid esters and nitriles exhibit excellent performance and are preferable. These monomers including the monomer of the present invention may be bonded to the polymer either in a block or random state.

Specific examples of the compound having the structure represented by the general formula [II] include tetrafluoropropyl acrylate, tetrafluoropropyl methacrylate, tetrafluorobutyl acrylate, tetrafluorobutyl methacrylate and the like.

Specific compounds having the structure represented by the above general formula [III] include trifluoroethyl acrylate, trifluoroethyl methacrylate, trifluoropropyl acrylate and trifluoropropyl methacrylate.

The monomer having the structural unit shown in the present invention is particularly preferably a copolymer with a structural unit having a phenolic hydroxyl group. The monomer having the structural unit shown in the present invention is preferably a copolymer with another vinyl-based monomer, and as the other vinyl-based monomer, those conventionally used can be used. However, unsaturated carboxylic acids such as acrylic acid, esters such as methyl acrylate, and vinyl cyanide compounds such as acrylonitrile are preferable. The ratio of the structural unit represented by the present invention is preferably 2 to 50 mol%, and the ratio of the structural unit having a phenolic hydroxyl group is 1
It is preferably 0 to 60 mol%. The proportion of the vinyl polymer in the photosensitive layer is preferably 0.5 to 70% by weight. The molecular weight of the vinyl polymer is preferably Mw of 20.
00-300,000, Mn of 1000-20,000, polydispersity (Mw
/ Mn) is in the range of 1.1 to 10.

Preferable novolak resins used in combination with the present invention are, for example, phenol / formaldehyde resin, cresol / formaldehyde resin, JP-A-55-
Phenol as described in Japanese Patent No. 57841
Cresol / formaldehyde copolymer resin, JP-A-5
Examples thereof include copolymer resins of p-substituted phenol and phenol, or cresol and formaldehyde as described in JP-A-5-127553. The novolak resin preferably has a number average molecular weight Mn of 3.00 × 10 ^{2 to} 7.50 × (polystyrene standard).
10 ³ , and the weight average molecular weight Mw is 1.00 × 10 ^{3 to} 3.
00 × 10 ⁴ , more preferably Mn of 5.00 × 10 ^2.
˜4.00 × 10 ³ , Mw 3.00 × 10 ^{3 to} 2.0
It is 0 × 10 ⁴ . The above novolak resins may be used alone or in combination of two or more. The proportion of the novolak resin in the photosensitive composition is preferably 5 to 95% by weight.

(Organic Acid / Inorganic Acid / Anhydride) The photosensitive composition of the present invention may contain an organic acid / inorganic acid / anhydride. Examples of the acid used in the present invention include organic acids described in JP-A No. 60-88942 and Japanese Patent Application No. 63-293107, and "Chemical Handbook New Edition" edited by The Chemical Society of Japan, No. 92-158. The inorganic acids described on the page can be mentioned.
Examples of organic acids include p-toluenesulfonic acid, dodecylbenzenesulfonic acid, mesitylenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzensulfonic acid,
Sulfonic acids such as m-benzenedisulfonic acid, sulfinic acids such as p-toluenesulfinic acid, benzylsulfinic acid and methanesulfinic acid, phosphonic acids such as phenylphosphonic acid, methylphosphonic acid and chloromethylphosphonic acid,
Aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, pentanoic acid, hexanoic acid and heptanoic acid, alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid, benzoic acid, o-, m-, p -Hydroxybenzoic acid,
o-, m-, p-methoxybenzoic acid, o-, m-, p-
Aromatic monocarboxylic acids such as methylbenzoic acid, 3,5-dihydroxybenzoic acid, phloroglysin carboxylic acid, gallic acid and 3,5-dimethylbenzoic acid can be mentioned. Also,
Saturated or unsaturated aliphatic dicarboxylic acids such as malonic acid, methylmalonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, itaconic acid, malic acid, tetrahydro Phthalic acid, 1,1-cyclobutanedicarboxylic acid,
1,1-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3
Examples thereof include alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid.

Among the above organic acids, more preferable one is p
-Toluenesulfonic acid, dodecylbenzenesulfonic acid,
Examples include sulfonic acid such as mesitylenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzensulfonic acid, and m-benzenedisulfonic acid, cis-1,2-cyclohexanedicarboxylic acid, and syringic acid. Examples of the inorganic acid include nitric acid, sulfuric acid, hydrochloric acid, silicic acid, phosphoric acid and the like, more preferably sulfuric acid and phosphoric acid.

