JP2547607B2 - Photosensitive composition - Google Patents

Description

The present invention relates to a photosensitive composition suitable for producing a lithographic printing plate, an IC circuit and a photomask. More specifically, the present invention relates to a photosensitive composition comprising a positive-working or negative-working photosensitive compound and a polymer compound having excellent abrasion resistance and developability.

[Conventional technology]

In a positive acting system, a photosensitive composition comprising an o-naphthoquinonediazide compound and a novolac type phenolic resin has been industrially used as a very excellent photosensitive composition for producing a lithographic printing plate or as a photoresist. It was

However, due to the nature of the novolac-type phenolic resin used as the main component, the adhesion to the substrate is poor, the skin is brittle, the coatability is poor, the abrasion resistance is poor, and the printing durability when used for lithographic printing plates is There were some points to be improved such as not being sufficient, and there was a limit in application.

In order to solve this problem, various polymer compounds have been investigated as binders. For example, Japanese Patent Publication 52-41
The polyhydroxystyrene or hydroxystyrene copolymer described in Japanese Patent Publication No. 050 has certainly improved film properties, but has the disadvantage of poor abrasion resistance. Further, in JP-A-51-34711, it is proposed to use a polymer compound having a structural unit of an acrylic acid derivative in the molecular structure as a binder. There were problems such as narrow range and insufficient abrasion resistance.

As a known polymer having further excellent abrasion resistance, there is a polyurethane resin, and in Japanese Patent Publication No. Sho 49-36961,
A combination system of a positive-acting diazo compound and a substantially linear polyurethane resin is disclosed. However, since the polyurethane resin does not have an alkali-soluble group, the solubility in an aqueous alkyl developing solution is essentially insufficient, and development is performed so that the photosensitive layer in the non-image area (exposed area) can be completely removed. Was very difficult to do.

Furthermore, Japanese Patent Application Laid-Open No. 61-20939 discloses a photosensitive composition using an anionic polyurethane resin. Such anionic polyurethane resins are aqueous, and are substantially different from the water-insoluble polyurethane resins of the present invention. Since the anionic polyurethane resin is water-based, its solubility in an organic coating solvent was insufficient. Further, it is not preferable because it deteriorates the stability of the diazo compound.

Most of the photosensitive substances used in the negative acting system are diazonium compounds, and the most commonly used compounds are diazo resins represented by formaldehyde condensate of p-diazophenylamine. .

The composition of the photosensitive layer of a photosensitive lithographic printing plate using a diazo resin is, for example, as described in U.S. Pat.No. 2,714,066, a diazo resin alone, that is, without using a binder, for example, As described in JP-A-50-30604, it can be classified into those in which a binder and a diazo resin are mixed.In recent years, many photosensitive lithographic printing plates using a diazonium compound have been It is made of a diazonium compound and a polymer serving as a binder in order to provide high printing durability.

As such a photosensitive layer, as described in JP-A-50-30604, a so-called alkali developing type in which unexposed portions are removed (developed) by an aqueous alkali developing solution, and an organic solvent-based developing solution Although a so-called solvent development type which is removed is known, an alkali development type has attracted attention from the viewpoint of occupational safety and health, and this is mainly determined by the properties of the binder. As a method for imparting alkali developing property to the binder, a carboxylic acid-containing monomer may be copolymerized as described in JP-A-50-30604, or US Pat.
There is a method of introducing a carboxylic acid into a polymer by reacting a hydroxyl group of polyvinyl alcohol with a cyclic acid anhydride such as phthalic anhydride as described in the specification. In addition, the abrasion resistance is poor, and only a lithographic printing plate having low printing durability can be obtained from the photosensitive lithographic printing plate containing such a binder in the photosensitive layer. On the other hand, polyvinyl acetal forms a tough film,
Although it has abrasion resistance, it has a drawback that only an organic solvent-developing photosensitive lithographic printing plate can be obtained. In addition, JP-A-61-2670
Japanese Patent Publication No. 42 discloses a polyvinyl acetal resin having a carboxyl group. Although the resin can be developed with an aqueous alkaline developer and has excellent abrasion resistance,
Adhesion to the substrate during development was insufficient.

Further, there is a polyurethane resin as a well-known polymer having excellent abrasion resistance, and in Japanese Patent Publication No. 49-36961 and Japanese Patent Publication No. 56-94346, a combination of a diazonium compound and a substantially linear polyurethane resin is disclosed. A combination system and a combination system of a diazonium salt condensate and a branched polyurethane resin are disclosed, respectively. But,
As described above, none of these polyurethane resins has an alkali-soluble group, and their inherent solubility in an aqueous alkaline developer is insufficient, and it is extremely difficult to develop them without leaving a residual film. Met. Further, JP-A-60191244 suggests a polyurethane resin having a carboxyl group and a cycloaddition type photosensitive group.
In the case of the polymer, the abrasion resistance of the polymer itself is not sufficient because it has a special photosensitive group and structure.

Furthermore, JP-A-62-123452 and JP-A-62-123453 disclose combination systems of a diazonium compound and a polyurethane resin having a carboxyl group. These resins are in fact developable with an aqueous alkaline developer and have excellent abrasion resistance. However, in the examples described in the above publication, the developability is somewhat insufficient under severe conditions.

On the other hand, many attempts have been made to use the photopolymerizable composition as a photosensitive image forming layer of a negative-working photosensitive lithographic printing plate.
-32714 discloses a basic composition comprising a polymer as a binder, a monomer and a photopolymerization initiator as disclosed in JP-A-32714, and an unsaturated double bond as a binder as disclosed in JP-B-49-34041. Compositions having improved curing efficiency by introducing a bond, Japanese Patent Publication Nos. 48-38403 and 53-27605, and British Patent 1,388,492
Compositions using a novel photopolymerization initiator as disclosed in the specification and the like are known, and some are provided for practical use. The sensitivity is greatly affected by the surface temperature of the photosensitive lithographic printing plate
Further, there is a disadvantage that polymerization is strongly inhibited by oxygen during image exposure.

