JPS63287948A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive compsn. having superior developability for aq. alkali developing soln. and high durability for printing by incorporating a polyurethane resin having carboxyl groups and fluorine-substituted hydrocarbon groups into the compsn. CONSTITUTION:The title photosensitive compsn. contains polyurethane resin having carboxyl groups and fluorine-substituted hydrocarbon groups. Also, a photosensitive compsn. consisting of an o-quinonediazide compd. as a photosensitive compd. in combination with a negatively acting diazonium compd., a polymerizable monomer, and a photopolymn. initiator, or a photosensitive compsn. consisting of a combination of a negatively acting diazonium compd., a polymerizable monomer, and a photopolymn. initiator, etc. may be used. Accordingly, either a positive photosensitive compsn. or a negative photosensitive compsn. can be obtained. Such photosensitive compsn. has superior coatability when it is coated on a base, and superior developability for aq. alkali developing soln. when its exposed part is developed after coating, drying, and image exposure. Since an obtd. relief image has high abrasion resistance and high adhesion to a base, a great number of satisfactory printed matters are obtd. when the compsn. is used in a printing form.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of the Invention] 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-naphthoquinonediazide 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. Ta.

However, due to the nature of the novolac type phenolic resin used as the main material, it has poor adhesion to the substrate, brittle film, poor coating properties, poor abrasion resistance, and printing durability when used in lithographic printing plates. There were some points that needed to be improved, such as an insufficient amount of energy, 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
Although the polyhydroxystyrene or hydroxystyrene copolymer described in Japanese Patent No. 1050 did have improved film properties, it had the drawback of poor abrasion resistance. Furthermore, in JP-A-51-34711, it is proposed to use a polymer compound having a structural unit of an acrylic acid derivative in its molecular structure as a binder; There were problems such as a narrow range and insufficient wear resistance.

Furthermore, polyurethane resins are known as polymers having excellent wear resistance, and Japanese Patent Publication No. 49-36961 discloses a combination system of a positive-acting diazo 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, so it cannot be developed to completely remove the photosensitive layer in the non-image area (exposed area). It was extremely difficult to do so.

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

Since the anionic polyurethane resin is water-based, 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 one is diazo resin, represented by a formaldehyde condensate of p-diazodiphenylamine.

The composition of the photosensitive layer of a photosensitive lithographic printing plate using a diazo resin may be a diazo resin alone, i.e. without a binder, as described, for example, 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 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;
and JP-A-56-94346 disclose 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, respectively. . 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.

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 novel photopolymerization initiators, such as those disclosed in British Patent No. 1,388.492, are known, and some of them have been put into practical use. Photosensitive compositions also have the disadvantage that their sensitivity is influenced by the surface temperature of the photosensitive lithographic printing plate during image exposure, and that they are strongly inhibited by oxygen during image exposure.

[Problem that the invention seeks to solve]

An object of the present invention is to overcome the above-mentioned drawbacks and to provide a novel photosensitive composition that has excellent developability with an aqueous alkaline developer and high printing durability.

[Structure of the invention]

The present inventors have achieved the above object (as a result of intensive study,
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 a photosensitive composition containing a polyurethane resin having a carboxyl group and a fluorine-substituted hydrocarbon group.

The photosensitive compounds contained in the photosensitive composition of the present invention include the following (i), (ii), (iii) or (iv).
: (i) o-quinonediazide compound.

(ii) Negative-acting diazonium compounds.

(iii) combination of a polymerizable monomer and a photoinitiator;

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

Photosensitive compounds selected from can be used.

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.

(1) Polyurethane resin The polyurethane resin suitably used in the present invention is a polyurethane resin mainly containing a group having a carboxyl group and a group having a fluorine-substituted hydrocarbon group in the main chain, and preferably has the following general formula: Included are polyurethane resins whose basic skeleton is a reaction product of a diisocyanate compound represented by (1) and a diol compound having a carboxyl group represented by general formula (n), (III) or (rV).

Mouth CN-R, -NCO (I) ■ Rs ■ DDH Hlow R2-^r-R, Off Rs (III) C00I
(HO-R,-N-R,-0)1 Rs (rV)DO
II where R1 is a substituent (e.g. alkyl, aralkyl,
Aryl, alkoxy, cyano, nitro, and halogeno groups are preferred. ) represents a divalent aliphatic or aromatic hydrocarbon that may have. If necessary, RI may contain other functional groups that do not react with incyanate groups, such as ether, ester, urethane, amide, ureido, and carbonyl groups.

