JP3534901B2 - Photosensitive composition, photosensitive lithographic printing plate and method for developing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive composition, a photosensitive lithographic printing plate and a method for developing the same, and more specifically, a photosensitive composition containing no cellsolve coating solvent and containing substantially no organic solvent. The present invention relates to a photosensitive lithographic printing plate which can be developed with an aqueous alkaline solution and a developing method thereof.

[0002]

BACKGROUND OF THE INVENTION Conventionally, a cellosolve type solvent has been used as a coating solvent for a photosensitive composition, but teratogenicity has been recognized in this solvent and various alternative solvents have been considered.
However, some of them have concerns about coating properties such as uneven coating.

Further, in the image forming method using a negative photosensitive composition, in the developing treatment after exposure, the photosensitive layer in the unexposed area is eluted with an organic solvent or an alkaline aqueous solution containing them to form an image. The method of forming was common. However, the use of a developer containing an organic solvent
It is feared that the odor of the solvent may deteriorate the working environment of the plate making process and may adversely affect the health of the worker.
Therefore, a negative photosensitive lithographic printing plate that can be developed with an alkaline aqueous solution containing substantially no organic solvent has been proposed, but there are still some that are not sufficiently developed for an alkaline aqueous solution.

[0004]

OBJECT OF THE INVENTION It is an object of the present invention to provide a photosensitive composition having excellent coatability, a photosensitive lithographic printing plate having excellent alkali aqueous solution developing suitability and a developing method thereof.

[0005]

The above-mentioned problems of the present invention are as follows. Diazo compounds, alkali-soluble polymer compounds, light weight
Compounding initiator, polymerizable unsaturated compound, n-propanol and
And a photosensitive composition containing diacetone alcohol ,

2. Diazo compound, alkali-soluble polymer
Compound, photopolymerization initiator, polymerizable unsaturated compound, propylene
Glycol monomethyl ether and diacetone al
A photosensitive composition comprising a call ,

3. Diazo compound, alkali-soluble polymer
Compound, photopolymerization initiator, polymerizable unsaturated compound, 3-meth
Contains xyl-1-butanol and diacetone alcohol
A photosensitive composition characterized by having:

4. Diazo compound, alkali-soluble polymer
Compound, photopolymerization initiator, polymerizable unsaturated compound, n-pro
Contains propanol and 4-hydroxy-2-butanone
The photosensitive composition characterized by that,

5. Diazo compound, alkali-soluble polymer
Compound, photopolymerization initiator, polymerizable unsaturated compound, propylene
Glycol monoethyl ether and 4-hydroxy
-2-Butanone-containing photosensitive composition,

6. Diazo compound, alkali-soluble polymer
Compound, photopolymerization initiator, polymerizable unsaturated compound, propylene
Glycol monomethyl ether acetate and 4-
A photosensitive composition comprising hydroxy-2-butanone ,

7. Diazo compound, alkali-soluble polymer
Compound, photopolymerization initiator, polymerizable unsaturated compound, propylene
Containing glycol glycol monoethyl ether and methyl lactate
It characterized feeling light composition to have,

8. Diazo compound, alkali-soluble polymer
Compound, photopolymerization initiator, polymerizable unsaturated compound, propylene
Glycol monoethyl ether and methyl carbito
Feel you characterized by containing Lumpur optical composition,

9. Diazo compound, alkali-soluble polymer
Compound, photoinitiator, polymerizable unsaturated compound, cyclohexene
Contains xanone and 4-hydroxy-2-butanone
You characterized feeling light composition that that, 10. Diazo compound and aromatic diazonium salt at 25 ℃
Solution in water or 50 wt% ethanol solution
Is a co-condensation resin with an aromatic compound having a pKa of 10 or less.
9. The feeling according to any one of 1 to 8 above
Light composition,

11 . 11. The photopolymerization initiator comprises a) a triazine-based compound, b) a mixture of a thioxanthone-based compound and an amine-based compound, or c) a mixed system of the a and b described in any one of 1 to 10 above. A photosensitive composition,

12 . On a hydrophilic support, the above-mentioned 1
11. A photosensitive lithographic printing plate characterized by being coated with one of the photosensitive compositions of

13 . The development method of the photosensitive lithographic printing plate produced by the method described in 12 above is characterized in that the development is performed with an alkaline aqueous solution having a pH of 12 or more.