When an acid anhydride is used, the type of acid anhydride is also arbitrary, and those derived from aliphatic / aromatic monocarboxylic acids such as acetic anhydride, propionic anhydride, benzoic anhydride, and succinic anhydride. , Maleic anhydride, glutaric anhydride, phthalic anhydride, and the like, and the like derived from aliphatic / aromatic dicarboxylic acids. Preferred acid anhydrides are glutaric anhydride and phthalic anhydride. These compounds may be used alone or in combination of two or more. The content of these acids is generally 0.05 to 5% by weight, and preferably 0.1 to 3% by weight, based on the total solid content of the entire photosensitive composition.

(Surfactant) The photosensitive composition of the present invention may contain a surfactant. As the surfactant, an amphoteric surfactant, an anionic surfactant, a cationic surfactant,
Nonionic surfactants, fluorine-based surfactants and the like can be mentioned.

Examples of the amphoteric surfactant include lauryl dimethylamine oxide, lauryl carboxymethyl hydroxyethyl, imidazolinium betaine and the like.
As the anionic surfactant, a fatty acid salt, an alkyl sulfate ester salt, an alkylbenzene sulfonate, an alkylnaphthalene sulfonate, an alkylsulfosuccinate,
Examples thereof include alkyl diphenyl ether disulfonate, alkyl phosphate, polyoxyethylene alkyl sulfate ester salt, polyoxyethylene alkyl allyl sulfate ester salt, naphthalene sulfonic acid formalin condensate, and polyoxyethylene alkyl phosphate ester. Examples of cationic surfactants include alkylamine salts, quaternary ammonium salts, and alkyl betaines. As the nonionic surfactant, polyoxyethylene alkyl ether,
Polyoxyethylene alkyl allyl ether, polyoxyethylene derivative, oxyethylene / oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxy Examples include ethylene alkylamines and alkyl alkanolamides.

Examples of the fluorinated surfactants include copolymers of acrylates or methacrylates containing a fluoroaliphatic group and (polyoxyalkylene) acrylates or (polyoxyalkylene) methacrylates. For example, JP-A Nos. 62-170950 and 62-2.
26143, U.S. Pat. No. 3,787,351 and the like (for example, Megafac F-171,173,1).
77, Defencer MCF300, 312, 313 (all manufactured by Dainippon Ink and Chemicals, Inc.), Modiper F-10
0, 102, 110 (manufactured by NOF CORPORATION) and the like. These compounds may be used alone or in combination of two or more. The proportion in the photosensitive composition is preferably 0.01 to 10% by weight, more preferably 0.01 to 5% by weight.

(Printout Material) A printout material capable of forming a visible image upon exposure can be added to the photosensitive composition. The printout material comprises an organic dye which changes its color tone by interacting with a compound which forms an acid or a free radical upon exposure. Examples of the compound which forms an acid or a free radical upon exposure include, for example, JP-A-50- O described in Japanese Patent No. 36209
-Naphthoquinonediazide-4-sulfonic acid halogenide,
An ester compound or amide compound of o-naphthoquinonediazide-4-sulfonic acid chloride and an electron-withdrawing substituent phenol or aniline acid described in JP-A-53-36223, JP-A-55-
Examples thereof include halomethylvinyloxadiazole compounds and diazonium salts described in JP-A 77742, JP-A-57-148784 and the like.

(Compound which produces an acid or a free radical upon exposure to light) Examples of the compound which produces an acid or a free radical upon exposure to light which can be used in the photosensitive composition of the present invention include, for example, halomethyloxadiazole compounds, A halomethyl-s-triazine compound or the like is used. The halomethyl oxadiazole compound is a compound having halomethyl group, preferably trichloromethyl group, in oxadiazoles.

These compounds are known, for example, Japanese Patent Publication Nos. 57-6096 and 61-51788,
Japanese Patent Publication No. 1-28369, JP-A-60-13853
No. 9, JP 60-177340, and JP 60-24.
It is described in Japanese Patent No. 1049. In addition, the halomethyl-s-triazine compound is a compound having one or more halomethyl groups, preferably a trichloromethyl group, in the s-triazine ring.

