JPH0727209B2 - Photosensitive composition - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a photosensitive composition suitable for producing a lithographic printing plate, an IC circuit and a photomask. For more details,
The present invention relates to a photosensitive composition composed of a positive-type or negative-type photosensitive compound and a polymer compound having excellent abrasion resistance.

[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 film is brittle, the coatability is poor, the abrasion resistance is poor, and the printing durability when used for lithographic printing plates is poor. 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, the polyhydroxystyrene or hydroxystyrene copolymer described in JP-B-52-41050 has certainly improved the film forming property, but has the drawback of being inferior in 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.

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

Furthermore, in JP-A-61-20939, a photosensitive composition using an anionic polyurethane resin is described. Such anionic polyurethane resin is water-based and is essentially different from the water-insoluble polyurethane resin 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.

The majority of those used as photosensitive substances in negative acting systems are diazonium compounds,
The most commonly used one is a diazo resin represented by a formaldehyde condensate of p-diazodiphenylamine.

The composition of the photosensitive layer of the photosensitive lithographic printing plate using a diazo resin, for example, as described in U.S. Pat.No. 2,714,066, the diazo resin alone, that is, without a binder, for example, As described in JP-A-50-30604, it can be classified into a mixture of a binder and a diazo resin, but in recent years, most of photosensitive lithographic printing plates using a diazonium compound have It is composed of a diazonium compound and a polymer that serves as a binder to provide high printing durability.

Examples of such a photosensitive layer include a so-called alkali developing type in which an unexposed portion is removed (developed) by an aqueous alkaline developer and an organic solvent-based developer as described in JP-A-50-30604. The so-called solvent-developable type that can be removed is known, but the alkali-developable type is drawing 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 an alkali developability to the binder, Japanese Patent Laid-Open No.
Carboxylic acid-containing monomers as described in U.S. Pat. No. 30,604,035 or hydroxyl groups of polyvinyl alcohol and cyclic acids such as phthalic anhydride as described in U.S. Pat. No. 2861058. There is a method of introducing a carboxylic acid into a polymer by reacting an anhydride, but the obtained polymer is structurally poor in abrasion resistance, and from a photosensitive lithographic printing plate containing such a binder in a photosensitive layer. Only a lithographic printing plate with low printing durability was obtained. On the other hand, polyvinyl acetal has a drawback that it forms a tough film and has abrasion resistance, but only an organic solvent-developing photosensitive lithographic printing plate can be obtained.

Further, there is a polyurethane resin as a known polymer having excellent abrasion resistance, and in JP-B-49-36961 and JP-A-56-94346, a combination of a diazonium compound and a substantially linear polyurethane resin is disclosed. Systems and combinations of diazonium salt polycondensates and branched polyurethane resins are disclosed, respectively. However, none of these polyurethane resins has an alkali-soluble group as described above, and the solubility in an aqueous alkaline developer is essentially insufficient, and it is extremely difficult to develop without a residual film. It was very difficult. Further, it has a drawback that it does not form an image having sufficient strength because it does not have a site that causes a photoreaction with the combined diazonium compound upon exposure and efficiently crosslinks.

On the other hand, many attempts have been made to use a photopolymerizable composition as a photosensitive image-forming layer of a negative-working photosensitive lithographic printing plate.
Basic composition consisting of polymer as binder, monomer and photopolymerization initiator as disclosed in Japanese Patent No. 2714, unsaturated double bond in polymer as binder as disclosed in Japanese Patent Publication No. 49-34041 Introducing a composition that improves the curing efficiency, JP-B-48-38403 and JP-B-53
-27605, and compositions using a novel photopolymerization initiator as disclosed in British Patent No. 1,388,492 and the like are known, and some of them are put to practical use. ,
Each of the photosensitive compositions had the drawback that the sensitivity was greatly affected by the surface temperature of the photosensitive lithographic printing plate during image exposure, and that polymerization was strongly inhibited by oxygen during image exposure.

[Problems to be solved by the invention]

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

[Structure of Invention]

As a result of intensive investigations by the present inventors to achieve the above object,
The inventors have found that these objects can be achieved by using a novel photosensitive composition, and have arrived at the present invention.

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

(Ii) Negative acting diazonium compounds.

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

(Iv) A combination of a negative acting diazonium compound, a polymerizable monomer and a photopolymerization initiator.

A photosensitive compound 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 described in detail.

(1) Polyurethane Resin The polyurethane resin preferably 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, preferably the following general formula: A polyurethane resin having as a basic skeleton a reaction product of a diisocyanate compound represented by (I) and a diol compound having a carboxyl group represented by the general formula (II), (III) or (IV) is included.

OCN-R _1- NCO (I) In the formula, R ₁ represents a divalent aliphatic or aromatic hydrocarbon which may have a substituent (for example, alkyl, aralkyl, aryl, alkoxy, cyano, nitro and halogeno groups are preferable). . If necessary, R ₁ may have another functional group that does not react with an isocyanate group, for example, an ether, ester, urethane, amide, ureido or carbonyl group.

