JPH0277748A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive compsn. developable with an aq. alkali soln. and giving a printing plate having high printing resistance by incorporating a photosensitive compd. and polyurethane resin having -CO-NH-CO- groups, insoluble in water and soluble in an alkaline aq. soln. CONSTITUTION:This photosensitive compsn. having high performance is composed essentially of mixture of an o-quinonediazido compd. and a diazonium compd. having negative action, a polymerizable monomer and a photopolymn. initiator or mixture of the diazonium compd., the polymerizable monomer and the photopolymn. initiator as photosensitive compds. and polyurethane resin having -CO-NH-CO- groups, insoluble in water and soluble in an alkaline aq. soln. The -CO-NH-CO- groups are preferably contained in the side chain of the polyurethane resin and the pref. basic skeleton of the resin is a reaction product of polyol having one or more -CO-NH-CO- groups in the molecule with polyisocyanate. The mol. wt. of the resin is 5,000-300,000 and the amt. of the resin in the photosensitive compsn. is regulated to 10-85wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a photosensitive composition suitable for manufacturing lithographic printing plates, IC circuits and photomasks.

More specifically, the present invention relates to a photosensitive composition comprising a photosensitive compound that acts on a positive or negative tone and a polymer compound with excellent abrasion resistance.

[Conventional technology]

In a positive-acting system, a photosensitive composition consisting of an 0-naphthoquinone diazide compound and a novolac type phenol resin is an extremely excellent photosensitive composition that is used industrially in the production of lithographic printing plates and as a photoresist. It's here.

However, due to the nature of the novolac type phenolic resin used as the main material, it has poor adhesion to the substrate, is brittle, has poor coating properties, has poor abrasion resistance, and does not have sufficient rigidity when used in lithographic printing plates. There were some points that needed to be improved, and there were limits to its application.

In order to solve this problem, various polymer compounds have been investigated as binders. For example, special public relations
Polyhydroxystyrene or hydroxymethyl described in Japanese Patent No. 1050.

Although the coating properties of these copolymers were certainly improved, they had the disadvantage of poor abrasion resistance. Also, JP-A-51-34
Publication No. 711 proposes the use of a polymer compound having a structural unit of an acrylic acid derivative in its molecular structure as a binder, but such a polymer compound has a narrow range of appropriate development conditions and also has poor abrasion resistance. There were also problems such as not having enough sex.

Polyurethane resins are also known as polymers with excellent wear resistance, and Japanese Patent Publication No. 49-3696'1 discloses a combination system of a positive-acting diazonium compound and a substantially linear polyurethane resin. . However, the polyurethane resin does not have an alkali-soluble group and has essentially insufficient solubility in an aqueous alkaline developer, making it extremely difficult to perform development without producing a residual film.

Furthermore, JP-A-61-20939 describes a photosensitive composition using an anionic polyurethane resin. Such anionic polyurethane resins are water-soluble and are essentially different from the water-insoluble polyurethane resins of the present invention.

Since the anionic polyurethane resin is water-soluble, its solubility in organic coating solvents was insufficient.

Moreover, it was undesirable because it deteriorated the stability of the diazo compound.

In addition, the majority of substances used as photosensitive substances in negative-acting systems are diazonium compounds.
The most commonly used resins include diazo resins represented by formaldehyde condensates of p-diazodiphenylamine.

The composition of the photosensitive layer of a photosensitive lithographic printing plate using a diazo resin is, for example, a diazo resin alone, that is, no binder is used, as described in U.S. Pat. No. 2,714,066. For example, JP-A-50-3060
As described in Publication No. 4, it can be classified as a mixture of binder and diazo resin, but in recent years, many photosensitive lithographic printing plates using diazonium compounds have a high printing durability. It is made of a diazonium compound and a polymer that acts as a binder.

As described in JP-A No. 50-30604, such a photosensitive layer is of the so-called alkaline development type, in which the unexposed area is removed (developed) with an aqueous alkaline developer, and the other is the so-called alkaline development type, in which the unexposed area is removed (developed) with an aqueous alkaline developer, and the photosensitive layer is developed with an organic solvent developer. Although the so-called solvent-developed type is known, from the viewpoint of occupational safety and health, the alkaline-developed type is attracting attention, and this is mainly determined by the properties of the binder. A method for imparting alkaline developability to the binder is to copolymerize a carboxylic acid-containing monomer as described in JP-A-50-30604, or as described in U.S. Pat. No. 2,861,058. There is a method of introducing carboxylic acid into a polymer by reacting the hydroxyl group of polyvinyl alcohol with a cyclic acid anhydride such as phthalic anhydride, but the resulting polymer has poor abrasion resistance due to its structure. However, from photosensitive lithographic printing plates containing such a binder in the photosensitive layer, only lithographic printing plates with low printing durability could be obtained. On the other hand, polyvinyl acetal forms a tough film and is abrasion resistant, but it has the disadvantage that only organic solvent-developable photosensitive lithographic printing plates can be obtained.

In addition, polyurethane resin is a known polymer with excellent abrasion resistance;
JP-A-56-94346 discloses a combination system of a diazonium compound and a substantially linear polyurethane resin, and a combination system of a diazonium salt polycondensate and a branched polyurethane resin.

However, as mentioned above, none of these polyurethane resins has an alkali-soluble group, and their solubility in an aqueous alkaline developer is essentially insufficient, making it extremely difficult to develop them without forming a residual film. It was difficult.

Furthermore, since it does not have a site that causes a photoreaction with the combined diazonium compound during exposure and crosslinks efficiently, it has the disadvantage that it does not form images with sufficient strength.