[Problems to be Solved by the Invention]

An object of the present invention is to provide a novel photosensitive composition which overcomes the above-mentioned drawbacks, has excellent developability with an aqueous alkaline developer, and can provide a printing plate having high printing durability.

More specifically, the present invention relates to the above-mentioned JP-A-62-123452.
No. 62-123453 and No. 62-123453, the purpose is to improve the developability of the photosensitive composition.

[Means for solving the problem]

The above object is a combination system of a diazonium compound acting as a negative type or a polymerizable monomer and a photopolymerization initiator, or an o-quinonediazide compound acting as a positive type,
In a photosensitive composition containing a water-insoluble and alkaline-water-soluble polyurethane resin having a carboxyl group,
It is achieved by a photosensitive composition, wherein the polyurethane resin is a polyurethane resin having at least 1 mol% of a structural unit derived from a compound obtained by ring-opening a tetracarboxylic dianhydride with a diol compound.

The polyurethane resin used in the present invention contains no photosensitive structural unit.

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 described in detail.

(1) Polyurethane Resin The polyurethane resin preferably used in the present invention contains in its skeleton a structural unit derived from a compound obtained by ring-opening a tetracarboxylic dianhydride with a diol compound.

Preferred tetracarboxylic dianhydrides include those represented by the general formula (I), (II) or (II).

In the formula, R ¹ is a single bond or a divalent aliphatic or aromatic hydrocarbon which may have a substituent (for example, alkyl, aralkyl, aryl, alkoxy, halogeno, ester and amide groups are preferable). , -CO -, - SO-, SO 2 -, -
Indicates O- or -S-. Preferably single bond, carbon number 1 to
15 divalent aliphatic _{hydrocarbon, -CO -, - SO 2 -} , - O
-Or -S- is shown. R ² and R ³ may be the same or different, and are a hydrogen atom, alkyl, aralkyl, aryl,
It represents an alkoxy or halogeno group. Preferably, it represents a hydrogen atom alkyl having 1 to 8 carbon atoms, an aryl having 6 to 15 carbon atoms, an alkoxy having 1 to 8 carbon atoms, or a halogeno group. ^{Two of} R ¹ , R ² and R ³ may combine to form a ring. R ⁴ and R ^{5, which} may be the same or different, each represents a hydrogen atom, an alkyl, an aralkyl, an aryl or a halogeno group. It preferably represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 15 carbon atoms. Also
Two of R ¹ , R ⁴ and R ⁵ may combine to form a ring. R ⁶ and R ⁷ may be the same or different and each represents a single bond, a double bond, or a divalent fatty acid hydrocarbon. It is preferably a single bond, a double bond or a methylene group. A represents a mononuclear or polynuclear aromatic ring. It preferably represents an aromatic ring having 6 to 18 carbon atoms.

Specific examples of the compound represented by the general formula (I), (II) or (III) include the following.

That is, pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3'-4,4'-
Diphenyltetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 4,4'-sulfonyldiphthalic acid dianhydride Anhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 4,4 '-[3,3'-(alkyl Phosphoryldiphenylene) -bis (iminocarbonyl)] diphthalic dianhydride, an adduct of hydroquinone diacetate and trimellitic anhydride, an adduct of diacetyldiamine and trimetic anhydride, and the like aromatic tetotacarboxylic dianhydride; 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride (Dainippon Ink and Chemicals, Inc., Epicron B-4400), 1,2, 3,4-cyclopentanthate Dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydrides such as tetrahydrofuran tetracarboxylic dianhydride; 1,2,
Examples thereof include aliphatic tetracarboxylic acid dianhydrides such as 3,4-butanetetracarboxylic acid dianhydride and 1,2,4,5-pentanetetracarboxylic acid dianhydride.

Examples of the method for introducing a structural unit derived from a compound obtained by ring-opening these tetracarboxylic dianhydrides with a diol compound into a polyurethane resin include the following methods.

A method of reacting a diisocyanate compound with an alcohol-terminated compound obtained by ring-opening tetracarboxylic acid dianhydride with a diol compound.

A method of reacting an alcohol-terminated urethane compound obtained by reacting a diisocyanate compound with a diol compound in excess with a tetracarboxylic dianhydride.

As the diisocyanate and compound used here,
Specifically, the following are included.

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,
Aromatic diisocyanate compounds such as 3,3′-dimethylbiphenyl-4,4′-diisocyanate; Aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate;
Aliphatic diisocyanate compounds such as isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, 1,3- (isocyanatomethyl) cyclohexane; 1,3- Examples thereof include a diisocyanate compound which is a reaction product of a diol and a diisocyanate such as an adduct of 1 mol of butylene glycol and 2 mol of tolylene diisocyanate.

In addition, specific examples of the diol compound used include the following.

That is, 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-pentanediol, 1,4-bis-β
-Hydroxyethoxycyclohexane, cyclohexanedimethanol, tricyclodecanedimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, ethylene oxide adduct of bisphenol F, bisphenol F propylene oxide adduct, hydrogenated bisphenol A ethylene oxide adduct, hydrogenated bisphenol A propylene oxide adduct, hydroquinone dihydroxyethyl ether, p-xylylene glycol, dihydroxyethyl sulfone, bis (2-hydroxyethyl)- 2,4-tolylenedicarbamate, 2,4-tolylene-bis (2-hydroxyethylcarbamide), bis (2-hydroxyethyl) -m-xylylene Carbamate, bis (2-hydroxyethyl) isophthalate.