R2 is a hydrogen atom, a substituent (for example, cyano, nitro, halogen atom (-F, -Cj, C0NHz, C0
0Rt, ORt, N HCON HR? ,−
N HCOOR1, -NHCORl, -0CONHR7
, -CONHR, -COR, (where R1 represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 15 carbon atoms). ) represents an alkyl, ``aralkyl, aryl, alkoxy, or aryloxy group which may have a hydrogen atom or a carbon number of 1 to 1.
It represents 8 alkyl groups and an aryl group having 6 to 15 carbon atoms. Rz, R-, and Rs may each be n- or different, and each represents a single bond or a substituent (for example, alkyl, aralkyl, aryl, alkoxy, cyano, nitro, or halogeno groups are preferable). Indicates a divalent aliphatic or aromatic hydrocarbon that may be present. Preferably carbon number 1-20
alkylene group, arylene group having 6 to 15 carbon atoms,
More preferably, it represents an alkylene group having 1 to 8 carbon atoms.

Further, if necessary, Rs, R-, and Rs may contain other functional groups that do not react with incyanate groups, such as carbonyl, ester, urethane, amide, ureido, and ether groups. Note that two of R2, R,, R,, R,
Alternatively, three may form a ring.

^r represents a trivalent aromatic hydrocarbon which may have a substituent, preferably an aromatic group having 6 to 15 carbon atoms.

Specifically, the diisocyanate compound represented by the general formula (r) includes those shown below.

That is, 2,4-tolylene diisocyanate, a dimer of 2゜4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m
-xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3°3'-dimethylbiphenyl-4,4'-
Aromatic diisocyanate compounds such as diisocyanate; aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate, etc.; isophorone diisocyanate, 4.4
'-methylenebis(cyclohexyl isocyanate),
Methylcyclohexane-2,4 (or 2,6) diisocyanate, l.

Ring group diisocyanate compounds such as 3-(incyanatomethyl)cyclohexane; diisocyanate compounds which are reaction products of diol and diisocyanate such as an adduct of 1 mol of 1,3-butylene glycol and 2 mol of tolylene diincyanate; etc. can be mentioned.

Further, the diol compound having a carboxyl group represented by the general formula (n), (III) or (IV) specifically includes those shown below.

i.e. thi, 3,5-dihydroxybenzoic acid, 2,2-bis(
hydroxymethyl)propionic acid, 2゜2-bis(2-
Hydroquinethyl)propionic acid, 2,2-bis(3-
hydroxypropyl)propionic acid, bis(hydroxymethyl)acetic acid, bis(4-hydroxyphenyl)acetic acid,
4.4-bis(4-hydroxyphenyl)pentanoic acid,
Tartaric acid, N,N-bis(2-hydroxyethyl)-3-
Examples include carboxy-propionamide, N,N-bis(2-hydroxyethyl)glycine, and the like.

The fluorine-substituted hydrocarbon group in the polyurethane resin of the present invention is a halogen having a fluorine-substituted hydrocarbon group (Cj7,8r, I ) compound or a sulfonate compound in the presence of a base, it can be incorporated into a polyurethane resin.

Further, a diisocyanate compound having a fluorine-substituted hydrocarbon group can also be incorporated into the polyurethane resin by using the diisocyanate compound of general formula (I) together.

Furthermore, a diol compound having a fluorine-substituted hydrocarbon group can also be incorporated into the polyurethane resin by using it in combination with a diol compound of general formula (II), (III) or (1'V).

Here, the fluorine-substituted hydrocarbon group refers to an aliphatic group which may have a substituent having at least one fluorine atom (for example, alkyl, aralkyl, aryl, alkoxy, halogeno, cyano, and nitro groups are preferable). Or represents an aromatic hydrocarbon group.

Preferably, an aliphatic hydrocarbon group having 1 to 18 carbon atoms or having 6 to 18 carbon atoms having two or more monovalent or divalent fluorine atoms
15 aromatic hydrocarbon groups are shown.

The polyurethane resin of the present invention is a diisocyanate compound represented by the general formula (N) and the general formula (n), (III
) or (IV) may be formed from two or more diol compounds having a carboxyl group.

Furthermore, a diol compound that does not have a carboxyl group and may have other substituents that do not react with incyanate may be used in combination to the extent that the alkali developability is not deteriorated.

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/Lz.