In order to solve these problems, for example,
As described in No. 123452, there is a method using a polyurethane resin containing carboxyl groups as a binder, but even photosensitive planographic printing plates containing such a binder in the photosensitive layer still do not have sufficient printing durability. I couldn't get it.

Furthermore, there were problems that should be improved, such as poor chemical resistance and insufficient printing durability, especially in printing using UV ink.

On the other hand, there have been many attempts to use a photopolymerizable composition as a photosensitive image forming layer of a negative-working photosensitive lithographic printing plate.
A basic composition consisting of a polymer as a binder, a monomer and a photopolymerization initiator as disclosed in Japanese Patent Publication No. 32714, a polymer as a binder as disclosed in Japanese Patent Publication No. 34041/1983, Composition with improved curing efficiency by introducing bonds, 1973-
Publications No. 38403 and Special Publication No. 53-27605,
Compositions using new photopolymerization initiators, such as those disclosed in British Patent No. L388,492, are known, and some of them have been put to practical use, but none of them have photosensitivity. The composition also has the disadvantage that its sensitivity is greatly affected by the surface temperature of the photosensitive lithographic printing plate at the time of image exposure, and polymerization is strongly inhibited by oxygen during image exposure.

[Problem to be solved by the invention]

Therefore, an object of the present invention is to provide a photosensitive composition in which a polymer compound used as a binder has excellent solubility in an alkaline aqueous solution and abrasion resistance, can be developed with an aqueous alkaline developer, and provides a lithographic printing plate with high stiffness resistance. It is to provide.

Another object of the present invention is to provide a photosensitive composition in which a polymer compound used as a binder has excellent chemical resistance and provides a lithographic printing plate with high printing durability even when printed with UV ink. be.

[Means to solve the problem]

As a result of the inventors' intensive research to achieve the above object,
It has been discovered that these objects can be achieved by using a novel photosensitive composition, and the present invention has been achieved.

That is, the present invention provides photosensitive compounds and -CO-NH-CO
The present invention provides a photosensitive composition characterized in that it contains a polyurethane resin which has - groups and is insoluble in water and soluble in an alkaline aqueous solution.

As the photosensitive compound contained in the photosensitive composition of the present invention, a photosensitive compound selected from the following (i), (ii), (mountain) or (iv) can be used.

(i) o-quinonediazide compound.

(ii) Negative-acting diazonium compounds.

(iii) A combination of a polymerizable monomer and a photopolymerization initiator.

(iv) A combination of a negative-acting diazonium compound, a polymerizable monomer and a photoinitiator.

Hereinafter, the polyurethane resin and other components used in the present invention, and the method for producing and using the photosensitive composition of the present invention will be explained in detail.

fll Polyurethane resin containing -CO-NH-CO- group The polyurethane resin having one CO -NH-CO- group used in the present invention and which is insoluble in water and soluble in an alkaline aqueous solution preferably has a A polyurethane resin containing one CD-NH-(:O- group) forming a ring in the main chain or together with the main chain, and more preferably in the side chain.
It is a polyurethane resin containing CD -NH-CO- groups.

-CO-NH-CD- preferably used in the present invention
A polyurethane resin having groups has one or more -
It is a polyurethane resin whose basic skeleton is a reaction product of a polyol compound having a CO-NH-CO- group and a polyisocyanate compound.

-CO-NL- which is more preferably used in the present invention
The polyurethane resin having a CD group is represented by the following formula (I)
or (II) is a polyurethane resin whose basic skeleton is a reaction product of a diol compound having a -C0- group and a diisocyanate compound.

HO-R'-A'-R2-OH CD ...... (1) NH CD In the formula, R1, R2, R3 and R5, R6 may be the same or different, and each may be a single bond or a substituted Indicates a divalent aliphatic or aromatic hydrocarbon group which may have a group. Preferably C
It represents an alkylene group of 1 to C20, an arylene group of 06 to CI5, and more preferably an alkylene group of 01 to C8. If necessary, R1, R2, R3, R5, and R6 may contain other functional groups that do not react with isocyanate groups, such as estenopeurethane, amide, ureido, and ether groups.

Note that two or more of RI SR2, R3, R5, and Re may form a ring.

R4 is alkyl, aryl, which may have a substituent,
It represents an aralkyl group, preferably an alkyl group of 01 to C8, an aryl group of C6 to CI5, or an aralkyl group.

AI and A2 each represent a C1 to C2G trivalent aliphatic or aromatic group which may have a nitrogen atom and a substituent.

B represents a trivalent alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic group which may have a substituent.

In addition, XI and X2 are each a single bond or C1H,
Indicates a divalent linking group consisting of one or more atoms selected from N, O, and S.

Examples of the diol compound represented by the general formula (I) or (II) include those shown below.

110　CHz　CCHz　OHCO Ko N.H. C.O. Hz (No, 2) C.B.

HO-CHzC-CHzOH CO NH n (No, 3) CHz HO-CHz CCHz OH CO (No, 4) These diol compounds having a -CO-NH-CO- group may be used alone or in combination of two or more. I can do things.

Furthermore, a diol compound that does not have a -CO-N)I-CO- group and may have other substituents that do not react with isocyanate can also be used in combination.

Specifically, such diol compounds include those shown below.