[0017]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in more detail below. 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.

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, trichlene,
A degreasing treatment using a solvent such as thinner, an emulsion degreasing treatment using an emulsion such as kesilon and triethanol, and the like are used. In addition, an alkaline aqueous solution such as caustic soda can be used for the degreasing treatment. 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.

The graining treatment method carried out to improve the adhesion to the photosensitive layer and to improve the water retention is as follows:
There are a so-called mechanical surface-roughening method for mechanically roughening the surface and a so-called electrochemical surface-roughening method for electrochemically roughening the surface. Examples of the mechanical surface roughening method include ball polishing, brush polishing, blast polishing, and buff polishing. 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. One of these
One or a combination of two or more methods makes it possible to grain the support.

Since smut is formed on the surface of the support obtained by the graining treatment as described above, it is generally necessary to appropriately perform washing with water or alkali etching in order to remove the smut. preferable. Examples of such a treatment include the alkaline etching method described in Japanese Patent Publication No. 48-28123 and Japanese Patent Laid-Open No. 53-53.
Examples thereof include a treatment method such as a sulfuric acid desmutting method described in 12739.

The support usually has abrasion resistance, chemical resistance,
An oxide film is formed by anodic oxidation in order to improve 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. Patent No. 1,41
There are a method of electrolyzing in sulfuric acid at a high current density described in 2,768, a method of electrolyzing using phosphoric acid described in US Pat. No. 3,511,661, and the like.

The support is subjected to a surface treatment such as an alkali silicate treatment, hot water treatment or the like, or a water-soluble polymer compound such as polyvinylphosphonic acid or an aqueous solution of potassium fluorozirconate after the anodization treatment. Preferably.

Then, a photosensitive layer containing the photosensitive composition of the present invention (claims 1 to 11 ) described below is coated on the surface-treated support to form the photosensitive lithographic printing plate of the invention ( Claim 12 ) is obtained. The photosensitive material used in this photosensitive layer is not particularly limited, and usually,
Various materials used for the photosensitive lithographic printing plate can be used. Hereinafter, this point will be described.

The claim by applying a (photosensitive layer) The photosensitive layer comprising a photosensitive composition according to claim 1 to 11 to the surface treated support on 12
To obtain a photosensitive lithographic printing plate. The photosensitive substance used in this photosensitive layer is a known diazo compound , alkali-soluble
A photosensitive composition containing a polymerizable polymer compound, a photopolymerization initiator, and a polymerizable unsaturated compound may be used.

The diazo compound in this photosensitive composition is, for example, preferably a diazo resin represented by a condensation product of an aromatic diazonium salt and formaldehyde or acetaldehyde. Particularly preferably, a reaction product of a salt of a condensate of p-diazophenylamine with formaldehyde or acetaldehyde, for example, hexafluoroborophosphate, tetrafluoroborate, perchlorate or periodate, and the condensate is formed. Examples thereof include diazo resin inorganic salt which is a product, and diazo resin organic salt which is a reaction product of the condensate and sulfonic acids as described in US Pat. No. 3,300,309. . Furthermore, diazo resins are preferably used with binders. As the binder, various polymer compounds can be used, but preferably, a monomer having an aromatic hydroxyl group as described in JP-A-54-98613, such as N- (4 -Hydroxyphenyl) acrylamide, N-
(4-hydroxyphenyl) methacrylamide, o-,
Copolymers of m- or p-hydroxystyrene, o-, m-, or p-hydroxyphenyl methacrylate with other monomers, described in U.S. Pat. No. 4,123,276. Polymers containing hydroxyethyl acrylate units or hydroxyethyl methacrylate units as main repeating units, such as shellac,
Natural resins such as rosin, polyvinyl alcohol, linear polyurethane resins as described in US Pat. No. 3,751,257, phthalated resins of polyvinyl alcohol, epoxy resins condensed from bisphenol A and epichlorohydrin , Cellulose acetate, cellulose acetate phthalate, and other cellulose derivatives.