1, 3-butylene glycol, 1,6-hexanediol, 2-butene-1,4-dionope 2°2.4-)
Dimethyl-1,3-bentanediol, 1,4-bis-
β-hydroxyethoxycyclohexane, cyclohexane dimetatool, hydrogenated bisphenol A1 hydrogenated bisphenol F1 ethylene oxide adduct of bisphenol A, bisphenol A
propylene oxide adduct of bisphenol F, ethylene oxide adduct of bisphenol F, ethylene oxide adduct of hydrogenated bisphenol A, propylene oxide adduct of hydrogenated bisphenol A, hydroquinone dihydroxyethyl ether, p-xylene Lenglyconopedihydroxyethyl sulfone, bis(2-hydroxyethyl)-2,4-
) lylene dicarbamate, 2,4-tolylene-bis(2
-hydroxydiethylrubamide), bis(2-hydroxyethyl)-m-xylylene dicarbamate, bis(2-hydroxyethyl)-m-xylylene dicarbamate,
-hydroxyethyl) isophthalate and the like.

The polyurethane resin used in the present invention contains the above diisocyanate compound and diol compound in an aprotic solution.
Add a known catalyst with activity according to each reactivity,
Synthesized by heating. The molar ratio of diisocyanate and diol compound used is preferably o, g
:t to 1.2:1, and when inocyanate groups remain at the polymer terminals, by treating with alcohols, amines, etc., the polymer is finally synthesized in a form in which no isocyanate groups remain.

The molecular weight of the polyurethane resin used in the present invention is preferably 1,000 or more on weight average, more preferably 5.
The range is from 000 to 100,000.

These polyurethane resins may be used alone or in combination. The content of these polyurethane resins contained in the photosensitive composition is about 5 to 90% by weight, preferably about 10 to 60% 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. Nos. 3.046.120 and 3.188.210;
There are esters of 2-diazonaphthoquinonesulfonic acid chloride and phenol-formaldehyde resins. Other useful O-naphthoquinone diazide compounds include:
It is reported and known in numerous patents. For example, JP-A-47-5303, JP-A-48-63802, JP-A-48-63803, JP-A-Machi No. 48-96575, JP-A-4
No. 9-38701, No. 13354 (1973), Special Publication No. 4 (Sho 4)
No. 1-11222, No. 9610 of the same year, opened and closed in 1972
-17481 Publication, U.S. Patent No. 2.797.213, U.S. Patent No. 3.454.400, U.S. Patent No. 3,544.32
No. 3, No. 3,573.917, No. 3.674.4
No. 95, No. 3.785.825, British Patent No. 1.2
No. 27.602, No. 1.251.345, No. 1.
No. 267.005, No. 1,329,888, No. 1
, 330.932, and German Patent No. 854,890.

The amount of these positive-acting O-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 diazonium compounds Examples of the diazonium compounds used in the present invention include the diazonium compounds described in U.S. Pat. No. 3,867,147 and the diazonium compounds described in U.S. Pat. No. 2,632,703. Diazo resins typified by condensates with carbonyl-containing compounds (for example, formaldehyde) are useful.

Preferred diazo resins include, for example, hexafluorophosphates, tetrafluoroborates, and phosphates of condensates of p-diazodiphenylamine and formaldehyde or acetaldehyde. Also, U.S. Patent No. 330030
Sulfonates of condensates of p-diazodiphenylamine and formaldehyde as described in No. 9 (e.g. p-)luenesulfonates, dodecylbenzenesulfonates, 2-methoxy-4-hydroxy-5- Also preferred are benzoylbenzenesulfonate, etc.), phosphinates (eg, benzenephosphinate, etc.), hydroxy group-containing compound salts (eg, 2,4-dihydroxybenzophenone salt, etc.), and organic carboxylates. .

Furthermore, 3-methoxy-4-diazo-diphenylamine as shown in JP-A No. 58-27141 is added to 4,4
Mesitylene sulfonate obtained by condensation with '-bis-methoxy-methyl-diphenyl ether is also suitable.

The content of these diazonium compounds in the photosensitive composition is 1 to 50% 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 at least one monomer per molecule, more preferably two monomers per molecule. It is a monomer or oligomer having a molecular weight of 10.000 or less and having an ethylenically unsaturated group capable of addition polymerization. Such monomers or oligomers include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth)acrylate, polypropylene glycol mono (meth)acrylate, phenoxyethyl (meth)acrylate; polyethylene glycol di(meth)acrylate, polyethylene Glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neobentyl glycol di(meth)acrylate, pentaerythritol tri(
meth)acrylate, pentaerythritol tetra (
meth)acrylate, dipentaerythritol hexa(
Meth)acrylate, hexanediol di(meth)acrylate, tri(acryloyloxyethyl)incyanate, polyhydric alcohol such as glycerin or trimethylolethane, which is converted into (meth)acrylate after adding ethylene oxide or propylene oxide. , urethane acrylates as described in Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034, and Japanese Patent Application Publication No. 51-37193; Examples include polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates prepared by reacting an epoxy resin with (meth)acrylic acid, which are described in Japanese Patent Publication No. 52-30490. Furthermore, Japan Adhesive Association Journal Vo
1, 20, Nα7. Those introduced as photocurable monomers and oligomers on pages 300 to 308 can also be used.