When synthesizing the polyurethane resin of the present invention by the above method, two or more kinds of diisocyanate compounds, diol compounds and tetracarboxylic acid dianhydrides may be used.

In the above reaction, the above-mentioned diol compound can be further used in combination as long as the alkali developability is not reduced.

If necessary, a diol compound having a carboxyl group represented by the general formula (IV), (V) or (VI) may be used in combination.

In the formula, R ⁸ is a hydrogen atom, a substituent (eg, cyano, nitro, halogen atom (—F, —Cl, —Br, —I), —CONH
₂ , -COOR ¹² , -CR ¹² , -COOH, -NHCONHR ¹² , -NHCOOR
¹² , -NHCOR ¹² , -OCONHR ¹² , -CONHR ¹² (where R ¹²
Represents an alkyl group having 1 to 10 carbon atoms and an aralkyl group having 7 to 15 carbon atoms. )). ) Optionally has alkyl, aralkyl, aryl, alkoxy,
Indicates an aryloxy group, preferably a hydrogen atom or a carbon number 1
~ 8 alkyl, and an aryl group having 6 to 15 carbon atoms are shown. R ⁹ , R ¹⁰ and R ¹¹ may be the same or different and each represents a single bond, a substituent (for example, alkyl, aralkyl,
Aryl, alkoxy and halogeno groups are preferred. )
A divalent aliphatic or aromatic hydrocarbon which may have Preferably, an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 15 carbon atoms, and more preferably 1 to 1 carbon atoms.
8 alkylene groups are shown. If necessary, R ⁹ ,
R ¹⁰ and R ¹¹ may have another functional group that does not react with an isocyanate group, for example, a carbonyl ester, urethane, amide, ureido or ether group. Note that R ⁸ ,
Two or three of R ⁹ , R ¹⁰ and R ¹¹ may form a ring.

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

Specific examples of the diol compound having a carboxyl group represented by the general formula (IV), (V) or (VI) include the following.

That is, 3,5-dihydroxybenzoic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (2-hydroxyethyl) 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,
Examples thereof include N-dihydroxyethylglycine and N, N-bis (2-hydroxyethyl) -3-carboxy-propionamide.

The polyurethane resin of the present invention may further contain a hydroxy or nitrile group, if necessary. The introduction of the hydroxy or nitrile group can be carried out, for example, by the method described in JP-A-62-123453.

The molecular weight of the polyurethane resin of the present invention is preferably 1,000 or more by weight average, and more preferably in the range of 5,000 to 200,000. The dispersity is preferably w / n = 1.1 or more, more preferably 1.5 to 20.

The content of the carboxyl group contained in the polyurethane resin of the present invention is preferably 0.4 meq / g or more, and more preferably in the range of 0.7 to 3.5 meq / g.

These polyurethane resins may be used alone or in combination. The content of these polymer compounds contained in the photosensitive composition is about 5 to 95% by weight, preferably about 10% by weight.
~ 90% by weight.

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

Examples of the o-naphthoquinonediazide compound used in the present invention include 1,2 described in JP-B-43-28403.
Most preferred are esters of diazonaphthoquinone sulfonic acid chloride with a pyrogallol-acetone resin. Other suitable o-quinonediazide compounds include the esters of 1,2-diazonaphthoquinonesulfonic acid chloride with phenol-formaldehyde resins described in U.S. Pat. Nos. 3,046,120 and 3,188,210. Other useful o-naphthoquinonediazide compounds have been reported in numerous patents. For example, JP-A-47-5303, JP-A-48-63802, and JP-A-48-6.
No. 3803, No. 48-96575, No. 49-38701, No. 48-13
No. 354, Japanese Patent Publication No. 41-11222, No. 45-9610, No. 49-
17481 publication, U.S. Pat.Nos. 2,797,213 and 3,454,400
No. 3,544,323, No. 3,573,917, No. 3,674,49
No. 5, No. 3,785,825, British Patent No. 1,227,602, No.
1,251,345, 1,267,005, 1,329,888, 1,330,932, and German Patent No. 854,890 may be mentioned.

The amount of these positive-acting o-quinonediazide compounds in the photosensitive composition of the present invention is 10 to 50% by weight.
And more preferably 20 to 40% by weight. Moreover, you may use together 2 or more types of o-quinone diazide compounds as needed.

(3) Negative-type diazonium compound Examples of the diazonium compound used in the present invention include diazonium compounds described in U.S. Pat. No. 3,867,147 and diazonium compounds described in U.S. Pat. No. 2,632,703. Active carbonyl-containing compounds (eg formaldehyde)
A diazo resin represented by a condensation product with is useful. Preferred diazo resins include, for example, hexafluorophosphate, tetrafluoroborate and phosphate salts of condensates of p-diazophenylamine with formaldehyde or acetaldehyde. In addition, sulfonates of a condensate of p-diazodiphenylamine and formaldehyde as described in U.S. Pat. No. 3,300,309 (for example, p-toluenesulfonate, dodecylbenzenesulfonate,
2-methoxy-4-hydroxy-5-benzoylbenzenesulfonate, etc.), phosphinate (eg, benzene phosphinate), hydroxy group-containing compound salt (eg, 2,4-dihydroxybenzophenone salt),
Organic carboxylic acid salts and the like are also preferable.

Furthermore, as shown in JP-A-58-27141, 3-
Also suitable are those obtained by condensing methoxy-4-diazo-diphenylamine with 4,4'-bis-methoxy-methyl-diphenyl ether to form a mesitylene sulfonate.