In the photosensitive composition of the present invention, the addition amount of the compound capable of generating an acid or a free radical upon exposure to light is 0.
01 to 30% by weight is preferable, and 0.1 is more preferable.
10 to 10% by weight, particularly preferably 0.2 to 3% by weight. These compounds may be used alone or in combination of two or more.

(Dye) 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 which 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 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 Co., Ltd.), Oil Blue #
603 (manufactured by Orient Chemical Industry Co., Ltd.), patent pure blue (manufactured by Sumitomo Mikuni Chemical Co., Ltd.), crystal violet,
Brilliant Green, Ethyl Violet, Methyl Violet, Methyl Green, Erythrosin B, Pesic Fuchsin, Malachite Green, Oil Red, m
-Cresol purple, rhodamine B, auramine,
Triphenylmethane-based, diphenylmethane-based, oxazine-based, xanthene-based, iminonaphthoquinone-based, azomethine-based, or anthraquinone-based dyes such as 4-p-diethylaminophenyliminaquinoquine and cyano-p-diethylaminophenylacetanilide are colored to colorless. Alternatively, it may be mentioned as an example of a color changing agent that changes to a different color tone.

On the other hand, as a discoloring agent that changes from colorless to colored, 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. The proportion of the above-mentioned discoloring agent in the photosensitive composition is preferably 0.01 to 10% by weight, more preferably 0.02 to
Used at 5% by weight. These compounds may be used alone or in combination of two or more. Particularly preferred dyes are Victoria Pure Blue BOH and Oil Blue # 6.
It is 03.

(Oil-sensitizer) An oil-sensitizer for improving the oil-sensitivity of the image area (for example, a half-esterified product of an alcohol of a styrene-maleic anhydride copolymer described in JP-A-55-527). , Pt-butylphenol-
Novolak resins such as formaldehyde resins, or partial esterification products of these with o-quinonediazide compounds, fluorine-based surfactants, p-hydroxystyrene 5
0% fatty acid ester, etc.) are preferably used. The amount of these additives added varies depending on the object of use and purpose, but is generally 0.01 to 30% by weight based on the total solid content. Dissolve each of these components in the following solvent,
By coating on the surface of the support and drying, a photosensitive layer can be provided to produce the photosensitive lithographic printing plate of the invention. There is no special limitation on the usage of the solvent.

(Solvent) As a solvent which can be used when the photosensitive composition used in the present invention is dissolved, methanol,
Ethanol, n-propanol, i-propanol, n
-Aliphatic alcohols such as butanol, n-pentanol and hexanol, allyl alcohol, benzyl alcohol, anisole, phenetole, n-hexane, cyclohexane, heptane, hydrocarbons such as octane, nonane and decane, diacetone alcohol, 3 -Methoxy-1
-Butanol, 4-methoxy-1-butanol, 3-ethoxy-1-butanol, 3-methoxy-3-methyl-
1-butanol, 3-methoxy-3-ethyl-1-1-pentanol-4-ethoxy-1-pentanol, 5-methoxy-1-hexanol, acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, methyl isobutyl ketone, Methyl pentyl ketone, methyl hexyl ketone, ethyl butyl ketone, dibutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, γ-butyrolactone, 3-hydroxy-2-butanone, 4-hydroxy-2-butanone, 4-hydroxy-2- Pentanone, 5-hydroxy-2-pentanone, 4-hydroxy-3-pentanone, 6-hydroxy-2-hexanone, 3-methyl-3-hydroxy-2-
Pentanone, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, ethylene glycol monoacetate, ethylene glycol diacetate, propylene glycol monoacetate, propylene glycol diacetate, ethylene glycol alkyl ethers and their acetates (MC, EC , Butyl cellosolve,
Phenyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, MC acetate, EC acetate), diethylene glycol monoalkyl ethers and their acetates (diethylene glycol monomethyl ether, monoethyl ether, mono i-propyl ether, monobutyl ether, Diethylene glycol monomethyl ether acetate, etc.), diethylene glycol dialkyl ethers (DMDG, DEDG, D
BDG, MEDG), triethylene glycol alkyl ethers (monomethyl ether, monoethyl ether, dimethyl ether, diethyl ether, methyl ethyl ether, etc.), propylene glycol alkyl ethers and their acetates (monomethyl ether, monoethyl ether, n-propyl ether) , Monobutyl ether, dimethyl ether, diethyl ether, monomethyl ether acetate, monoethyl ether acetate, etc.), dipropylene glycol alkyl ethers (monomethyl ether, monoethyl ether, n-propyl ether, monobutyl ether, dimethyl ether, diethyl ether), ethyl formate , Propyl formate,
Carboxylic esters such as butyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, dimethylformamide, dimethylsulfoxide, dioxane, tetrahydrofuran, methyl lactate ,
Examples thereof include ethyl lactate, methyl benzoate, ethyl benzoate, propylene carbonate and the like. These solvents can be used alone or in combination of two or more.