The composition ratio of these monomers or oligomers to the polyurethane resin of the present invention is preferably in the range of 5:95 to 70:30 by weight, and more preferably in the range of 10:90 to 50:5.
It is 0.

Photopolymerization initiators 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. 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 alpha-hydrocarbons as disclosed in the specification, multi-branched quinone compounds as disclosed in U.S. Pat. No. 3.046.127 and U.S. Pat. Triarylimidazole dimer/p-
Combination of Aminophenyl Ketones, U.S. Patent No. 3.870
．． benzothiazole compounds disclosed in U.S. Pat. No. 524, acridine and phenazine compounds disclosed in U.S. Pat. No. 3,751,259, and acridine and phenazine compounds disclosed in U.S. Pat. This includes oxadiazole compounds, etc.

Preferably trihalomethyl-3-) represented by the following general formula (V) or (Vl)! Examples include J azine compounds and trihalomethyloxadiazole compounds.

In the formula, R9 is a substituted or unsubstituted aryl group,
The alkenyl group Rs represents Rs, -CX, or a substituted or unsubstituted alkyl group. X represents a chlorine atom or a bromine atom.

Examples of the compound represented by the general formula (V) include those described by Kuhai et al., Bull, Chem, Soc, Japan, Vol.
Compounds described in Volume 2, Page 2924 (1969), British Patent No. 1.388.492, West German Patent No. 2.718
．． No. 259, and the compounds described in West German Patent No. 3.337,024. Specifically, the following compounds are included.

That is, 2-722-4,6-bis(trichloromethyl)-3-)riazine, 2-(p-chlorophenyl)-
4,6-bis(trichloromethyl)-8-triazine,
2-(p-)lyl)-4,6-bis(trichloromethyl)-3-triazine, 2-(1comethoxyphenyl)-4,6-bis(trihalomethyl)-3-)lyazine, 2- (2',4'-dichlorophenyl)-4,6-bis(trichloromethyl)-5-triazine, 2°4.6
- tris(trichloromethyl)-3-triazine, 2
-methyl-4,6-bis(trichloromethyl)-3-)
Riazine, 2-n-nonyl-4゜6-bis(trichloromethyl)-5-)lyazine, 2-(cχ,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-3- ) riazine, 2-studitolyl-4,6-bis(
trichloromethyl)-3-11-riazine, 2-(p-
methylstyryl)-4,f3-bis(trichloromethyl)-3-triazine, 2-(p-methoxystyryl)-
4,6-bis(trichloromethyl)-3-)riazine, 2-(4-methoxy-naphth-1-yl)-4゜6-
Bis(trichloromethyl)-3-triazine, 2-(,
4-ethoxy-naphth-1-yl)-4゜6-bis(trichloromethyl)-3-)riazine, 2-(4-(2
-ethoxyethyl)-naphth-1-yl]-4,6-bis(trichloromethyl)-5-triazine, 2- (4
,7-dimethoxy-naphthol-1-yl)-4,6-bis(trichloromethyl)-S-triazine, 2-(acenaphth-5-yl)-4,6-bis(trichloromethyl)
-3-) riazine, 2-(4-styrylphenyl)-4
, 6-bis(trichloromethyl)-5-)riazine, and the like.

Further, as the compound represented by the general formula (VI), for example, JP-A No. 54-74728, JP-A No. 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-Oxadiazolepe2-(4-chlorostyryl)-
5-) Lichloromethyl-1,3°4-oxadiazole, 2-(4-methylstyryl)-5-trichloromethyl-i, 3,4-oxacyal-7'-yl, 2-(4-methoxystyryl) -5-) +, l chloromethyl-i,
3. 4-Oxadiazolebe 2-(4-butoxystyryl)-5-trichloromethyl-1,,3,4-oxadiazole, 2-(4-styrylstyryl)-5
-trichloromethyl-1,3,4-oxadiazole,
2-phenyl-5-trichloromethyl-1,3,4-oxadiazole, 2(4-methoxyphenyl)-5-)
Lichloromethyl-1,3,4-oxadiazolebe 2
- (3,4-dimethquininyl)-5-trichloromethyl-1,3,4-oxadiol, 2-(4-
styrylphenyl)-5-trichloromethyl-1,3,
Included are 4-oxadiazole, 2-(1-naphthyl)-5-trichloromethyl-1,3,4-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, Japanese Patent Publication No. 54-1
Merocyanine dye shown in JP-A No. 51024, aromatic Thiobi IJ shown in JP-A No. 58-40302
Examples include IJium salts, aromatic biryllium salts, and other light absorbers such as 9-phenylacridine, 5-nitroacenaphthene, and ketocoumarin. Furthermore, these include N-phenylglycine, 2-menicaptobenzothiazole, N,
A system in which a hydrogen donor such as ethyl N'-dimethylaminobenzoate is combined can also be effectively used in the present invention.