The content of these diazonium compounds in the photosensitive composition is 1 to 50% by weight, preferably 3 to 20% by weight. If necessary, two or more diazonium compounds may be used in combination.

(4) Combination of Polymerizable Monomer and 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 atmospheric pressure, at least one in one molecule, more preferably Is a monomer or oligomer having a molecular weight of 10,000 or less and having two or more addition-polymerizable ethylenically unsaturated groups. Examples of 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, polypropylene. Glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Hexanediol di (meth) acrylate, tri (acryloyloxyethyl) isocyanate, glycerin and trimethylolethane After the polyhydric alcohol and the like by adding an ethylene-les oxide or propylene oxide (meth) those acrylated, JP-B
Urethane acrylates as described in 48-41708, JP-B-50-6034 and JP-A-51-37193,
JP-A-48-64183, JP-B-49-43191, JP-B-52-30
Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid described in JP-A No. 490 can be mentioned. Furthermore, those introduced as photocurable monomers and oligomers in Japan Adhesive Association magazine vol. 20, No. 300 to 308 pages can also be used.

The content of these monomers or oligomers in the photosensitive composition is 5 to 70% by weight, preferably 10 to 50% by weight.

The photopolymerization initiator which can be added to the photosensitive composition of the present invention is a vicinal polyketaldonyl compound disclosed in U.S. Pat.No. 2,367,660, U.S. Pat.
7,661 and 2,367,670 disclosed in the specification
Carbonyl compounds, acyloin ethers disclosed in U.S. Pat.No. 2,448,828, U.S. Pat.
Patent No. 2 discloses an aromatic acyloin compound substituted at the α-position with a hydrocarbon, U.S. Patent Nos. 3,046,127 and 2,951,758, a polynuclear quinone compound disclosed in U.S. Patent No. 3,549,367. Combination of triarylimidazole dimer / p-aminophenyl ketone disclosed in U.S. Pat.No. 3,870,524, benzothiazole-based compound disclosed in U.S. Pat.
Acridine and phenazine compounds disclosed in U.S. Pat. No. 751,259; and oxadiazole compounds disclosed in U.S. Pat. No. 4,212,970.

Preferably, a trihalomethyl-S-triazine compound or a trihalomethyloxadiazole compound represented by the following general formula (VII) or (VIII) is used.

In the formula, R ¹⁴ represents a substituted or unsubstituted aryl group or alkenyl group, and R ¹³ represents R ¹⁴ , —CX ₃ 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 (VII) include Wakabayashi et al., Bull. Chem. Sco. Japan, Vol. 42, page 2924 (196).
9 years), compounds described in British Patent No. 1,388,492, West German Patent No. 2,718,259, and West German Patent No. 3,337,024. Specifically, the following compounds are included.

That is, 2-phenyl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-chlorophenyl)-
4,6-bis (trichloromethyl) -S-triazine, 2
-(P-tolyl) -4,6-bis (trichloromethyl)-
S-triazine, 2- (p-methoxyphenyl) -4,6
-Bis (trichloromethyl) -S-triazine, 2-
(2 ', 4'-dichlorophenyl) -4,6-bis (trichloromethyl) -S-triazine, 2,4,6-tris (trichloromethyl) -S-triazine, 2-methyl-4,6-
Bis (trichloromethyl) -S-triazine, 2-n-
Nonyl-4,6-bis (trichloromethyl) -S-triazine, 2- (α, α, β-trichloroethyl) -4,6-
Bis (trichloromethyl) -S-triazine, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methylstyryl) -4,6-bis (trichloromethyl) -S-triazine 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (4-methoxy-naphth-1-yl) -4,
6-bis (trichloromethyl) -S-triazine, 2-
(4-Ethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -S-triazine, 2- [4- (2-
Ethoxyethyl) -naphth-1-yl] -4,6-bis (trichloromethyl) -S-triazine, 2- (4,7-
Dimethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -S-triazine, 2 (acenaphtho-5-
Il) -4,6-bis (trichloromethyl) -S-triazine, 2- (4-styrylphenyl) -4,6-bis (trichloromethyl) -S-triazine and the like.

Examples of the compound represented by the general formula (VIII) include compounds described in JP-A-54-74728, JP-A-55-77742, and JP-A-59-148784.
The compounds specifically shown below 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-trichloromethyl-1,3,
4-oxadiazole, 2- (4-methoxystyryl)
-5-trichloromethyl-1,3,4-oxadiazole,
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
-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-trichloromethyl-
1,3,4-oxadiazole and the like are included.

If necessary, a sensitizer can be added to the photosensitive composition of the present invention. Specifically, the aromatic thiazole compounds disclosed in JP-B-59-28328, JP-A-54-1510.
Merocyanine dyes disclosed in Japanese Patent No. 24, JP-A-58-
Aromatic thiopyrylium salts and aromatic pyrylium salts disclosed in 40302, other 9-phenylacridine, 5-
Examples include light absorbers such as nitroacenaphthene and ketocoumarins. Furthermore, N-phenylglycine, 2-
A system in which a hydrogen donor such as menicatobenzothiazole and ethyl N, N'-dimethylaminobenzoate is combined is also effectively used in the present invention.

The amount of the photopolymerization initiator and / or the sensitizer in the present invention is in the range of 0.01% by weight to 20% by weight based on the total amount of the photopolymerizable ethylenically unsaturated compound and the polyurethane resin of the present invention. Yes, more preferably 0.5 wt% to 1
A good result is obtained at 0% by weight.