In the tenth aspect , the diazo compound is
It is a cocondensation resin of an aromatic diazonium salt and an aqueous solution thereof at 25 ° C. or an aromatic compound having a pKa of 10 or less in a 50 wt% ethanol solution. As the aromatic compound having a pKa of 10 or less, those having a COOH or SO ₃ H group are preferable, and benzoic acid, hydroxybenzoic acid, phenylacetic acid and the like are particularly preferable.

As the photosensitive composition used in the present invention, the following compounds other than the above can be used. 1) Photocrosslinking-type photosensitive resin composition The photosensitive component in the photocrosslinking-type photosensitive resin composition is composed of a photosensitive resin having an unsaturated double bond in the molecule. For example, US Pat. No. 3,030, No. 208, No. 3, 4
No. 35,237 and No. 3,622,320, etc., the photosensitive group in the polymer main chain is used as a photosensitive group.

[0028]

[Chemical 1] And a photosensitive resin having a photosensitive group in the side chain of the polymer, a photosensitive resin having a maleimide group in the side chain of the polymer as described in JP-A-62-294238, and the like. To be

2) Photopolymerizable photosensitive resin composition A photopolymerizable composition containing an addition polymerizable unsaturated compound, which comprises a monomer having a double bond or a monomer having a double bond. A typical example of such a composition comprising a polymer binder is disclosed in, for example, US Pat. No. 2,760,8.
No. 63 and No. 2,791,504.

As an example, a composition containing methylmethacrylate, a composition containing methylmethacrylate and polymethylmethacrylate, a composition containing methylmethacrylate, polymethylmethacrylate and polyethyleneglycolmethacrylate monomers, methylmethacrylate, an alkyd resin. A photopolymerizable composition such as a composition containing a polyethylene glycol dimethacrylate monomer is used.
This photopolymerization type photosensitive resin composition includes a photopolymerization initiator usually known in this technical field (for example, benzoin derivative such as benzoin methyl ether, benzophenone derivative such as benzophenone, thioxanthone derivative, anthraquinone derivative, acridone derivative, etc. ) Is added.

[0031]

In the eleventh aspect , as the photopolymerization initiator, a) a triazine compound, b) a mixture of a thioxanthone compound and an amine compound, or c) the a and b.
It consists of a mixed system with.

[0033]

[Chemical 2] R ¹ is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, sec. -Butyl group, ter
t. -Represents a butyl group and halogen. a and b are 0 ≦ a + b
Represents an integer that satisfies ≦ 4.

[0034]

[Chemical 3] R ² , R ³ and R ⁴ are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec. -Butyl group, tert. Represents a butyl group. Ar represents a substituted or unsubstituted phenylene group, naphthylene group, or heterocyclic aromatic group.

[0035]

[Chemical 4] Ar represents a substituted or unsubstituted phenylene group, naphthylene group, or heterocyclic aromatic group. R ⁵ is a hydrogen atom, an alkyl group, an alkoxy group, a dialkylamino group, an alkylthio group, hydroxy group, halogen, -COOR ^6, -
^{_{O- (CH 2) f -COOR 6}} ,

[0036]

[Chemical 5] ^{-R 8 -COOR 6, -R 8 -CONHR} 6, -NHC
Represents OR ⁹ . (R ⁶ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group. R ⁷ is a hydrogen atom or a methyl group, R ⁸ is an alkylene group, R ⁹ is an alkyl group, a substituted alkyl group or an alkoxy group. Represents an aryl group or a substituted aryl group, and f and g represent an integer of 1 to 10.) c represents an integer of 0 to 2. X represents halogen. d, e
Represents an integer of 0 to 3, but is within the range of f + g ≦ 5.

(Alkali-Soluble Resin) As the alkali-soluble resin used in the photosensitive composition of the present invention, novolak resins, vinyl polymers having phenolic hydroxyl groups, and JP-A-55-57841 are described. Examples thereof include condensation resins of polyhydric phenol and aldehyde or ketone.