Namely, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, 1,3-butylene glycol, 1.
6-hexanediol, 2-butene-1,4-diol, 2゜2.4-trimethyl-1,3-bentanediol, 1,4-bis-β-hydroxyethoxycyclohexane, cyclohexane dimetatool, tricyclode Candimetatool, hydrogenated bisphenol A, hydrogenated bisphenol F, ethylene oxide adduct of bisphenol A,
Propylene oxide adduct of bisphenol A, bisphe/-)IiFO:):1 tylene oxide adduct, propylene oxide adduct of bisphenol F, ethylene oxide adduct of hydrogenated bisphenol A, propylene oxide adduct of hydrogenated bisphenol A, Hydroquinone dihydroxyethyl ether, P-xylylene glycol, dihydroxyethyl sulfone, bis(2-
hydroxyethyl)-2,l-)lylene dicarbamate, 2. ．． 71-) Rylene-bis(2-hydroxyethylcarbamide), bis(2-hydroxyethyl)-m-xylylene dicarbamate, bis(2-hydroxyethyl)isophthalate, 3.5-dihydroxybenzoic acid, 2
．． 2-bis(hydroxymethyl)propionic acid, 2.2
-bis(2-hydroxyethyl)propion 2-bis(
Examples thereof include 3-hydroxypropyl)propionic acid, bis(hydroxymethyl)acetic acid, his(4-hydroxyphenyl)acetic acid, 4,4-bis(4-hydroxyphenyl)pentanoic acid, and tartaric acid.

Furthermore, the diisocyanate compounds preferably used in the present invention include those shown below.

That is, 2.1-1-lylene diisocyanate, 2.

Dimer of 4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate Isocyanate, 3.

Aromatic diisocyanate compounds such as 3'-dimethylbiphenyl-4,4'-diisocyanate; hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate, etc. Aliphatic diisocyanate compounds such as isophorone diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, 1
.

Alicyclic diisocyanate compounds such as 3-(isocyanatomethyl)cyclohexane; reaction products of diols and diisocyanates such as adducts of 1 mole of L3-butylene glycol and 2 moles of tolylene diisocyanate; Examples include diisocyanate compounds.

The polyurethane resin of the present invention is synthesized by heating the above diisocyanate compound and diol compound in an aprotic solvent, adding a known catalyst having an activity corresponding to the reactivity of each compound.

The molar ratio of the diisocyanate and diol compound to be used is preferably 0.8:1 to 1.2=1, and if the isocyanate group remains at the end of the polymer, it can be treated with alcohols or amines, etc. , it is finally synthesized in a form in which no isocyanate groups remain.

The weight average molecular weight of the polyurethane resin of the present invention is preferably 2,000 or more, more preferably 5,000 or more.
, OOO~300,000. The polyurethane resins of the present invention may be used alone or in combination. The content of these polyurethane resins contained in the photosensitive composition is about 5 to 95% by weight, preferably about 10 to 95% by weight.
It is 85% by weight.

(2) Positive type 0-quinonediazide compound On the other hand, the positive type 0-quinonediazide compound used in the present invention is preferably an 0-naphthoquinonediazide compound.

The most preferred 0-naphthoquinone diazide compound used in the present invention is an ester of 1,2-diazonaphthoquinone sulfonic acid chloride and pyrogallol-acetone resin described in Japanese Patent Publication No. 43-28403. Other suitable O-quinonediazide compounds include 1, which is described in U.S. Pat.
There are esters of 2-diazonaphthoquinonesulfonic acid chloride and phenol-formaldehyde resins. Other useful 0-naphthoquinone diazide compounds include:
It is reported and known in numerous patents. For example, JP-A-47-530'3, JP-A-48-63802, JP-A-48-63803, JP-A-48-96575, JP-A-49-38701, JP-A-48-13354, JP-A-Sho.4
No. 1-11222, No. 1973-9610, No. 49-
No. 17481, U.S. Patent Box 2.797,213,
Same No. 3,454,400, Same No. 3,544.323, Same No. 3,573,917, Same No. 3,674,495
No. 3,785,825, British Patent No. 1,227
, No. 602, No. 1.251,345, No. 1.26
No. 7.005, No. 1,329,888, No. 1, 3
Examples include those described in various specifications such as No. 30,932 and German Patent No. 854,890.

The amount of these positive-acting 0-quinonediazide compounds in the photosensitive composition of the present invention is 10 to 50% by weight.
The content is more preferably 20 to 40% by weight.

(3) Negative-acting diazonium compound The negative-acting diazonium compound used in the present invention is disclosed in U.S. Patent Box 3.
, 867.147, and the diazonium compounds described in U.S. Pat. Diazo resins such as those represented by the following are useful. Preferred diazo resins include, for example, hexafluorophosphates, tetrafluoroborates, and phosphates of condensates of p-diazodiphenylamine and formaldehyde or acetaldehyde. Also, US Patent Box 3,30
Sulfone i of the condensate of p-diazodiphenylamine with formaldehyde as described in No. 0,309
Salts (e.g. p-)luenesulfonate, dodecylbenzenesulfonate, 2-methoxy-4-hydroxy-5
-benzoylbenzenesulfonate, etc.), bosphinate (eg, benzenephosphinate, etc.), hydroxy group-containing compound salts (eg, 2,4-dihydroxybenzophenone salt, etc.), organic carboxylic acid salts, and the like are also preferred.

゛Furthermore, JP-A-58'-2'7. Also suitable are mesitylene sulfonate obtained by condensing 3-methoxy-4-diazo-diphenylamine with 4,4'-bis-methoxy-methyl-diphenyl ether as shown in No. 141.

The content of these diazonium compounds in the photosensitive composition is 1 to 60% by weight, preferably 3 to 20% by weight.

Moreover, two or more types of diazonium compounds may be used in combination, if necessary.