(5) Other components In the composition of the present invention, in addition to the above-mentioned polyurethane resin, phenol formaldehyde resin, cresol formaldehyde resin, phenol-modified xylene resin, polyhydroxystyrene, polyhalogenated hydroxystyrene and carboxyl group-containing epoxy resin, A well-known alkali-soluble polymer compound such as polyacetal resin acrylic resin and methacrylic resin can be contained. The alcal-soluble polymer compound is used in an amount of 70% by weight or less based on the total composition.

Various additives can be further added to the photosensitive composition used in the present invention.

For example, alkyl ethers (eg ethyl cellulose, methyl cellulose) for improving coating properties, surfactants (eg fluorosurfactant), plasticizers for imparting film flexibility and abrasion resistance (eg tricresidyl). Phosphate, dimethyl phthalate, dibutyl phthalate, trioctyl phosphate, tributyl phosphate,
Tributyl citrate, polyethylene glycol, polypropylene glycol, etc.), a printout agent for obtaining a visible image immediately after exposure, a stabilizer, and an acridine dye or a cyanine dye as a colorant for visualizing an image portion after development. ,
Pigments such as styryl dye, triphenylmethane dye and phthalocyanine, and other fillers can be added.

When combined with an o-quinonediazide compound, a cyclic acid anhydride may be added to enhance sensitivity. Examples of the cyclic acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-endooxy-, as described in U.S. Pat.No. 4,115,128.
Δ ⁴ -tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-
Examples include phenyl maleic anhydride, succinic anhydride, and pyromellitic dianhydride. By containing these cyclic anhydrides in an amount of 1 to 15% by weight in the total composition, the sensitivity can be increased up to about three times. A typical example of the printing-out agent for obtaining a visible image immediately after exposure is a combination of a photosensitive compound that releases an acid upon exposure and an organic dye capable of forming a salt. Specifically, JP-A-50-36209
And the combination of o-naphthoquinonediazide-4-sulfonic acid halogenide and a salt-forming organic dye described in JP-A-53-8128, JP-A-53-36223 and JP-A-54-74728. The combination of the trihalomethyl compound and the salt-forming organic dye described in the publication can be mentioned. Suitable dyes, including salt-forming organic dyes, include oil-soluble dyes and basic dyes. In particular,
Oil Yellow # 101, Oil Yellow # 130, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black B
S, Oil Black T-505 (all manufactured by Orient Chemical Industries, Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI4253)
5), rhodamine B (CI45170B), malachite green (CI42000), methylene blue (CI52015) and the like.

When further combined with a diazonium compound, as a stabilizer, phosphoric acid, phosphorous acid, pyrophosphoric acid, oxalic acid, boric acid, p-toluenesulfonic acid, benzenesulfonic acid, dipicolinic acid, malic acid, tartaric acid, 2-methoxy. -4-Hydroxy-5-benzoyl-benzenesulfonic acid, butylnartalenesulfonic acid, p-hydroxybenzenesulfonic acid, polyacrylic acid and its copolymer, polyvinylphosphonic acid and its copolymer, polyvinylsulfonic acid and its copolymer Polymer, 5-nitronaphthalene-1-phosphonic acid, 4-chlorophenoxymethylphosphonic acid, sodium phenyl-methyl-pyrazolone sulfonate, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-phosphonoethane-1,2,2 -Tricarboxylic acid, 1-hydroxyethane-1,1-disulfonic acid, etc. No.

When combining a polymerizable monomer and a photopolymerization initiator, a small amount of thermal polymerization is prevented in order to prevent unnecessary thermal polymerization of the polymerizable ethylenically unsaturated compound during the production or storage of the photosensitive composition. It is desirable to add agents. 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 primary cerium salt and the like.

The addition amount of these additives varies depending on the intended purpose, but generally 0.5 to 30 relative to the total solid content of the photosensitive layer.
% By weight.

(B) Photosensitive lithographic printing plate The photosensitive composition of the present invention is dissolved in a suitable organic solvent and has a dry coating weight of 0.5 to 5 g / m ² on a support having a hydrophilic surface.
And a photosensitive lithographic printing plate can be obtained. As the solvent used here, methanol, ethanol, isopropanol, n-butanol, t-butanol, ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1 -Methoxy-2-propanol, 1-methoxy-2-propyl acetate, methyl lactate, ethyl lactate, N, N-dimethylformamide, N, N-dimethylacetamide, γ-butyrolactone, N-methylpyrrolidone, tetramethylurea, tetrahydrofuran , Dioxane, dimethyl sulfoxide, sulfolane, toluene, ethyl acetate, etc., and these solvents may be used alone or in combination. A small amount of water may be added. The concentration (solid content) in the above components is 2 to 50% by weight. When coating the photosensitive solution dissolved in these solvents and drying it: 50 ℃ -120 ℃
It is desirable to dry with. The drying may be carried out at a low temperature at the beginning, followed by preliminary drying, followed by drying at a high temperature. Alternatively, drying may be carried out directly at a high temperature by selecting an appropriate solvent and concentration.

A lithographic printing plate having a photosensitive layer coated on a support having a hydrophilic surface is exposed to an image and then developed with a developer containing weak alkaline water to obtain a positive or negative relay image with respect to the original image. Suitable light sources for exposure include carbon arc lamps, mercury lamps, xenon lamps, metal halide lamps, strobes, and ultraviolet laser beams. As a developing solution for a photosensitive lithographic printing plate having a photosensitive layer of the present invention, each of JP-A-51-77401, JP-A-51-80228, JP-A-53-44202 and JP-A-55-52054 is used. Organic solvents having a solubility in water of 10% by weight or less at room temperature as described in the publication (benzyl alcohol, ethylene glycol monophenyl ether, etc.), alkaline agents (triethanolamine, monoethanolamine, etc.), anionic surfactants (Aromatic sulfonate, dialkyl sulfosuccinate, alkyl naphthalene sulfonate, A weakly alkaline aqueous solution consisting of branched alkyl sulfates, etc.), water and, if necessary, antifouling agents (sodium sulfite, sulfopyrazolone sodium salt) and water softeners (ethylenediaminetetraacetic acid 4Na, NCH ₂ COONa) ₃ ) Can be done.