Examples of the novolac resin used in the present invention include phenol / formaldehyde resin, cresol / formaldehyde resin, JP-A-55-57841.
Phenol-cresol-formaldehyde copolymer resin as described in JP-A-55-127
Examples thereof include copolymer resins of p-substituted phenol and phenol or cresol and formaldehyde as described in Japanese Patent No. 553.

The novolak resin preferably has a number average molecular weight Mn of 3.00 × (polystyrene standard).
10 ^{2 to} 7.50 × 10 ³ , and the weight average molecular weight Mw is 1.
00 × 10 ^{3 to} 3.00 × 10 ⁴ , more preferably Mn
Is 5.00 × 10 ^{2 to} 4.00 × 10 ³ , and Mw is 3.0.
It is 0 × 10 ^{3 to} 2.00 × 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. Further, the vinyl copolymer having a phenolic hydroxyl group preferably used in the present invention is a polymer having a unit having the phenolic hydroxyl group in the molecular structure, and is represented by the following general formula [I] to
Polymers containing at least one structural unit of [V] are preferred.

[0040]

[Chemical 6]

[In the formula, 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 an optionally substituted alkylene group connecting a nitrogen atom or an oxygen atom and an aromatic carbon atom, m represents an integer of 0 to 10, and B represents
Represents a phenylene group which may have a substituent or a naphthylene group which may have a substituent. ]

The polymer used in the present invention preferably has a copolymer type structure, and is represented by the above general formula [I].
~ Examples of the monomer unit that can be used in combination with the structural unit represented by the general formula [V] include ethylenically unsaturated offylenes such as ethylene, propylene, isobutylene, butadiene, and isoprene, for example, styrene and α-. Styrenes such as methylstyrene, p-methylstyrene and p-chlorostyrene, acrylic acids such as acrylic acid and methacrylic acid, and unsaturated aliphatic dicarboxylic acids such as itacone, maleic acid and maleic anhydride,
For example, methyl acrylate, ethyl acrylate, -n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, Α such as ethyl methacrylate
-Esters of methylene aliphatic monocarboxylic acid, for example, nitriles such as acrylonitrile, methacrylonitrile, etc., amides such as acrylamide, such as acrylanilide, p-chloroacrylanilide, m-nitroacrylanilide, m-methoxyacrylanilide, etc. Anilides such as vinyl acetate, vinyl propionate,
Vinyl esters such as vinyl benzoate and vinyl acetate,
For example, methyl vinyl ether, ethyl vinyl ether,
Isobutyl vinyl ether, vinyl ethers such as β-chloroethyl vinyl ether, vinyl chloride, vinylidene chloride, vinylidene cyanide, such as 1-methyl-1-methoxyethylene, 1,1-dimethoxyethylene, 1,2-dimethoxyethylene, 1,1 -Dimethoxycarbonylethylene, ethylene derivatives such as 1-methyl-1-nitroethylene, such as N-vinylpyrrole, N
There are N-vinyl type monomers such as -vinylcarbazole, N-vinylindole, N-vinylpyrrolidene and N-vinylpyrrolidone. These vinyl-based monomers are present in the polymer compound with a structure in which the unsaturated double bond is cleaved.

Of the above-mentioned monomers, aliphatic monocarboxylic acid esters and nitriles are preferable because they exhibit excellent performance for the purpose of the present invention. These monomers may be bound to the polymer used in the present invention in either a block or random state.

The proportion of the vinyl polymer used in the present invention in the photosensitive composition is preferably 0.5 to 70% by weight. As the vinyl polymer, the above polymers may be used alone or in combination of two or more kinds.
It can also be used in combination with other polymer compounds.