The amount of the photopolymerization initiator and/or sensitizer in the present invention is
A range of 0.01% to 20% by weight of the photopolymerizable ethylenically unsaturated compound and the polyurethane resin of the present invention is sufficient, and more preferably 0.5% by weight.
Good results are obtained at 10% by weight.

(5) Other components In addition to the above-mentioned polyurethane resin, the composition of the present invention contains phenol formaldehyde resin, talesol formaldehyde resin, phenol-modified xylene' resin, polyhydroxystyrene, borino-10-genated hydroxystyrene, and carboxyl group-containing Known alkali-soluble polymer compounds such as Evokin resin, polyacetal resin, acrylic resin, and methacrylic resin can be contained. Such alkali-soluble polymer compound is used in an amount of 70% by weight or less of the total composition.

In the m-viewing medium of the present invention, print-out agents to obtain a visible image immediately after exposure, dyes as image coloring agents, face powder, stabilizers, surfactants, plasticizers, and other fillers may be added. Can be done.

Further, when combined with an O-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, 3,6-nindooxy-Δ4-tetrahydrophthalic anhydride, as described in U.S. Pat. No. 4,115,128. Examples include tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, and pyromellitic anhydride. 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.

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 O-naphthoquinonediazide-4-sulfonic acid halide and salt-forming organic dye described in JP-A No. 128, JP-A-53-36223, JP-A-5474
The combination of a trihalomethyl compound and a salt-forming organic dye described in Japanese Patent No. 728 can be mentioned.

Dyes other than the above-mentioned salt-forming organic dyes 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 green BG, oil blue BO3, oil blue #60.
3. Oil Black BY, Oil Black BS, Oil Black T-505 (manufactured by Orient Chemical Industry Co., Ltd.), Victoria Picoa Blue, Crystal Violet (CI42555), Methyl Violet (C
I42535), rhodamine B (CI45170B),
Examples include malachite green (CI42000) and methylene blue (CI52015).

Furthermore, when combined with a diazonium compound, stabilizers include phosphoric acid, phosphorous acid, sinuic acid, p-toluenesulfonic acid, dipicolinic acid, malic acid, tartaric acid, 2-methoxy-4-hydroxy-5-benzoyl-benzene. Examples include sulfonic acid, butylnaphthalenesulfonic acid, p-hydroxybenzenesulfonic acid, and the like.

Furthermore, when a polymerizable monomer is combined with a photoinitiator, a small amount of thermal polymerization can be applied to prevent unnecessary thermal polymerization of the polymerizable ethylenically unsaturated compound by wiping it during production 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,
Pyrogallonope t-butylcatechol, Benso 1-
Non, 4,4'-thiobis(3-methyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, N-nitronphenylhydroxyamine Examples include cerous salts.

The composition of the present invention is applied onto a support after being dissolved in a solvent that dissolves each of the above components. The solvent used here is
Methanol, ethanol, impropatol, n-butanol, t-butanol, ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, l-methoxy-2- Examples include propatool, 1-methoxy-2-propyl acetate, N,N-dimethylformamide, tetrahydrofuran, dioxane, dimethyl sulfoxide, toluene, and ethyl acetate, and these solvents may be used alone or in combination. The concentration (solid content) of the above components is 2 to 50% by weight.

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/m' 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,
Includes plastic films such as cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc., and paper or plastic films laminated or vapor-deposited with the metals listed above. . 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.