The support to which the photosensitive composition of the present invention is applied is, for example, paper, paper laminated with plastics (for example, polyethylene, polypropylene, polystyrene, etc.), for example, aluminum (including aluminum alloy), zinc, and the like. Plates of metal such as copper, plastics such as cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc. Film, a paper or plastic film on which the above metal is laminated, or vapor-deposited. Among these supports, the aluminum plate is particularly preferable because it is dimensionally remarkably stable and inexpensive. Furthermore,
A composite sheet in which an aluminum sheet is bonded onto a polyethylene terephthalate film as described in JP-B-48-18327 is also preferable. The surface of the aluminum plate is wire brush graining, a mechanical method such as brush graining, ball graining, liquid honing graining, buff graining, etc., in which a nylon brush is roughened while pouring a slurry of abrasive particles.
₃ , chemical graining using HCl as an etchant, electrolytic graining using nitric acid or hydrochloric acid as an electrolytic solution, or composite graining performed by combining these surface roughening methods to sharpen the surface. Alternatively, it is subjected to an etching treatment with an alkali, and subsequently anodized with a direct current or an alternating current power source in sulfuric acid, phosphoric acid, oxalic acid, boric acid, chromic acid, sulfamic acid or a mixed acid thereof to form a strong passivation film on the aluminum surface. Those are preferable.
Although the aluminum surface is hydrophilized by such a passivation film itself, furthermore, if necessary, US Pat. No. 2,714,066
Silicate treatment (sodium silicate, potassium silicate) described in U.S. Pat. No. 3,181,461 and US Pat. No. 3,181,461; potassium fluorozirconate treatment described in U.S. Pat. No. 2,946,638; U.S. Pat. No. 3,201,24
Phospho morizdate treatment described in No. 7,
Alkyl titanate treatment described in British Patent No. 1,108,559, polyacrylic acid treatment described in German Patent No. 1,091,433, German Patent No. 1,134,09
Polyvinylphosphonic acid treatment described in No. 3 specification and British Patent No. 1,230,447, phosphonic acid treatment described in Japanese Patent Publication No. 44-6409, U.S. Patent No. 3,307,95
No. 1, phytic acid treatment described in JP-A-58
No. 16893 and JP-A-58-18291, a composite treatment comprising a hydrophilic organic polymer compound and a divalent metal, and a sulfonic acid described in JP-A-59-101611. Those which have been subjected to a hydrophilic treatment by undercoating of a water-soluble polymer having a group are particularly preferred. Another hydrophilic treatment method includes silicate electrodeposition described in US Pat. No. 3,658,662.

It is also preferable that after the graining treatment, the anodic oxidation, and the sealing treatment are performed. Such sealing treatment is performed by immersion in hot water and a hot aqueous solution containing an inorganic salt or an organic salt, a steam bath, or the like.

〔Example〕

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

Synthesis Example 1. 1,4- (or 1,5) -bis (2-hydroxyethoxycarbonyl) -2,5 (or 2,4) -dicarboxybenzene Synthesis of pyromellitic dianhydride 43.6g (0.20mole) dissolved in ethylene glycol 250g, pyridine 15.9g (0.20m
ole) was added. Then, the mixture was heated and stirred at 90 ° C. for 3 hours.
By evaporating the reaction solvent under vacuum, a light brown viscous solid was obtained. This was washed with acetonitrile to give a light brown powder. The yield after drying was 51.8 g (yield 76%). The structure was confirmed by NMR.

Synthesis Example 2 Synthesis of Polyurethane Resin-1- In a 500 ml three-necked round bottom flask equipped with a condenser and a stirrer, 17.1 g (0.0
5mole), 6.3 g (0.07mole) of 1,4-butanediol, and 8.5 g (0.08mole) of diethylene glycol were added, and N, N-
It was dissolved in 100 ml of dimethylacetamide. To this 4,4'-
Diphenylmethane diisocyanate 35.1g (0.14mole)
And 1,6-hexanediisocyanate 10.1g (0.06mole)
Was added. Furthermore, dibutyltin dilaurate as a catalyst
0.10 g was added, and the mixture was heated with stirring at 100 ° C. for 5 hours. Then, 200 ml of N, N-dimethylformamide and 50 ml of acetic acid were added for dilution. Pour the reaction solution into water 4 with stirring,
A white polymer was deposited. The polymer is filtered off,
After washing with water, it was dried under vacuum to obtain 75 g of a polymer.

When the molecular weight was measured by gel permeation chromatography (GPC), the weight average (polystyrene standard) was 35,000. Further, the carboxyl group content (acid value) was measured by titration, and it was 1.25 meq / g. (Polyurethane resin (a) of the present invention).

Synthesis Example 3. Synthesis of polyurethane resin-2-diphenylmethane-4,4'-bis (hydroxyethyl carbamate) 37.4 g (0.10 mole) and 32.2 g (0.10 mole) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride were dissolved in 100 ml of N, N-dimethylacetamide. Pyridine 15.
8g (0.20mole) and 4-dimethylaminopyridine 2.5g
(0.02mole) was added, and the mixture was heated with stirring at 90 ° C for 7 hours.
After that, 200 ml of N, N-dimethylformamide and 50 ml of acetic acid
Diluted with. The reaction solution was poured into water 4 with stirring to precipitate a white polymer. This polymer was separated by filtration, washed with water, and dried under vacuum to obtain 65 g of a polymer.