(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 surfactant include copolymers of acrylates or methacrylates containing a fluoroaliphatic group and (polyoxyalkylene) acrylates or (polyoxyalkylene) methacrylates. These compounds may be used alone or in combination of two or more. Particularly preferably FC-430
(Sumitomo 3M Co., Ltd.) Fluorine-based polyethylene glycol # -2000 (Kanto Chemical Co., Inc.). 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) As a compound which can be used in the photosensitive composition of the present invention to produce an acid or a free radical upon exposure, for example, a halomethyloxadiazole compound, 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.

The amount of the compound which forms an acid or a free radical upon exposure to light in the photosensitive composition of the present invention 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, there are 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.

(Coating Solvent) Examples of the coating solvent for the photosensitive composition include the following. n-propanol and diacetone alcohol
Combination, propylene glycol monomethyl a
Ter- and diacetone alcohol combination, 3-me
Of toxy-1-butanol and diacetone alcohol
Combination, n-propanol and 4-hydroxy-
2-butanone combination, propylene glycol mono
Of ethyl ether and 4-hydroxy-2-butanone
Combination, propylene glycol monomethyl ether
Combination of acetate and 4-hydroxy-2-butanone
Combined, propylene glycol monoethyl ether and
And methyl lactate, propylene glycol mono
Combination of ethyl ether and methyl carbitol
Cyclohexanone and 4-hydroxy-2-butane
Non combination.

[0060]

[0061]

These solvents are 1 to 9 of all the solvents, respectively.
It is preferably 5 wt%, more preferably 10 to 80 wt%, and may contain other third solvent.

(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.

On the surface of the photosensitive layer provided as described above, a mat layer is provided in order to shorten the vacuuming time in contact exposure using a vacuum baking frame and to prevent baking blur. preferable. Specifically, JP-A-50-1258
No. 05, Japanese Patent Publication No. 57-6582, No. 61-28986.
The method of providing a mat layer as described in each of the publications, the method of heat-bonding a solid powder as described in JP-B-62-62337 and the like can be mentioned.

An overcoat layer made of a polymer having an excellent oxygen barrier property such as polyvinyl alcohol or acidic celluloses may be provided on the surface of the photosensitive layer for the purpose of preventing oxygen inhibition of photopolymerization.

(Matting Agent) 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 further reducing the fine mesh during exposure due to poor adhesion. It is to prevent the dots from collapsing. As a coating method of the matte layer, there is disclosed in Japanese Patent Laid-Open No. 55-
No. 12974 includes a method of heat-sealing powdered solid powder and a method of spraying polymer-containing water described in JP-A No. 58-182636 and drying, and any method may be used. It is desirable that the matte layer itself be soluble in an alkaline developer or be removable by this.

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

(Exposure) When the photosensitive lithographic printing plate thus obtained is used, 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.

(Treatment) In the present invention (claim 13 ), each of the developing solution and the developing replenishing solution used for the developing treatment of the photosensitive lithographic printing plate has a pH of 12 or more containing an alkali metal silicate. The alkali metal of the alkali metal silicate includes lithium, sodium and potassium, and potassium is the most preferable. 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.

The developing solution and the developing replenisher may contain water-soluble or alkali-soluble organic and inorganic reducing agents. Examples of the organic reducing agent include, for example, 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, 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.

[0076]

EXAMPLES The present invention will be described in more detail with reference to the following examples. Preparation of support The surface of an aluminum plate (material 1050, temper H16) having a thickness of 0.3 mm was degreased with a 3% aqueous sodium hydroxide solution, and this was applied in a 2% hydrochloric acid bath at 25 ° C and a current of 3 A / dm ² . Electrolytically etched at a density. After washing with water, anodic oxidation treatment was performed for 2 minutes in a 5.3% sulfuric acid bath under the condition of 1.5 A / dm ² . Next, with a 2% sodium metasilicate aqueous solution,
After sealing at 85 ° C for 10 seconds, washing with hot water at 90 ° C,
It was dried to obtain an aluminum plate support as a base.

Example 1 A photosensitive composition coating solution having the following composition was applied to the obtained support using a wire bar and dried at 80 ° C. for 2 minutes to obtain a photosensitive lithographic printing plate sample 1. At this time, the coating amount of the photosensitive composition coating liquid was set to be 1.6 g / m ² as a dry weight.