(4) Polymerizable monomer/photopolymerization initiator The monomer that can be added to the photosensitive composition of the present invention has a boiling point of 100° C. or higher at normal pressure, and is present in a small amount (one per molecule, more preferably A monomer or oligomer having a molecular weight of 10.000 or less and having two or more addition-polymerizable ethylenically unsaturated groups.Such monomers or oligomers include polyethylene glycol mono (meth)acrylate, polypropylene glycol mono (meth) Monofunctional acrylates and methacrylates such as acrylate, phenoxyethyl (meth)acrylate; polyethylene glycol di(meth)ac root, polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neobentyl glycol di( meth)acrylate, pentaerythritol tri(
meth)acrylate, pentaerythritol tetra(meri)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol di(meth)acrylate, tri(acryloyloxyethyl)isocyanate, polyhydric alcohols such as glycerin and trimethylolethane (Meth) acrylate after adding ethylene oxide or propylene oxide to it, as described in Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 5 (1-6034), and Japanese Unexamined Patent Application Publication No. 51-37193. urethane acrylates, polyester acrylates described in JP-A No. 48-64183, JP-B No. 49-4.3191, and JP-B No. 52-30490;
Examples include polyfunctional acrylates and methacrylates such as epoxy acrylates made by reacting epoxy resin with (meth)acrylic acid. In addition, Japan Adhesive Association Journal v
o1.20.11kL7. Those introduced as photocurable monomers and oligomers on pages 300 to 308 can also be used.

These monomers or oligomers and -CO of the present invention
The composition ratio of the polyurethane resin having -NH-CO- groups is preferably in the range of 5:95 to 70:30, and more preferably in the range of 10:90 to 50:50.

Photoinitiators that can be added to the photosensitive composition of the present invention include vicinal polyketaldonyl compounds disclosed in U.S. Pat. No. 2,367.660, U.S. Pat. No. 2,367.661 and α-carbonyl compounds disclosed in U.S. Pat. No. 2,367.670, asiroin ethers disclosed in U.S. Pat. Aromatic acyloin compounds substituted with a hydrocarbon at the α-position disclosed in the specification, polynuclear quinone compounds disclosed in U.S. Patent Nos. 3,046,127 and 2,951,758, Triaryl imidazole dimer disclosed in U.S. Patent No. 3,549.367/
Combination of p-aminophenyl ketones, US Pat. No. 3,8
Hendithiazole compounds disclosed in U.S. Pat. No. 70,524, acridine and phenazine compounds disclosed in U.S. Pat. No. 3,751,259, and U.S. Pat. No. 4,212,970. This includes oxadiazole compounds, etc.

Preferred examples include trihalomethyl-8-triazine compounds and trihalomethyloxadiazole compounds represented by the following general formula (1) or (]'V).

In the formula, R8 represents a substituted or unsubstituted aryl or alkenyl group, and R7 represents R8, -CY, or a substituted or unsubstituted alkyl group. Y represents a chlorine atom or a bromine atom.

Examples of the compound represented by the general formula (III) include Wakabu et al., Bull, Chem, Sco, Japan.
n, Vol. 42, p. 2924 (1969), British Patent No. 1,388,492, West German Patent No. 2
, 718,259, and West German Patent No. 3,337,0
Examples include the compounds described in No. 24. Specifically, the following compounds are included.

i.e., 2-phenyl-4,6-bis(trichloromethyl)-3-triazine, 2-(p-chlorophenyl)-4
, 6-bis(trichloromethyl)-8-triazine, 2
-(p-tolyl)-4,6-bis(trichloromethyl)
-3-) riazine, 2-(p-methoxyphenyl)-4
, 6-bis(trichloromethyl)-3-1-riazine,
2-(2',4'-dichlorophenyl-4,6-bis(trichloromethyl)-3-)riazine, 2°4.6-
1-Lis(trichloromethyl)-3-triazine, 2-
Methyl-4,6-bis(trichloromethyl)-3-triazine, 2-n-nonyl-4゜6-bis(trichloromethyl)-1-triazine, 2-(α,α,β-trichloroethyl)-4, 6-bis(trichloromethyl)-3-)
Riazine, 2-styryl-4,6-bis(trichloromethyl)-8-triazine, 2-(p-methylstyryl)
-4,6-bis(trichloromethyl)-3-) riazine, 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-3-) riazine, 2-(4-methoxy-naphtho-1) -yl)-4゜6-bis(trichloromethyl)-3-)riazine, 2-(4-ethoxy-naphtho-
1-yl)-4゜6-bis(trichloromethyl)-3l
-Riazine, 2-(4-(2-ethoxyethyl)-naphth-1-yl)-4,6-bis(trichloromethyl)
-8-triazine, 2-(4,7-dimethoxy-naphthol-1-yl)-4,6-bis(trichloromethyl)-3
-) riazine, 2-(acenaphth-5-yl)-4,6
-bis(trichloromethyl)-3-) riazine, 2-
(4-styrylphenyl)-4,6-bis(trichloromethyl)-3-)riazine and the like are included. - Further, as the compound represented by the general formula (IV), for example, JP-A-54-74728, JP-A-55-7774
Examples thereof include compounds described in Publication No. 2 and JP-A-59-148784.

Specifically, the following compounds are included.

That is, 2-styryl-5-trichloromethyl-1,3,
4-Oxadiazole, 2-(4-chlorostyryl)-
5-Trichloromethyl-1,3゜4-oxadiazole, 2-(4-methylstyryl)-5-)dichloromethyl-1,3,4-oxadiazole, 2-(4-methoxystyryl)-5 -trichloromethyl-1,3,4-oxadiazole, 2-(4-butoxystyryl)-5-)
Dichloromethyl-1,3,4-oxadiazole, 2-
(4-styrylstyryl)-5-1-dichloromethyl-
1,3,4-oxadiazole, 2-phenyl-5-trichloromethyl-1,3,4-oxadiazole, 2-
(4-methoxyphenyl)-5-trichloromethyl-1
,3,4-oxadiazole,2-(3,4-dimethoxyphenyl)-5-trichloromethyl-1,3,4-
Oxadiazole, 2-(4-styrylphenyl)-5
-Trichloromethyl-1. 3.4-oxadiazole, 2-(1-naphthyl)-5-)dichloromethyl-1,
s, 4-oxadiazole and the like.