When the molecular weight was measured by GPC, the weight average (polystyrene standard) was 31,000. Further, the acid value measured by titration was 2.82 meq / g (polyurethane resin (b) of the present invention).

Synthetic Example 4. Synthesis of Polyurea Resin-3- (3) 30 g of the polyurea resin synthesized in Synthetic Example 3 was dissolved in 200 ml of N, N-dimethylformamide, and 5.4 g (0.053 mole) of triethylamine was added. To this, 66 g (0.053 mole) of ethylene glomohydrin was added dropwise with stirring at 80 ° C over 10 minutes. Then, stirring was continued at 80 ° C. for 3 hours. Add 30 ml of acetic acid and pour into water 2 with stirring,
A white polymer was deposited. This polymer was separated by filtration, washed with water, and dried under vacuum to obtain 32 g of a polymer.

When the molecular weight was measured by GPC, the weight average (polystyrene standard) was 28,000. Further, the acid value measured by titration was 1.32 meq / g (polyurethane resin (c) of the present invention). Further, it was confirmed by NMR that a part of the carboxyl group was converted into hydroxyethyl ester.

Synthesis Examples 5 to 16 Polyurethane resins (d) to (o) of the present invention shown in Table 1 were synthesized in the same manner as in Synthesis Examples 2 to 4 below.

Further, the molecular weight was measured by GPC, and the acid value was measured by titration. Table 1 shows the measured acid values. The weight average molecular weight (polystyrene standard) is 25,000 to 48,000.
Met.

In the table, R represents represents H or -CH ₂ CH ₂ -OH. The subscripts indicate the ratio of charged models when synthesizing polyurethane resin.

Examples 1 to 4 An aluminum plate having a thickness of 0.30 mm and a nylon brush and 400
The surface was grained with an aqueous suspension of mesh pumice and then thoroughly washed with water. After etching by immersion in 10% sodium hydroxide at 70 ° C. for 60 seconds, the substrate was washed with running water, neutralized with 20% nitric acid, and washed with water. This is V _A = 12.7V
Under the above conditions, electrolytic surface roughening treatment was performed in a 1% aqueous nitric acid solution using an alternating current having a sinusoidal waveform with an anode-time electric quantity of 160 coulomb / dm ² . When the surface roughness was measured, it was 0.6μ (R
a display). Subsequently, it was immersed in a 30% sulfuric acid aqueous solution, desmutted at 55 ° C. for 2 minutes, and then anodized in a 20% sulfuric acid aqueous solution at a current density of 2 A / dm ^{2 to} a thickness of 2.7 g / m ² .

Next, by changing the kind of the polyurethane resin used in the present invention in the following photosensitive solution [A], four kinds of photosensitive solution [A] -1 to
[A] -4 was prepared, and this photosensitive solution was applied on an anodized aluminum plate and dried at 100 ° C. for 2 minutes to prepare each photosensitive lithographic printing plate [A] -1 to [A] -4. Was produced. The coating amount at this time was 2.5 g / m ² in dry weight.

The polyurethane resins of the present invention used in Photosensitive solutions [A] -1 to [A] -4 are shown in Table 2.

Next, as a comparative example, the following photosensitive solution [B] was used.
And a photosensitive lithographic printing plate [B] was prepared.
The coating weight% after drying was 2.5 g / m ² .

A positive transparent original image of a line drawing and a halftone dot image was brought into close contact with the photosensitive layers of the photosensitive lithographic printing plates [A] -1 to [4] and [B] and exposed with a carbon arc lamp of 30 amps from a distance of 70 cm.

The exposed photosensitive lithographic printing plates [A] -1 to 4 and [B] were immersion developed at 25 ° C. for 60 seconds in an 8 times diluted aqueous solution of DP-4 (trade name: manufactured by Fujitsu Film Ltd.).

Next, the lithographic printing plates [A] -1 to [4] and [B] thus obtained were mounted on a KOR type printer manufactured by Heidelberg and printed on high-quality paper using a commercially available ink. Planographic printing plate [A]
When the final number of printed sheets of -1 to 4 and [B] was examined, it was as shown in Table 2.

As can be seen from Table 2, the planographic printing plates [A] -1 to 4 (Examples 1 to 4) using the photosensitive composition of the present invention have a larger number of printed sheets than the comparative example [B]. , The printing durability is very good.

Examples 5 to 8 Instead of the polyurethane resin of the present invention in the photosensitive liquids [A] of Examples 1 to 4, photosensitive liquids [C] using the polyurethane resins of Comparative Examples shown below were used, and Examples 1 to 4 were used. It was applied and dried in the same manner as in. The dry weight was 2.5 g / m ² .
Next, from the distance of 70 cm to the photosensitive lithographic printing plates [A] -1 to [4] and [C], a carbon arc lamp of 30 amps was used to measure 60.
The entire surface is exposed for 15 seconds, and a 15 times diluted aqueous solution of DP-4 is at 15 ° C.
Immersion development was carried out. The development time until the photosensitive film was completely dissolved and removed was measured and was as shown in Table 3.

As can be seen from Table 3, the lithographic printing plates [A] -1 to 4 (Examples 5 to 8) using the photosensitive composition of the present invention were compared with Comparative Examples [C] -1 and 2. The development time is short and the developability is excellent.