Further, the photosensitive lithographic printing plate sample 1 thus obtained was developed using a developer having the following composition. The coatability and the development suitability were evaluated by the following evaluation methods. The results are summarized in Table 1.

Photosensitive composition Photopolymerizable monomer: trimethylolpropane triacrylate 2.5 g Binder: HyPMA / AN / EA / EMA (30/30/10/30) (Mw.40,000) 5.0 g (HyPMA = 4-hydroxyphenylmethacrylamide, AN = acrylonitrile, EA = ethyl acrylate, EMA = ethyl methacrylate) Photoinitiator: 2,4-bis (trichloromethyl) -6- (p-methoxystyryl) -S-triazine 5 g Diethylthioxanthone 0.5 g p-Dimethylaminobenzoic acid ethyl ester 0.5 g Diazo resin: p-diazodiphenylamine PF ₆ salt co-condensate with p-hydroxybenzoic acid (molar ratio 60/40, molecular weight 2,000) 1.0g polyacrylic acid 0.5g Surfactant (FC-430, manufactured by Sumitomo 3M) 0.01 g Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) 0.2 g Solvent: n-propanol (viscosity 2.26 cps, surface tension 23.8 dyne / cm, specific gravity) 0.8050 g / cm ² ) 100 g Diacetone alcohol (viscosity 3.2 cps, surface tension 29.8 dyne / cm, specific gravity 0.9406 g / cm ² ) 100 g

Developer potassium silicate (1160 g), caustic potash (133 g), water (5133 ml): (pH = 12.8)

Evaluation Method Applicability Evaluation The above photosensitive layer was applied to the sand using a wire bar and dried.
Whether the film surface was uniform was visually evaluated based on the following judgment conditions. Further, the film thickness was measured (20 samples), and the degree of variation from the average was measured and evaluated.

Development suitability evaluation step 2 k using a film original containing a tablet
w Using a metal halide lamp, 3 at 8 mW / cm ²
It was exposed for 0 seconds. X1.0, x1.5, x of the above developer
Using a vat with a developer diluted with 2.0 or × 3.0, 30 ℃
And developed for 30 seconds. It was visually evaluated whether there was a defective development such as a residual film. Judgment condition ⊚: No residual film ○: Some residual dye is observed (Abs 0.4 or less at reflection density at 600 nm) Δ: Residual film ×: No development

Example 2 The solvent in the photosensitive composition of Example 1 was 100% propylene glycol monomethyl ether (viscosity 1.75 cps).
g, diacetone alcohol (viscosity 2.9 cps) 100
A photosensitive lithographic printing plate sample 2 was obtained in the same manner as in Example 1 except that g was changed. The photosensitive lithographic printing plate sample 2 thus obtained was developed using the above-mentioned developing solution in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1.

Example 3 The solvent in the photosensitive composition of Example 1 was replaced with 3-methoxy-1-.
A photosensitive lithographic printing plate sample 3 was obtained in the same manner as in Example 1 except that 100 g of butanol (viscosity 1.42 cps) and 100 g of diacetone alcohol (viscosity 3.2 cps) were used. The photosensitive lithographic printing plate sample 3 thus obtained was developed using the above-mentioned developing solution in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1.

Example 4 The solvent in the photosensitive composition of Example 1 was changed to n-propanol (viscosity 2.26 cps, surface tension 23.8 dyne / c).
m, specific gravity 0.8050 g / cm ² ) 100 g, 4-hydroxy-2-butanone (viscosity 3.5 cps, surface tension 4
0.42 dyne / cm, specific gravity 1.023 g / cm ² )
A photosensitive lithographic printing plate sample 4 was obtained in the same manner as in Example 1 except that the amount was changed to 100 g. The resulting photosensitive lithographic printing plate sample 4 was developed using the above-mentioned developing solution in the same manner as in Example 1,
It evaluated similarly. The results are shown in Table 1.