A sensitizer can be added to the photosensitive composition of the present invention if necessary. Specifically, aromatic thiazole compounds shown in Japanese Patent Publication No. 59-28328,
Merocyanine dyes shown in JP-A No. 151O24, aromatic thiopyrylium salts and aromatic pyrylium salts shown in JP-A-58-40302, and other light absorbers such as 9-phenylacridine, 5-nitroacenaphthene, ketochlorins, etc. Can be mentioned. Furthermore, these include N-phenylglycine, 2-mercaptobenzothiazole, N,N'-
Systems in combination with hydrogen donors such as ethyl dimethylaminobenzoate are also effectively used in the present invention.

The amount of the photopolymerization initiator and/or sensitizer in the present invention is
Photopolymerizable ethylenically unsaturated compound and -CO of the present invention
A range of 0.01% to 20% by weight based on the total amount of polyurethane resin having -NH-CO- groups is sufficient, and more preferably 0.5% to 10% by weight gives good results. .

When a diazonium compound is further added to these photosensitive compositions, the diazonium compound is preferably used in an amount of 1 to 50% by weight, more preferably 2 to 35% by weight of the total composition.

(5) Other components In addition to the polyurethane resin having -CO -NH-CO- groups, the composition of the present invention includes phenol formaldehyde resin, cresol formaldehyde resin, phenol-modified xylene resin, polyhydroxystyrene, polyhalogen Known alkali-soluble polymer compounds such as hydroxystyrene and carboxyl group-containing epoxy resins, polyacetal resins, acrylic resins, methacrylic resins, and carboxyl group-containing polyurethane resins can be contained. Such alkali-soluble polymer compound is used in an amount of 70% by weight or less of the total composition.

The composition of the present invention contains a printing-out agent for obtaining a visible image immediately after exposure, a dye as an image coloring agent, a pigment, a stabilizer,
Additives such as surfactants, plasticizers and other fillers can be added.

Typical print-out agents for obtaining a visible image immediately after exposure include a combination of a photosensitive compound that releases an acid upon exposure and an organic dye that can form a salt. Specifically, JP-A-50-36209, JP-A-53-8
The combination of 0-naphthoquinonediazide-4-sulfonic acid halide and salt-forming organic dye described in JP-A No. 128, JP-A-53-36223, JP-A-54-7
Examples include the combination of a trihalomethyl compound and a salt-forming organic dye described in Japanese Patent No. 4728.

Dyes other than the salt-forming organic dyes mentioned above can also be used as image colorants. Suitable dyes include oil-soluble dyes and basic dyes, including salt-forming organic dyes. Specifically, Oil Yellow #101, Oil Yellow #130, Oil Pink #312, Oil Clean BG, Oil Blue BO3, Oil Blue #60.
3. Oil blank BY, Oil black BS, Oil black T-505 (manufactured by Orient Chemical Industry Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI
42535), Rhodamine B (CI 45170 B)
, malachite green (CI42000), methylene blue (CI52015), and the like.

Further, when combined with an 0-quinonediazide compound, a cyclic acid anhydride may be added to increase sensitivity. Examples of the cyclic acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and 3,6-nindooxy-△4-tetrahydrophthalic anhydride as described in U.S. Pat. , tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride, and the like. By containing these cyclic acid anhydrides in an amount of 1 to 15% by weight based on the total composition, the sensitivity can be increased up to about 3 times.

When combined with a diazonium compound, stabilizers such as phosphoric acid, phosphorous acid, pyrophosphoric acid, oxalic acid, boron M, p
-4 luenesulfonic acid, benzenesulfonic acid, p-hydroxybenzenesulfonic acid, 2-methoxy-4-hydroxy-5-penzoylhenzenesulfonic acid, malic acid, tartaric acid, dipicolinic acid, polyacrylic acid and their copolymers Polyvinylphosphonic acid and its copolymers, Polyvinylsulfonic acid and its copolymers, 5-nitronaphthalene-1-phosphonic acid, 4-chlorophenoxymethylphosphonic acid, sodium phenyl-methyl-pyrazolone sulfonate, 2-phosphonobutane Tricarboxylic acid-1,2
,4,1-phosphonoethanetricarboxylic acid-1,2,2
, 1-hydroxyethane-1,1-disulfonic acid and the like.

When using a combination of a polymerizable monomer and a photopolymerization initiator, a small amount of thermal polymerization is carried out to prevent unnecessary thermal polymerization of the polymerizable ethylenically unsaturated compound during manufacture or storage of the photosensitive composition. It is desirable to add inhibitors. Suitable thermal polymerization inhibitors include hydroquinone, p
-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4.4'-thiobis(3-methyl-6-t-butylphenol), 2.2'-methylenebis(4- Methyl-
(6-t-butylphenol), 2-mercaptobenzimidazole, N-nitrosophenylhydroxyamine cerous salt, and the like.

In addition, alkyl ethers (e.g. ethyl cellulose, methyl cellulose), surfactants (e.g. fluorine surfactants), film flexibility,
Plasticizers (for example, tricresyl phosphate, dimethyl phthalate, dibutyl phthalate, trioctyl phosphate, tributyl phosphate, tributyl citrate, polyethylene glycol, polypropylene glycol, etc.) can be added to impart wear resistance. The amount of these additives added varies depending on the purpose for which they are used, but
Generally 0.5 to 30% by weight based on the total solid content of the photosensitive layer
It is.