(Coating Layer) In the photosensitive lithographic printing plate according to the present invention, a coating layer made of a water-insoluble organic solvent-soluble polymer compound capable of forming a film can be formed on the photosensitive layer.

(Matting Agent) On the surface of the photosensitive layer provided as described above, a matting layer is formed in order to shorten the vacuuming time during contact exposure using a vacuum baking frame and to prevent baking blur. Is preferably provided. Specifically, JP-A-5
0-125805, Japanese Patent Publication No. 57-6582, 61
No. 28986, a method of providing a mat layer as described in JP-B No. 28986, and a method of heat-bonding a solid powder as described in JP-B No. 62-62337 are listed. The purpose of the matte layer is to improve the vacuum adhesion between the 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. Is. As a method for applying the matte layer, a method of heat-sealing powdered solid powder described in JP-A-55-12974 and a spray of polymer-containing water described in JP-A-58-182636. The mat layer itself can be dissolved in an alkali developing solution or can be removed by this method.

(Inclusion Compound) The photosensitive composition of the present invention may contain an inclusion compound. Next, the inclusion compound will be described. The clathrate is a state in which a three-dimensional structure formed by combining atoms or molecules has voids, and another or molecules enter into the three-dimensional structure at a constant composition ratio to form a specific structure. Therefore, the clathrate compound refers to a compound having a property of incorporating another molecule or atom into the vacancy formed by itself.
The driving force that causes this inclusion is hydrophobic interaction,
Ionic interactions, hydrogen bonds, van der Waals forces, etc. are considered. Specific examples of the inclusion compound, cyclodextrin, crown ether, cyclophane, azacyclophane, calixarene, cyclotriveratrylene, spherand, capitand, those having a clathrate ability in a single molecule such as a cyclic oligopeptide, Urea, thiourea, theoxycholic acid, apocholic acid, cholic acid, dinitrodiphenyl, hydroquinone, perhydrotriphenylene, tri-o-thymoid, oxyflavan, dicyanoamminenickel, dioxytriphenylmethane, methylnaphthalene, spirocoumarin, perhydro Examples thereof include those having a clathrate ability in a multi-molecular system such as triphenylene. Further, natural polymers such as cellulose, starch, chitin, chitosan, and proteins, and synthetic polymers such as polyvinyl alcohol also include various compounds. These compounds can be used alone or in combination of two or more.

(Coating) As a coating method for coating the photosensitive composition or the coating layer or the mat layer on the surface of the support, conventionally known methods such as spin coating, wire bar coating, dip coating and air knife can be used. Coating, roll coating,
Blade coating and curtain coating are used.

(Exposure) In using the photosensitive lithographic printing plate thus obtained, a conventionally used method can be applied. For example, a transparent original image having a line image, a halftone image or the like can be applied to the photosensitive surface. A relief image is obtained by exposing the film in close contact with it and then removing the photosensitive layer in the non-image area with a suitable developing solution. Suitable light sources for exposure include mercury lamps, metal halide lamps, xenon lamps,
Chemical lamps, carbon arc lamps, etc. are used.

(Processing) In the present invention, the developing solution and the developing replenishing solution used for the developing process of the photosensitive lithographic printing plate both contain an alkali metal silicate. The alkali metals of alkali metal silicates include lithium, sodium,
Potassium is included, of which potassium is most preferred. At the time of development, it is preferable that the development replenisher is appropriately replenished in accordance with the development processing amount of the photosensitive lithographic printing plate.