Example 5 100 g of propylene glycol monoethyl ether (viscosity 1.8 cps) was added to the solvent in the photosensitive composition of Example 1.
4-hydroxy-2-butanone (viscosity 3.5 cps) 1
A photosensitive lithographic printing plate sample 5 was obtained in the same manner as in Example 1 except that the amount was changed to 00 g. Obtained photosensitive lithographic printing plate sample 5
Was developed using the above developing solution in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1.

Example 6 The solvent in the photosensitive composition of Example 1 was changed to propylene glycol monomethyl ether acetate (viscosity 1.3 cps).
100 g, 4-hydroxy-2-butanone (viscosity 3.5
cps) was changed to 100 g to obtain a photosensitive lithographic printing plate sample 6 in the same manner as in Example 1. The photosensitive lithographic printing plate sample 6 thus obtained was developed using the above-mentioned developing solution in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1.

Example 7 The same as Example 1 except that the solvent in the photosensitive composition of Example 1 was changed to 100 g of methyl lactate (viscosity 2.9 cps) and 100 g of propylene glycol monoethyl ether (viscosity 1.8 cps). Thus, a photosensitive lithographic printing plate sample 7 was obtained. The photosensitive lithographic printing plate sample 7 thus obtained was developed using the above-mentioned developing solution in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1.

Example 8 The solvent in the photosensitive composition of Example 1 was 100 g of propylene glycol monoethyl ether (viscosity 1.8 cps),
A photosensitive lithographic printing plate sample 8 was obtained in the same manner as in Example 1 except that 100 g of methyl carbitol (viscosity 3.9 cps) was used. The photosensitive planographic printing plate sample 8 thus obtained was used in Example 1.
Similarly to the above, development processing was performed using the above-mentioned developing solution, and the same evaluation was performed. The results are shown in Table 1.

Example 9 The solvent in the photosensitive composition of Example 1 was 100 g of cyclohexanone (viscosity 2.2 cps), 4-hydroxy-2-
A photosensitive lithographic printing plate sample 9 was obtained in the same manner as in Example 1 except that 100 g of butanone (viscosity 3.5 cps) was used.
The photosensitive lithographic printing plate sample 9 thus obtained was developed using the above-mentioned developing solution in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1.

Comparative Example 1 The solvent in the photosensitive composition of Example 1 was methyl ethyl ketone (viscosity 0.42 cps, surface tension 24.6 dyne / c).
m, specific gravity 0.8063 g / cm ² ) 100 g, propylene glycol monomethyl ether (viscosity 1.75 cp
s, surface tension 27.1 dyne / cm, specific gravity 0.923
Photosensitive lithographic printing plate sample 10 was obtained in the same manner as in Example 1 except that 100 g was used instead of 4 g / cm ² ). The photosensitive lithographic printing plate sample 10 thus obtained was developed using the above-mentioned developing solution in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1.

Comparative Example 2 The solvent in the photosensitive composition of Example 1 was propylene glycol monomethyl ether (viscosity 1.75 cps, surface tension 27.1 dyne / cm, specific gravity 0.9234 g / c).
m ² ) A photosensitive lithographic printing plate sample 11 was obtained in the same manner as in Example 1 except that 200 g was used. The photosensitive lithographic printing plate sample 11 thus obtained was developed using the above-mentioned developing solution in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1.

Comparative Example 3 100 g of methanol (viscosity 0.59 cps, surface tension 22.6 dyne / cm, specific gravity 0.792 g / cm ² ) as a solvent in the photosensitive composition of Example 1 and methyl lactate (viscosity 2.9 cps) were used. A photosensitive lithographic printing plate sample 12 was obtained in the same manner as in Example 1 except that the surface tension was 34.5 dyne / cm and the specific gravity was 1.096 g / cm ² ) 100 g. The photosensitive lithographic printing plate sample 12 thus obtained was developed using the above-mentioned developing solution in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1.

Comparative Example 4 Example except that the solvent in the photosensitive composition of Example 1 was changed to 200 g of methyl lactate (viscosity 2.9 cps, surface tension 34.5 dyne / cm, specific gravity 1.096 g / cm ² ). A photosensitive lithographic printing plate sample 13 was obtained in the same manner as in 1. The photosensitive lithographic printing plate sample 13 thus obtained was developed using the above-mentioned developing solution in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1.