The photosensitive composition of the present invention is applied onto a support after being dissolved in a solvent that dissolves each of the above components. Solvents used here include methanol, ethanol, isopropanol, n
-butanol, t-butanol, ethylene dichloride, cyclohexanone, acetone, methyl ethyl ketone,
Ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-
Methoxyethyl acetate, l-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N,
Examples include N-dimethylformamide, tetrahydrofuran, dioxane, dimethyl sulfoxide, ethyl acetate, methyl lactate, and ethyl lactate, and these solvents may be used alone or in combination.

Also suitable are mixed solvents in which a small amount of water or a solvent such as toluene that does not dissolve the diazo resin or polymer compound is added to these solvents or mixed solvents. The concentration (solid content) of the above components is 1 to 50% by weight.

When applying and drying a photosensitive liquid dissolved in these solvents, it is desirable to dry at 50°C to 120°C. The drying method may be performed by starting at a low temperature and drying at a high temperature after preliminary drying, or by selecting an appropriate solvent and concentration, it may be directly dried at a high temperature.

The coating amount varies depending on the application, but for example, for photosensitive planographic printing plates, the solid content is generally 0.5 to 3.
．． 0 g/rtr is preferred. As the coating amount decreases, the photosensitivity increases, but the physical properties of the photosensitive film deteriorate.

Supports to which the photosensitive composition of the present invention is applied include, for example, paper, plastics (such as polyethylene,
Paper laminated with polypropylene, polystyrene, etc., such as aluminum (also includes aluminum alloys).

), zinc, copper, etc., such as cellulose diacetate, cellulose triacetate, cellulose propionate,
Films of plastics such as cellulose acetate, cellulose acetate butyrate, cellulose butyrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc., and paper or plastic films laminated with or vapor-deposited with metals such as those mentioned above are included. . Among these supports, aluminum plates are particularly preferred because they are extremely dimensionally stable and inexpensive. Furthermore, a composite sheet in which an aluminum sheet is bonded to a polyethylene terephthalate film as described in Japanese Patent Publication No. 48-18327 is also preferred.

Further, in the case of a support having a surface of metal, particularly aluminum, it is desirable to perform an appropriate hydrophilic treatment.

Examples of such hydrophilic treatment include, for example, mechanical methods such as wire brush danishing, polishing, which roughens the aluminum surface with a nylon brush while pouring a slurry of particles, and pole danishing.
F, fil, ctl, , HC7! After roughening the surface by chemical graining using etchant as an etchant, electrolytic graining using nitric acid or hydrochloric acid as an electrolyte, or composite graining using a combination of these roughening methods, acid or Etched with alkali and then anodized in sulfuric acid, phosphoric acid, oxalic acid, boric acid, chromic acid, sulfamic acid, or a mixed acid thereof using a DC or AC power source to form a strong passive film on the aluminum surface. is preferred. Such a passive film itself makes the aluminum surface hydrophilic, but if necessary, the aluminum surface is further hydrophilized as described in US Pat. No. 2,714,066 and US Pat. No. 3,181,461. Silicate treatment (sodium silicate, potassium silicate), U.S. Patent No. 2,
Potassium fluorozirconate treatment as described in U.S. Pat. No. 946.638, phosphomolybdate treatment as described in U.S. Pat. Alkyl titanate treatments as described, polyacrylic acid treatments as described in German Patent No. 1i091,433, German Patent No. 1.134,093 and British Patent Section 1,230,
447, phosphonic acid treatment described in Japanese Patent Publication No. 44-6409, phytic acid treatment described in U.S. Patent No. 3,307,951, Japanese Patent Publication No. 58-168
Composite treatment consisting of a hydrophilic organic polymer compound and a divalent metal described in JP-A-58-18291 and JP-A-58-18291, and a sulfonic acid group described in JP-A-59-101651. Particularly preferred are those which have been subjected to hydrophilic treatment by undercoating with a water-soluble polymer having the following. Other hydrophilic treatment methods include silicate electrodeposition described in US Pat. No. 3,658,662.

The photosensitive composition of the present invention coated on a support can form a line image,
Exposure through a transparent original having a halftone image or the like and subsequent development with an aqueous alkaline developer gives a negative or positive relief image to the original.

Light sources used for exposure include carbon arc lamps, mercury lamps, xenon lamps, metal halide lamps, strobes, ultraviolet rays, and laser beams.

〔Effect of the invention〕

The photosensitive composition of the present invention has excellent developability when the exposed area is developed with an aqueous alkaline developer after coating, drying, and image exposure. The relief image obtained has good abrasion resistance and good adhesion to the support, and when used as a printing plate, many good prints can be obtained.

Furthermore, even when printing is performed using UV ink, a large number of good printed materials can be obtained.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Synthesis Examples and Examples, but the content of the present invention is not limited thereto.

80m of methanol in a 1β three-way flask equipped with a gold charcoal cooling tube and a stirrer! , concentrated hydrochloric acid 134mj! and 38.4 g (0.2 mole) of 4-nitrophthalimide were added and stirred at room temperature. This reaction mixture was added with 33.9 g of iron powder (0
, 607 mole) was added little by little over 1 hour.