In addition, in the case of a support having a surface of metal, especially aluminum, surface treatments such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, etc., or anodization treatment are performed. It is preferable that Further, as described in U.S. Pat. after being anodized and then immersed in an aqueous solution of an alkali metal silicate, treated by a combination of mechanical and electrolytic roughening as described in U.S. Pat. No. 4,476,006. Also suitable are aluminum supports. The above-mentioned anodizing treatment may be performed using, for example, an aqueous or non-aqueous solution of an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, or boric acid, or an organic acid such as oxalic acid or sulfamic acid, or a salt thereof, either alone or in combination of two or more. It is carried out by passing an electric current through an aluminum plate as an anode in an electrolytic solution.

It is also preferable that the material is grained, anodized, and then sealed. Such pore sealing treatment is performed using a sodium silicate aqueous solution,
This is carried out by immersion in hot water and a hot aqueous solution containing an inorganic or organic salt, a steam bath, and the like.

Also effective is silicate electrodeposition as 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 positive or negative relief image to the original.

Light sources used for exposure include carbon arc lamps, mercury lamps, xenon lamps, tungsten lamps, and metal halide lamps.

〔Effect of the invention〕

The photosensitive composition of the present invention has excellent coating properties when applied onto a support, and also excellent developability when developing exposed areas 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.

"Examples" 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.

Synthesis Example 1 In a 500rd 3-day round bottom flask equipped with a condenser and a stirrer, 125 g (0.50 mol) of 4,4′-diphenylmethane diisocyanate and 67 g of 2°2-bis(hydroxymethyl)propionic acid ( 0.50 mol) was added and dissolved in dioxane 290me. N as a catalyst
, N-diethylaniline (1 g) was added thereto, and the mixture was heated under reflux for 6 hours with stirring. After that, the reaction solution was mixed with 41 ml of water and 40 ml of acetic acid.
The mixture was poured into the solution of No. 1 with stirring to precipitate a white polymer. This polymer was filtered off, washed with water, and dried under vacuum to obtain 185 g of polymer.

When the molecular weight was measured by gel permeation chromatography (GPC), the weight average (polystyrene standard) was 28.000. Further, the carboxyl group content was measured by titration and found to be 2.47 meq/g.

Furthermore, 40 g of this polymer was placed in a 300-sized round bottom flask equipped with a condenser and a stirrer, and DMF 20
It was dissolved at 0-. Add 2.6 ml of triethylamine to this solution.
g (0,026 mol) and heated to 80°C, I
10.3 g (0,026 mol) of H,IH,7H-dodecafluoro-1-hebutyl bromide were added. Stirring was then continued for 2 hours.

After the reaction is complete, add 41.5% of the reaction solution to water. The mixture was poured into a solution of 200 kg of acetic acid with stirring to precipitate a white polymer.

This polymer was filtered, washed with water, and dried under vacuum to obtain 44 g of polymer.

It was confirmed by NMR measurement that IH,LH,7H-dodecafluoro-1-hebutyl group had been introduced, and the acid value was further measured by titration, and it was found that L, 70111e
q/g [Polyurethane (a) used in the present invention]
.

Synthesis Example 2 500 mj equipped with a condenser and a stirrer! 94g of m-xylylene diacetate in a 3-necked round flask (
0.50 mol), N-(1,1-bis(hydroxymethyl)propyl)pentafluorobenzenesulfonamide and 47 g (0.35 mol) of 2,2-bis(hydroxymethyl)propionic acid were added, and 330 ml of dioxane was added.
! dissolved in. 1 g of N,N'-diethylaniline was added as a catalyst, and the mixture was heated under reflux for 6 hours with stirring. Thereafter, the reaction solution was poured into a solution of 41 parts water and 40 parts acetic acid with stirring to precipitate a white polymer. This polymer was filtered, washed with water, and dried under vacuum to obtain 180 g of polymer.

When the molecular weight was measured by GPC, the weight average (polystyrene standard) was 24.000. Furthermore, when the acid value was measured by titration, it was 1.72 meQ/g. (Polysrene used in the present invention)).

Synthesis Examples 3 to 14 Polyurethane resins used in the present invention were synthesized in the same manner as Synthesis Example 1 or 2 using the diisocyanate and diol compounds shown in Table 1.

The molecular weight was measured by GPC, and the acid value was measured by titration. The measured acid values are shown in Table 1.

Moreover, the molecular weights were all weight average (polystyrene standard) from 11.000 to 36.000.

Examples 1 to 5 The surface of an aluminum plate having a thickness of 0.30 mm was grained using a nylon brush and 400 mesh Pumistone water B35 solution, and then thoroughly washed with water. After etching by immersing in IJum (10% hydroxide) at 70° C. for 60 seconds, washing with running water, neutralizing with 20% nitric acid, and washing with water. This was carried out at 160 chrome/d 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 with an anode special electricity amount of m'. When the surface roughness was measured, it was 0.6μ (expressed as Ra).