The preferred developing solution and developing replenishing solution are [SiO 2
₂ ] / [M] (in the formula, [SiO ₂ ] represents the molar concentration of SiO ₂ and [M] represents the molar concentration of alkali metal), and the SiO ₂ concentration is It is an aqueous solution of an alkali metal silicate that is 0.5 to 5.0% by weight based on the total weight. Further, it is particularly preferable that the developing solution [SiO
₂ ] / [M] is 0.25 to 0.75, the SiO ₂ concentration is 1.0 to 4.0% by weight, and the development replenisher [SiO ₂ ]
/ [M] is 0.15 to 0.5, and the SiO ₂ concentration is 1.0 to 3.0% by weight.

The above-mentioned developing solution and developing replenishing solution may contain water-soluble or alkali-soluble organic and inorganic reducing agents. Examples of the organic reducing agent include hydroquinone, metol, phenol compounds such as methoxyquinone, phenylenediamine, amine compounds such as phenylhydrazine, and the like, examples of inorganic reducing agents include sodium sulfite, potassium sulfite, and the like. Sulfites such as ammonium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, sodium phosphite, potassium phosphite, sodium hydrogen phosphite, potassium hydrogen phosphite, sodium dihydrogen phosphite, potassium dihydrogen phosphite Phosphite, hydrazine, sodium thiosulfate, etc.
Examples thereof include sodium dithionite. These water-soluble or alkali-soluble reducing agents can be contained in the developing solution and the developing replenishing solution in an amount of 0.05 to 10% by weight. Further, the developing solution and the developing replenishing solution may contain an organic acid carboxylic acid.

These organic acid carboxylic acids include aliphatic carboxylic acids having 6 to 20 carbon atoms, and aromatic carboxylic acids having a benzene ring or naphthalene ring substituted with a carboxyl group.

The aliphatic carboxylic acid has 6 to 2 carbon atoms.
Alkanoic acid of 0 is preferable, and specific examples thereof include caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, mistyric acid, palmitic acid,
Stearic acid and the like can be mentioned, with carbon number 6 being particularly preferred.
~ 12 alkanoic acids. Further, the aliphatic carboxylic acid may be a fatty acid having a double bond in the carbon chain or a fatty acid having a branched carbon chain. The aliphatic carboxylic acid may be used as a sodium or potassium salt or an ammonium salt.

Specific examples of the aromatic carboxylic acid include benzoic acid, o-chlorobenzoic acid, p-chlorobenzoic acid, o-hydroxybenzoic acid, p-hydroxybenzoic acid, p-tert-butylbenzoic acid, o-aminobenzoic acid, p-aminobenzoic acid, 2,4-dihydroxybenzoic 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-
Naphthoic acid and the like can be mentioned.

The aromatic carboxylic acid may be used as a sodium or potassium salt or an ammonium salt. The content of the aliphatic carboxylic acid and the aromatic carboxylic acid may be at least 0.1 to 30% by weight. The developer and development replenisher may contain various anionic, nonionic and cationic surfactants and organic solvents. Furthermore, the developer and development replenisher should be
Known additives can be added.

[0071]

EXAMPLES The present invention will be described more specifically with reference to the following examples. (Preparation of support) An aluminum plate (material 1050, temper H16) having a thickness of 0.3 mm was degreased for 1 minute in a 5% sodium hydroxide aqueous solution kept at 65 ° C., and then washed with water, 25 It was immersed for 1 minute in a 10% sulfuric acid aqueous solution kept at 0 ° C., neutralized, and washed with water. This aluminum plate was electrolytically surface-roughened by an alternating current in a 1.8 wt% nitric acid aqueous solution under the conditions of a temperature of 25 ° C., a current density of 100 A / dm ² , and a treatment time of 60 seconds. Then, desmutting treatment is performed in a 5% aqueous sodium hydroxide solution at 60 ° C. for 10 seconds, and then anodizing is performed in a 20% sulfuric acid solution at a temperature of 20 ° C., a current density of 3 A / dm ² , and a treatment time of 1 minute. Processed. Then, soak in a 1% sodium nitrite aqueous solution kept at 80 ° C for 30 seconds, wash with water, and then at 3 ° C at 3 ° C.
Dried for minutes. Furthermore, after immersing in an aqueous solution of carboxymethyl cellulose (concentration: 0.1 wt%) kept at 85 ° C. for 30 seconds, it was dried at 80 ° C. for 5 minutes to prepare a support.