(At this time, the temperature inside the flask rises and the solvent refluxes.) After adding the iron powder, continue stirring until the temperature inside the flask reaches 30°C. After the reaction is complete, mix this mixture with 1.
4β with stirring, and stirred for 30 minutes. The precipitate was taken out by filtration, thoroughly washed with 1β of water, and then dried to obtain a yellow solid of 4-aminophthalimide. (
40 g of 2,2-bis(hydroxymethyl)propionic acid was placed in a 500 mN Mitsuro flask equipped with a stirrer, condenser, and dropping funnel.
mol) and 100 mA of acetic anhydride were added thereto, and the mixture was stirred under an ice-water tower. 100 ml of pyridine was added dropwise to this mixture using a dropping funnel over a period of about 30 minutes. After the dropwise addition was completed, the ice water bath was removed, and the mixture was stirred for 2 hours while being heated to 60° C. in an oil bath. After the reaction was completed, the mixture was made acidic by adding hydrochloric acid, and extracted with chloroform using a separator I. After washing the chloroform layer with water, it was dehydrated with anhydrous sodium sulfate.

The solvent was distilled off from this chloroform solution under reduced pressure to obtain 57 g of a white solid of 2,2-bis(acetoxymethyl)propionic acid.

Next, 30 g (0,137 mole) of 2,2-bis(acetoxymethyl)propionic acid and 20 ml of thionyl chloride were added to a 30 g (0,137 mole) 2,2-bis(acetoxymethyl)propionic acid and 20 ml of thionyl chloride.
Pour into a 0ml Mitsuro flask and heat to 80℃ while heating.
Stir for hours.

After the reaction was completed, unreacted thionyl chloride and the like were sufficiently removed by distillation under reduced pressure, and then placed in an ice water bath to sufficiently cool the reaction product. This reaction product contains 4-aminophthalimide 22
．． 2 g (0,137 mole), 80 m of pyridine
! A mixture of 20 mj2 of tetrahydrofuran and tetrahydrofuran was added dropwise over about 1 hour. After the dropwise addition was completed, the ice bath was removed, and the mixture was stirred for 2 hours while being heated to 60°C in an oil bath. After the reaction was completed, the reaction mixture was poured into water 11 with stirring, acidified with hydrochloric acid, and stirred for 30 minutes. 4-(
A pale yellow solid of N-(1,1-bis(acetoxymethyl)ethylcarbonyl)amino)phthalimide was obtained. (Yield: 25g) Next, 4-(N-(1,1-bis(acetoxymethyl))
Ethylcarbonyl)amine)phthalimide 21.7 g
(0.06 mole) and sodium hydroxide 5.6
g (0.14 mole), ethanol 50mn, water 50mj! 300mj equipped with a stirrer and cooling pipe! The mixture was placed in a Mitsuro flask and heated under reflux for 2 hours.

After the reaction is completed, the reaction mixture is poured into water 11 with stirring,
The mixture was acidified with hydrochloric acid and stirred for 30 minutes.

Remove the precipitate by filtration and add 500 tall of water (
By washing and drying, a pale yellow solid of 4-(N-(1,1-bis(hydroxymethyl)ethylcarbonyl)amino)phthalimide was obtained. (Yield 10g) Next, 4-(N-(1,1-bis(hydroxymethyl))
Ethylcarbonyl)amino)phthalimide 3, 35 g
(0,012 mole) and 1.07 g (0,08 m
ole), 4. 4'-diphenylmethane diisocyanate 5.26 g (0,021 mole)
, N, 18 g of N-dimethylacetamide in a stirrer,
Place in a 100mJ Mitsuro flask equipped with a cooling tube,
The mixture was stirred for 4 hours while heating to 00°C. This reaction mixture was cooled, 5 mk of methanol was added thereto, and the mixture was stirred for a while, then poured into 500 mm+ of water with stirring, and stirred for 30 minutes.

The precipitate was filtered and dried to obtain 9 g of white solid. The weight average molecular weight (polystyrene standard) of this polyurethane resin was measured by gel permeation chromatography and found to be 53, OOO tear. (Polyurethane resin (a) of the present invention).

The diisocyanate compounds and diol compounds shown in Table 1 below were reacted to synthesize corresponding polyurethane resins (b) and (c).

Example 1-3L The surface of an aluminum plate having a thickness of 0.30 mm was grained using a nylon brush and a water suspension of 400 mS of bumiston, and then thoroughly washed with water. After etching by immersing it in 10% sodium hydroxide at 70°C for 60 seconds, it was washed with running water, neutralized with 20% nitric acid, and washed with water.

This was carried out at 160 corons/dm2 in a 1% nitric acid aqueous solution using a sinusoidal alternating waveform current under the condition of VA=12.7V.
Electrolytic surface roughening treatment was performed using a special anode electricity amount of . When the surface roughness was measured, it was 0.6μ (expressed as Ra).

Subsequently, it was immersed in a 30% aqueous sulfuric acid solution and desmutted at 55°C for 2 minutes, and then the thickness of the anodic oxide film was 2°7 at a current density of 2A/d+n2 in a 20% aqueous sulfuric acid solution.
It was anodized so that it became g/m2.

Next, by changing the type of polyurethane resin used in the present invention in the following photosensitive liquid (A), three types of photosensitive liquids (A)-1 to (A) were prepared.
-3 was prepared, and this photosensitive solution was applied onto an anodized aluminum plate and dried at 100°C for 2 minutes to produce each photosensitive lithographic printing plate [A)-1 to CA)-3. . The coating amount at this time was 2.5 g/m2 in terms of dry weight.

The polyurethane resins used in the present invention for photosensitive solutions (A)-1 to (A)-3 are shown in Table 2.

Photosensitive liquid (A) Next, as a comparative example, the following photosensitive liquid CB) was applied in the same manner as photosensitive liquid (A) to prepare a photosensitive planographic printing plate CB). The coating weight after drying was 2.5 g/m''.