Subsequently, it was immersed in a 30% sulfuric acid aqueous solution and heated at 55°C for 2 hours.
After desmutting for a minute, it was anodized in a 20% aqueous sulfuric acid solution at a current density of 2 A/d+n' to a thickness of 2.7 g/m'.

Next, by changing the type of polyurethane resin used in the present invention in the following photosensitive liquid [A], five types of photosensitive liquids (A)-1 to [A] were prepared.
-5 was prepared, and this photosensitive solution was applied onto an anodized aluminum plate and dried at 100°C for 2 minutes to produce photosensitive lithographic printing plates CA)-1 to [A)-5, respectively.

The coating amount at this time was 2.5 g/m' in terms of dry weight.

The polyurethane resins used in the present invention for photosensitive liquid 1:A]-1 to [A'', .-5 are shown in Table 2.

Photosensitive liquid [Δ] Next, as a comparative example, the following photosensitive liquid [B] was applied in the same manner as photosensitive liquid [A] to prepare a photosensitive lithographic printing plate [B'l].

The coating weight after drying was 2.5 g/m''.

Photosensitive liquid CB) A positive transparent original of the line drawing and halftone image was brought into close contact with the photosensitive layer of the photosensitive lithographic printing plates [A]-1 to 5 and CB], and
Exposure was carried out with an ampere carbon arc lamp from a distance of 70 cm.

Exposed photosensitive lithographic printing plates 1: A)-1 to 5 and CB
) was immersed and developed in an 8-fold diluted aqueous solution of DP-4 (trade name: manufactured by Fuji Photo Film ■) at 25° C. for 60 seconds.

The obtained lithographic printing plates [A)-1 to [A]-5 and CI were used to print on high-quality paper using a commercially available ink using a KOR type printing machine manufactured by Heidelberg. Lithographic printing plates [A]-1 to 5 and [B)
The final number of copies printed was as shown in Table 2).

Table 2 As can be seen from Table 2, the lithographic printing plates (A)-1 to 5 (Examples 1 to 5) using the photosensitive composition of the present invention had better printing performance than the comparative example CB). It has a large number of sheets and has excellent printing durability.

In addition, instead of the resin of the present invention in photosensitive liquid CA), Nissan #5715 (Shi5tane 95715, B, F) was used as a commercially available polyurethane resin that does not have a carboxyl group.
When coating, exposing, and developing were carried out in the same manner using the following method (manufactured by Gudrich Co., Ltd.), poor development occurred and a clear image could not be obtained. - From this, it can be seen that the resin of the present invention has extremely excellent developability in an aqueous alkaline developer compared to polyurethane resins that do not have carboxyl groups.

Example 6 - IO The surface of an aluminum plate with a thickness of 0.24 ffffl was grained using a nylon brush and an aqueous suspension of 400 mesh of bumiston (washed with water). After etching by immersing in an aqueous solution at 70°C for 60 seconds, washing with running water and neutralizing with 20% nitric acid, the surface was roughened using the electrochemical surface roughening method described in JP-A-53-67507, ie, VA = 12. 7V, Vc =9.
Electrolytic surface roughening treatment was carried out using an IV sinusoidal alternating waveform current in a 1% nitric acid aqueous solution with an anode specific electricity amount of 1.60 croons/dm2. Subsequently, it was immersed in a 30% sulfuric acid aqueous solution and desmutted at 55° C. for 2 minutes, and then anodized in a 7% sulfuric acid aqueous solution so that the coating amount of aluminum oxide was 2.0 g/m'. Thereafter, it was immersed in a 3% aqueous solution of sodium silicate at 70° C. for 1 minute, washed with water and dried.

The following photosensitive solutions (C:]-1 to [CD-5] shown below were applied to the aluminum plate obtained as described above using a wheeler and dried at 80°C for 2 minutes.The dry weight was 2.0g/ m
"Met.

The polyurethane resins used in the present invention for photosensitive solutions [C)-1 to [CD-5] are shown in Table 3.

Photosensitive liquid [CD] Next, as a comparative example, photosensitive liquid C was prepared using the following polymer instead of the polyurethane resin used in the present invention in the above photosensitive liquid.
D) was applied and dried in the same manner. Dry weight is 2.0g/m
'Met.

(Polymer used in comparative example) A polymer with H structure, a / b / c /
The molar ratio of d was 9/24158/9.

Moreover, the molecular weight is 55.
It was 000.