[0095]

[Table 1] Note, Marangoni: It refers to drying unevenness in which a large number of spiral cells are seen in the coating film.

[0096]

According to the present invention, it is possible to provide a photosensitive composition having excellent coating properties, a photosensitive lithographic printing plate having excellent alkaline aqueous solution development suitability, and a developing method thereof.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI G03F 7/32 G03F 7/32 (72) Inventor Naruo Tsuji 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Mitsubishi Chemical Corporation (72) Inventor Fumiyuki Matsuo 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Mitsubishi Chemical Corporation (56) Reference JP-A-63-259558 (JP, A) JP-A-5-5984 (JP, A) JP-A-5-19471 (JP, A) JP-A-6-258821 (JP, A) JP-A-3-1141 (JP, A) JP-A-62-38471 (JP, A) JP-A-5 -197137 (JP, A) JP 5-197138 (JP, A) JP 2-242253 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03F ^7/ 00- 7/16 G03F 7/32

Claims (13)

(57) [Claims] 1. A diazo compound, an alkali-soluble polymer
Compound, photopolymerization initiator, polymerizable unsaturated compound, n-propa
A photosensitive composition comprising a nol and diacetone alcohol . 2. A diazo compound and an alkali-soluble polymer
Compound, photopolymerization initiator, polymerizable unsaturated compound, propylene
Glycol monomethyl ether and diacetone alco
The photosensitive composition characterized by containing Lumpur. 3. A diazo compound and an alkali-soluble polymer
Compound, photopolymerization initiator, polymerizable unsaturated compound, 3-methoxy
Contains Ci-1-butanol and diacetone alcohol
A photosensitive composition comprising: 4. A diazo compound, an alkali-soluble polymer
Compound, photopolymerization initiator, polymerizable unsaturated compound, n-propa
A photosensitive composition comprising a norl and 4-hydroxy-2-butanone . 5. A diazo compound, an alkali-soluble polymer
Compound, photopolymerization initiator, polymerizable unsaturated compound, propylene
Glycol monoethyl ether and 4-hydroxy-
A photosensitive composition comprising 2-butanone . 6. A diazo compound, an alkali-soluble polymer
Compound, photopolymerization initiator, polymerizable unsaturated compound, propylene
Glycol monomethyl ether acetate and 4-hi
A photosensitive composition comprising droxy-2-butanone . 7. A diazo compound, an alkali-soluble polymer
Compound, photopolymerization initiator, polymerizable unsaturated compound, propylene
Contains glycol monoethyl ether and methyl lactate
It characterized feeling light composition to. 8. A diazo compound and an alkali-soluble polymer
Compound, photopolymerization initiator, polymerizable unsaturated compound, propylene
Glycol monoethyl ether and methyl carbitol
Feel you characterized by containing Le light composition. 9. A diazo compound, an alkali-soluble polymer
Compound, photopolymerization initiator, polymerizable unsaturated compound, cyclohexene
Sanon and 4-hydroxy-2-butanone containing <br/> be that sensitive optical composition, characterized in that. 10. A diazo compound is an aromatic diazonium salt.
And its aqueous solution at 25 ° C, or 50 wt% of ethanol
Cocondensation with an aromatic compound having a pKa of 10 or less in a nor solution
Claims 1, characterized in that a coupling resin 9 either
The photosensitive composition as described in 1 above. 11. The photopolymerization initiator is a) a triazine-based compound.
B) a mixture of thioxanthone compounds and amine compounds
Compound, or c) consisting of a mixed system of a and b
The feeling according to any one of claims 1 to 10, characterized in that
Photogenic composition. 12. The method according to claim 1 , which is provided on a support having hydrophilicity.
To 11 of any one of the photosensitive compositions.
A photosensitive lithographic printing plate characterized by: 13. Development with an alkaline aqueous solution having a pH of 12 or more
Manufactured by the method according to claim 12.
Method for developing a photosensitive lithographic printing plate.