(Photosensitive Solution) Novolac resin (phenol / m-cresol / p-cresol molar ratio 10/54/36, weight average molecular weight 4000) 5.4 g pyrogallolacetone resin (weight average molecular weight 3000) and o- Condensation product of naphthoquinone di azido-5-sulfonyl chloride (esterification rate: 30%) 1.5 g Acrylic resin (copolymer-1 shown in Table 1) 1.3 g Hydroxypropyl-β-cyclodextrin )) 0.15 g polyethylene glycol # 2000 0.2 g Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) 0.08 g 2,4-bis (trichloromethyl) -6- (p-methoxystyryl) -s-triazine 0.15 g S-381 (manufactured by Asahi Glass Co., Ltd.) 0.03 g cis-1,2-cyclohex Sandicarboxylic acid 0.2g MC (methyl cellosolve) 100ml

(Synthesis of Copolymers-1 to 11) A monomer mixture having a monomer composition ratio (mol%) shown in Table 1 was used to convert the monomer mixture in such a manner that the total concentration of the monomers would be 7.15 mol%. A solution was prepared, and azobisisobutyronitrile in an amount of 2.1 mol% equivalent to the total monomer ratio was added to the solution, and the mixture was refluxed at 80 ° C. for 6 hours under a nitrogen stream while stirring. After completion of the reaction, hydroquinone in a total monomer ratio of 0.04% by weight was added and the reaction solution was poured into water to precipitate a copolymer, which was collected by filtration and dried at 60 ° C. for 3 days.

[0074]

[Table 1] Molecular weight measurement: Hitachi 653 type GPC column: shodx KF-802xKF-803xK
F-804 (monomer in the table) HyPMA: p-hydroxyphenylmethacrylamide AN: acrylonitrile EA: ethyl acrylate MMA: methyl methacrylate: N, N-dimethylaminoethyl methacrylate: EO-modified phenoxyphosphoric acid acrylate: dicyclo Pentanyl acrylate: EO-modified dicyclopentenyl acrylate: Glycidyl methacrylate: Isobornyl acrylate: Tetrahydrofurfuryl acrylate: Tetrafluoropropyl acrylate

(Preparation of photosensitive lithographic printing plate sample 1) The photosensitive liquid was applied onto the support using a wire bar to prepare a photosensitive lithographic printing plate sample 1 shown in Table 2, and the sample 1 was prepared.
Was evaluated by the following evaluation method, and the results are shown in Table 3.

(Preparation of photosensitive lithographic printing plate samples 2 to 8 and comparative samples 9 to 11) Of the above-mentioned photosensitive liquid applied to sample 1,
The same photosensitive solution except that the copolymer-1 was changed as shown in Table 2 was coated on the support using a wire bar to prepare photosensitive lithographic printing plate samples 2 to 8 and comparative samples 9 to 11, respectively. Created. Each sample was evaluated by the following evaluation method, and the results are shown in Table 3.

[0077]

[Table 2]

(Evaluation method) = Sensitivity = A step tablet for sensitivity measurement (No. 2, Eastman Kodak Co., Ltd., 21 steps of gray scale with a density difference of 0.15) was adhered to the sample, and a 4Kw metal halide lamp (large) was attached. Nippon Screen Co., Ltd., “Vio Quick”
Was used as a light source and exposed from a distance of 90 cm. Next, this sample was developed at 27 ° C. for 20 seconds with a developer obtained by diluting SDR-1 (manufactured by Konica) developer 6 times with water. The sensitivity was defined as the exposure time at which 3.0 steps of the step tablet was completely cleared.

= Appropriate development condition = (difference in halftone dot sensitivity variation) A plate control wedge (UGRA
PCW) was brought into close contact, and a 4 Kw metal halide lamp (Bio Quick manufactured by Dainippon Screen Co., Ltd.) was used as a light source and exposed for 20 seconds from a distance of 90 cm. Next, this sample was developed with a developer obtained by diluting SDR-1 (manufactured by Konica) developer 4 times and 9 times with water at 27 ° C. for 20 seconds. Above plate control wedge (UGRA PC
Visually observe the reproducibility of the circular patch with a magnifying glass of W). (The smaller the circular patch variation of UGRA PCW, the smaller the halftone dot sensitivity variation difference, and the wider the range of suitable developing conditions.)