Each of the photosensitive planographic printing plates (C)-1 to 5 obtained using the photosensitive liquid (C3-1 to 5 and [D] and CDE) was imaged for 1 minute from a distance of 1 m using a PS light manufactured by Fuji Photo Film ■. After exposing to light and immersing it in the following developing solution at room temperature for 1 minute, the surface was lightly rubbed with absorbent cotton to remove the unexposed area, and a lithographic printing plate with a bright blue image (C3-1 to 5 and [D]) was prepared.
I got it.

(Developer) Each printing plate was printed on high-quality paper using a commercially available ink using a KOR type printing machine manufactured by Heidelberg.

When the final number of printed sheets of lithographic printing plates 1:C) 1 to 5 and CD) was examined, they were as shown in Table 3.As can be seen from Table 3, the photosensitive composition of the present invention was for'
, )da lithographic printing plate CC)-1~5 (Execution VA6~10
) has a larger number of prints than the comparative example [D], and has very excellent printing durability.

Examples 11 to 14 The aluminum obtained in Example 6 was prepared using the following photosensitive solution [:E
Apply E-1 to [E]-4 using a wheeler and heat at 80°C.
and dried for 2 minutes. The dry weight was 2.0 g/m'.

The polyurethane resins used in the present invention for photosensitive liquids CE)-1 to EE-4 are shown in Table 4.

Photosensitive liquid [EE] Next, as a comparative example, benzyl methacrylate-methacrylic acid (molar ratio 73/27) copolymer was used instead of the polyurethane resin used in the present invention in the photosensitive liquid, and the weight average molecular weight was 45,000 (polystyrene standard). )) Photosensitive solution C using
F) was applied in the same manner and dried. Dry weight is 2.0g/m
"Met.

Each of the photosensitive lithographic printing plates CE]-1 to 4 and rF) obtained using the photosensitive solutions r, , E]-1 to 4 and [F) was coated with a PS light manufactured by Fuji Photo Film @ from a distance of 1 m. 1
After exposing the image for 1 minute and immersing it in the developer used in Example 6 at room temperature for 1 minute, the surface was lightly rubbed with absorbent cotton to remove the exposed area, and a bright blue image was formed on the lithographic printing plate CE3.
-1 to 4 and [F2 were obtained.

Each printing plate was used to print on high-quality paper using a commercially available ink on a Heidelberg KOR printing machine.

The final number of printed sheets of the lithographic printing plates (E)-1 to 4 supports [F] was examined and was as shown in Table 4.

Table 4 As shown in Table 4, lithographic printing plates (El l~4 (Examples 11~14) using the photosensitive composition of the present invention)
Compared to Comparative Example [F], the number of prints was larger (and the rigidity resistance was very excellent).

Examples 15-16 The following photosensitive liquid [G] was applied to the aluminum plate obtained in Example 6.
-1 to [:G:l-2 were applied using a wheeler, and 80
Dry for 2 minutes at °C. The dry weight was 2.0 g/m''.

The polyurethane resins used in the present invention for the photosensitive liquids CGE-1 to CG]-2 are shown in Table 5.

Photosensitive liquid [G] Next, as a comparative example, methyl methacrylate-methacrylic acid (molar ratio 80/20) copolymer (weight average molecular weight 5
2,000 (polystyrene standard))
) was applied and dried in the same manner. Dry weight is 2.0g/m''
Met.

Photosensitive lithographic printing plates [GE-1 to 2 and [H] obtained using photosensitive liquids CG)-1 to 2 and [H] were imaged for 1 minute from a distance of 1 m using a PS light manufactured by Fuji Photo Film ■, respectively. After exposing to light and immersing it in the developer used in Example 6 at room temperature for 1 minute, the surface was lightly rubbed with absorbent cotton to remove the unexposed area, and the planographic printing plates CG)-1 to 2 with bright blue images were prepared. Got CHE.

Each printing plate was used to print on high-quality paper using a commercially available ink on a Heidelberg KOR printing machine.

The final number of printed sheets of the lithographic printing plates [G3-1 to G3-2 and [H] was examined and was as shown in Table 5.

Table 5 As can be seen from Table 5, the lithographic printing plates CG)-1 to 2 (Examples 15 to 16) using the photosensitive composition of the present invention had a lower number of printed sheets than the comparative example [H]. It has a high printing durability and has excellent printing durability.

〔Effect of the invention〕

The photosensitive composition of the present invention has excellent developability with an aqueous alkaline developer and has high printing durability.

Claims (1)

[Claims] A photosensitive composition comprising a polyurethane resin having a carboxyl group and a fluorine-substituted hydrocarbon group.