Photosensitive solution CB) Positive transparent originals of line drawings and halftone dot images were brought into close contact with the photosensitive layers of photosensitive lithographic printing plates (A)-1 to (A)-3 and CB), and heated at 70 cm using a 30 ampere carbon arc lamp. Exposure was done from a distance.

The exposed photosensitive lithographic printing plates (A)-1 to (A)-3 and CB) were transferred to DP-4 (trade name: manufactured by Fuji Photo Film Co., Ltd.)
It was immersed and developed for 60 seconds at 25°C in an 8-fold diluted aqueous solution.

Obtained lithographic printing plates (A)-1 to (A)-3 and (B)
was attached to a Heidelherg KOR type printing machine, and printed on high-quality paper using commercially available regular ink and UV ink. The final number of printed sheets of the lithographic printing plates (A)-1 to (A)-3 and CB) was examined and was as shown in Table 2.

As shown in Table 2, lithographic printing plates (A)-1 to (A)-3 (Examples 1 to 3) using the photosensitive composition of the present invention
Compared to Comparative Example [B], the number of prints was larger regardless of whether normal ink or UV ink was used, and the rigidity resistance was extremely excellent.

The surface of a JIS 1050A aluminum plate with a thickness of 0.24 mm was grained using a nylon brush and an aqueous suspension of 400 mesh pumice stone, and then thoroughly washed with water. After etching by immersing in aqueous sodium hydroxide solution at 70°C for 60 seconds, rinsing with running water for 20 minutes.
After neutralizing and cleaning with 1% nitric acid, the anode was heated to 160 coulombs/d m in a 1% nitric acid aqueous solution using the electrochemical roughening method described in Japanese Patent Application Laid-Open No. 53-67507, that is, using a sinusoidal alternating current waveform. Electrolytic surface roughening treatment was performed on a large amount. Continued 30
% sulfuric acid aqueous solution and desmutted for 2 minutes at 55°C.
．． Anodization treatment was performed to achieve a density of 0 g/m.

Thereafter, it was immersed in a 3% aqueous solution of JISa sodium silicate at 70° C. for 1 minute, washed with water, and dried.

Photosensitive solutions (C)-1 to (C)-3 shown below were applied to the aluminum plate obtained as described above using a wheeler, and dried at 80° C. for 2 minutes. Dry weight is 2.0 g/
It was rd.

The polyurethane resins used in the present invention for photosensitive solutions (C)-1 to (C)-3 are shown in Table 3.

Photosensitive liquid (C) Next, as a comparative example, a polyurethane resin (4,4'-diphenylmethanedi A photosensitive liquid (D
) was applied and dried in the same manner. Dry weight is 2.0 g/
It was td.

Photosensitive lithographic printing plates (C)-1 to (C)-3 and C obtained using photosensitive solutions (C)-1 to (C)-3 and CD)
D) 1 piece of Fuji Photo Film 0 Kiku PS Light for each
After imagewise exposure for 1 minute from a distance of m, and immersion in the following developer for 1 minute at room temperature, the surface was lightly rubbed with absorbent cotton to remove the unexposed area, and the planographic printing plates [c]-1 to l: c)-3
and CD) were obtained.

Each printing plate obtained in this way was mounted on a Heidelherg GTO type printing machine, and commercially available regular ink and UV
Printed on high-quality paper using ink.

The final number of printed sheets of the lithographic printing plates (C)-1 to (C)-'3 and ('D) was examined and was as shown in Table 3.

As shown in Table 3, lithographic printing plates (C)-1 to (C)-3 (Examples 4 to 6) using the photosensitive composition of the present invention
Compared to the comparative example CD), the number of prints is larger regardless of whether normal ink or UV ink is used, and the rigidity resistance is extremely excellent.

Practical Test 11 (Practical Example 11) The following photosensitive liquid (
Apply E)-1 to (E)-2 using a wheeler and apply 80
Dry for 2 minutes at °C. The dry weight was 2.0 g/m.

The polyurethane resins used in the present invention for photosensitive solutions (E)-1 to [E]-2 are shown in Table 4.

Photosensitive liquid (E) Next, as a comparative example, in place of the polyurethane resin used in the present invention in the photosensitive liquid, the above-mentioned JP-A-62-123 was used.
A photosensitive liquid CF) using the polyurethane resin described in 452 Synthesis Example (J) was applied and dried in the same manner. Dry weight is 2.0
g/m.

Each photosensitive lithographic printing plate CE obtained using photosensitive liquids [E)-1, (E)-2 and CF] 1゜CE)-2 and CF) was coated with Fuji Photo Film ■ PS Light. Image exposure was carried out for 1 minute at a distance of 1 m, and after immersing in the developer shown above for 1 minute at room temperature, the surface was lightly rubbed with absorbent cotton.
Remove the unexposed area and prepare a planographic printing plate [E] 1. [:E
)-2 and [F] were obtained.

Each printing plate thus obtained was attached to a GTO type printing machine manufactured by Heidelberg, and printed on high-quality paper using commercially available ink. Lithographic printing plates [E]-1, (E)-2 and [
The final number of copies printed for [F] was as shown in Table 4.

As shown in Table 4, lithographic printing plates [:E]-1 and [E]-2 (Example 7) using the photosensitive composition of the present invention
and 8) have a larger number of prints than the comparative example [F],
It has excellent printing durability.

Table 4

Claims (1)

[Claims] A photosensitive composition comprising a photosensitive compound and a polyurethane resin having a -CO-NH-CO- group, which is insoluble in water and soluble in an alkaline aqueous solution.