Examples 9 to 12 A JIS 1050A aluminum plate having a thickness of 0.24 mm was grained on its surface using a nylon brush and an aqueous suspension of 400 mesh pumice, and then thoroughly washed with water. 10% of this
After being immersed in an aqueous solution of sodium hydroxide at 70 ° C. for 60 seconds for etching, washed with running water and neutralized with 20% nitric acid, the electrochemical surface roughening method described in JP-A-53-67507, namely V _A
= 12.7V, V _C = 9.1% using sine wave alternating waveform current of 9.1V
Electrolytic surface roughening treatment was performed in a nitric acid aqueous solution at an anode electricity amount of 160 coulomb / dm ² . 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 such that the coating amount of aluminum oxide was 2.0 g / m ² . Then, it was immersed in a 3% aqueous solution of JIS No. 3 sodium silicate at 70 ° C for 1 minute, washed with water and dried.
Photosensitive solutions [D] -1 to [D] -4 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 2.0 g / m ² .

The polyurethane resins of the present invention used in Photosensitive solutions [D] -1 to [D] -4 are shown in Table 4.

Next, as a comparative example, a photosensitive solution [E] containing the following polymer in place of the polyurethane resin of the present invention in the photosensitive solution [E]
Was similarly applied and dried. The dry weight was 2.0 g / m ² .

(Polymer used in Comparative Example) A / b / c / d is a molar ratio of 9/24 /
58/9.

The molecular weight is 55,0 by weight average (polystyrene standard).
00.

Each of the photosensitive lithographic printing plates [D] -1 to 4 and [E] obtained by using the photosensitizing liquids [D] -1 to 4 and [E] was adjusted to 1 m with a PS light manufactured by Fuji Photo Film Co., Ltd. Image exposure for 1 minute from the distance, the company's automatic developing machine 800H, the company's developer DN
A lithographic printing plate was developed and gummed at 30 ° C for 20 seconds using a -3C volume ratio (1: 1) diluted aqueous solution and a GUM FN-2 volume ratio (1: 1) diluted aqueous solution. It was created.

Each printing plate was mounted on a GTO type printer manufactured by Heidelberg and printed on a high-quality paper using a commercially available ink. When the final number of printed sheets of the planographic printing plates [D] -1 to [4] and [E] was examined, it was as shown in Table 4.

As can be seen from Table 4, the lithographic printing plates [D] -1 to 4 (Examples 9 to 12) using the photosensitive composition of the present invention produced a larger number of printed sheets than the comparative example [E]. , The printing durability is very good.

Examples 13 to 16 Instead of the polyurethane resin of the present invention in the photosensitive liquids [D] of Examples 9 to 12, photosensitive liquids [F] using the polyurethane resins of Comparative Examples shown below were used, and Examples 9 to 12 were used. It was applied and dried in the same manner as in. The dry weight was 20 g / m ² . The photosensitive lithographic printing plates [D] -1 to 4 and [F] were subjected to immersion development at 25 ° C. in a diluted aqueous solution of DN-3C in a volume ratio (1: 2 (water)). When the developing time was measured until the photosensitive film was completely dissolved and removed, it was as shown in Table 5.

A part of the carboxyl groups of which was hydroxyethyl esterified (acid value 1.20 meq / g) As can be seen from Table 5, lithographic printing plates [D] -1 to 4 (implemented using the photosensitive composition of the present invention In Examples 13 to 15), the developing time is shorter and the developability is excellent as compared with Comparative Examples [F] -1 and 2.

Examples 17 to 18 Photosensitive solutions [G] -1 to [G] -2 shown below were applied to the aluminum plates obtained in Examples 9 to 12 using a wheeler, and 80
It was dried at 0 ° C for 2 minutes. The dry weight was 2.0 g / m ² .

The polyurethane resins of the present invention used in the photosensitive liquids [G] -1 to [G] -2 are shown in Table 6.

Next, as a comparative example, a benzyl methacrylate-methacrylic acid (molar ratio 73/27) copolymer (weight average molecular weight 45, 45
000 (polystyrene standard)) was similarly applied and dried, and the dry weight was 2.0% / m ² .

Each of the photosensitive lithographic printing plates [G] -1 to 2 and [H] obtained by using the photosensitizing liquids [G] -1 to 2 and [H] was adjusted to 1 m with a PS light manufactured by Fuji Photo Film Co., Ltd. Image exposure from a distance for 1 minute, and the developer used in Examples 9 to 12 at room temperature for 1 minute.
After soaking for a minute, the surface was lightly rubbed with absorbent cotton to remove the unexposed area, and a bright blue image of the planographic printing plate [G] -1.
2 and [H] were obtained.

Each printing plate was mounted on a KOR type printing machine manufactured by Heidelberg and printed on high-quality paper using a commercially available ink. When the final printing number of planographic printing plates [G] -1 and [G] -2 was examined, it was as shown in Table 6.

As can be seen from Table 6, the lithographic printing plates [G] -1 and 2 (Examples 17 to 18) using the photosensitive composition of the present invention have a larger number of printed sheets than the comparative example [H], Excellent printing durability.

[Effects of the Invention] The photosensitive composition of the present invention has excellent developability in an aqueous alkaline developer, and the lithographic printing plate obtained by using the composition has high printing durability.

Claims (1)

(57) [Claims] 1. A combined yarn of a negative-acting diazonium compound or a polymerizable monomer and a photopolymerization initiator,
Alternatively, in a photosensitive composition containing a positive-working o-quinonediazide compound and a water-insoluble and alkaline-water-soluble polyurethane resin having a carboxyl group, the polyurethane resin contains a tetracarboxylic acid dianhydride. A photosensitive composition comprising a polyurethane resin having a structural unit obtained by reacting an alcohol-terminated compound obtained by ring opening with a diol compound with a diisocyanate compound.