= Printing durability = A sample tablet for sensitivity measurement (No. 2, Eastman Kodak Company, 21-step gray scale with 0.15 density difference) was adhered to the sample, and a 4Kw metal halide lamp (Dainippon Screen) was used. (Bio Quick Co., Ltd.)
Was used as a light source and exposed from a distance of 90 cm. Next, this sample was developed at 27 ° C. for 20 seconds with a developer obtained by diluting SDR-1 (manufactured by Konica) developer 6 times with water. The lithographic printing plate thus obtained was applied to a printing machine GTO manufactured by Heidelberg Co., Ltd., and coated paper, printing ink (New Bright Red manufactured by Toyo Ink Mfg. Co., Ltd.), and fountain solution (SEU-3 manufactured by Konica;
2.5%) was used for printing, and printing was continued until defective solidification of the image of the printed matter appeared or ink was non-printed in the non-image area, and the number of printed sheets at that time was counted.

= Suitability of Ballpoint Pen = A register mark was drawn on a sample with a register printer and development was carried out after 2 minutes, and suitability of the ballpoint pen was evaluated according to how the photosensitive layer was attacked by the pilot's ballpoint pen. (Similar to development condition sensitivity) Criteria ○: Non-image area is not affected at all Δ: Part of non-image area is affected ×: Non-image area is affected and support is exposed

[Suitability of Cellophane Adhesive Tape] Cellophane adhesive tape (Nichiban) was applied to the plate of the sample, left for 24 hours, then peeled off, exposed and developed. The suitability of the cellophane adhesive tape was evaluated based on the degree of poor development in the area where the cellophane adhesive tape was attached. (Similar to development condition sensitivity) Judgment criteria ○: No effect at all x: Development failure is recognized

= Chemical resistance = The sample was developed (similar to the sensitivity of developing conditions), and the obtained sample was immersed in a stock solution of Ultra Plate Cleaner (Dainichi Seika Co., Ltd.) for 15 minutes and then immersed in the stock solution for 45 minutes. After that, it was washed with water and visually compared with the image area before immersion for evaluation. Judgment Criteria ○: No erosion in the image area Δ: Slight erosion in the image area and slightly exposed grain of the support under the photosensitive layer ×: Significant erosion in the image area, support under the photosensitive layer The grain of the body is completely exposed

[0084]

[Table 3]

[0085]

According to the present invention, the developing property is not deteriorated,
It is possible to provide a photosensitive composition and a photosensitive lithographic printing plate which can improve chemical resistance, printing durability, suitability for suitable developing conditions, suitability for ballpoint pen, suitability for cellophane adhesive tape.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical display location G03F 7/033 G03F 7/033 (72) Inventor Shinichi Matsubara 1 Sakura-cho, Hino-shi, Tokyo Konica Stock In the company

Claims (3)

[Claims] 1. A positive photosensitive composition containing an o-quinonediazide compound and an alkali-soluble resin, wherein the alkali-soluble resin is a polymer containing at least one structural unit represented by the following general formula [I]. A photosensitive composition comprising: Embedded image R ₁ , R ₂ , and R ₃ represent hydrogen, an alkyl group, or a phenyl group, and X represents any of the following (1) to (7). Embedded image R ₄ represents an alkylene group having 1 to 5 C, and R ₅ and R ₆ represent hydrogen, an alkyl group or a phenyl group. Embedded image R ₇ is an alkylene group having a C number of 1 to 5, and R ₈ and R ₉ are hydrogen or an aliphatic or aromatic group containing an alkyl group, which may be the same or different. [Chemical 4] 2. A positive-type photosensitive composition containing an o-quinonediazide compound and an alkali-soluble resin, wherein the alkali-soluble resin has a structural unit containing a phenolic hydroxyl group and the following general formulas [II] and [III]: A photosensitive composition, which is a copolymer containing at least one structural unit shown. Embedded image R _{1 to} R ₉ represent hydrogen, an alkyl group, or a phenyl group. 3. A photosensitive lithographic printing plate characterized by comprising a photosensitive layer containing the photosensitive composition according to claim 1 or 2 on an aluminum support which has been subjected to a graining treatment and an anodizing treatment. .