R ₂ is a hydrogen atom, a substituent (for example, cyano, nitro, a halogen atom (-F, Cl), -CONH ₂ , -COOR ₇ , -OR ₇ , -NHCONH
_{R 7, -NHCOOR 7, -NHCOR 7} , -OCONHR 7, -CONHR 7, -COR 7 ( wherein, R ₇ represents an alkyl group, an aralkyl group having 7 to 15 carbon atoms having 1 to 10 carbon atoms.) Etc. are included in each group. ) Is optionally present, alkyl, aralkyl, aryl, alkoxy, aryloxy groups are preferred, and hydrogen atom, alkyl having 1 to 8 carbons and aryl group having 6 to 15 carbons are preferred. R ₃ , R ₄ and R ₅ may be the same or different and each represents a single bond, a substituent (for example, alkyl, aralkyl,
Aryl, alkoxy, cyano, nitro and halogeno groups are preferred. ) Represents a divalent aliphatic or aromatic hydrocarbon which may have. It is preferably an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 15 carbon atoms, and more preferably an alkylene group having 1 to 8 carbon atoms. If necessary, R ₃ , R ₄ , and R ₅ may have other functional groups that do not react with the isocyanate group, such as carbonyl, ester, urethane, amide, ureido, and ether groups. Note that
Two or three of R ₂ , R ₃ , R ₄ and R ₅ may form a ring.

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

Specific examples of the diisocyanate compound represented by the general formula (I) include those shown below.

That is, 2,4-tolylene diisocyanate, 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,
Aromatic diisocyanate compounds such as 3'-dimethylbiphenyl-4,4'-diisocyanate; aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate; isophorone diisocyanate, 4,4 ' Alicyclic diisocyanate compounds such as methylenebis (cyclohexylisocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, 1,3- (isocyanatomethyl) cyclohexane; 1 mole of 1,3-butylene glycol and tolylene diene Examples thereof include a diisocyanate compound which is a reaction product of a diol and a diisocyanate such as an adduct with 2 moles of isocyanate.

Specific examples of the diol compound having a carboxyl group represented by formula (II), (III) or (IV) include those shown below.

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, N
-Bis (2-hydroxyethyl) -3-carboxy-propionamide, N, N-bis (2-hydroxyethyl)
Glycine and the like can be mentioned.

The fluorine-substituted hydrocarbon group in the polyurethane resin of the present invention is a halogen (Cl, Br, I) having a fluorine-substituted hydrocarbon group as a part of the carboxy group derived from the general formula (II), (III) or (IV). ) It can be contained in a polyurethane resin by reacting with a compound or a sulfonate compound in the presence of a base.

The polyurethane resin can also be contained by using a diisocyanate compound having a fluorine-substituted hydrocarbon group in combination with the diisocyanate compound of the general formula (I).

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

The fluorine-substituted hydrocarbon group as used herein is an aliphatic that may have a substituent having at least one fluorine atom (for example, alkyl, aralkyl, aryl, alkoxy, halogeno, cyano, and nitro groups are preferable). Alternatively, it represents an aromatic hydrocarbon group.

Preferably, an aliphatic hydrocarbon group having 1 to 18 carbon atoms and having 2 or more monovalent or divalent fluorine atoms or 6 to 15 carbon atoms.
Represents one aromatic hydrocarbon group.

The polyurethane resin of the present invention includes the diisocyanate compound represented by the general formula (I) and the general formulas (II) and (II
It may be formed from two or more kinds of diol compounds having a carboxyl group represented by I) or (IV).

Further, a diol compound which does not have a carboxyl group and may have another substituent that does not react with isocyanate may be used together to the extent that alkali developability is not deteriorated.

Specific examples of such diol compounds include those shown below.

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-
Hydroxyethoxy cyclohexane, cyclohexanedimethanol, tricyclodecane dimethanol, 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-xylylenediene Rubameto, bis (2-hydroxyethyl) isophthalate.

The polyurethane resin used in the present invention contains the above diisocyanate compound and diol compound in an aprotic solution,
Add a known active catalyst according to each reactivity,
It is synthesized by heating. The molar ratio of diisocynate and diol compounds used is preferably 0.8: 1.
When the isocyanate group remains at the polymer terminal, it is treated with alcohols or amines to finally synthesize the isocyanate group in a form in which no isocyanate group remains.

The molecular weight of the polyurethane resin used in the present invention is preferably 1,000 or more on a weight average basis, more preferably 5,000 to 1
It is in the range of 0,000.

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

The o-naphthoquinonediazide compound used in the present invention is described in JP-B-43-28403, 1,2-
Most preferred are esters of diazonaphthoquinone sulfonic acid chloride with pyrogallol-acetone resin. Other suitable o-quinonediazide compounds are the esters of 1,2-diazonaphthoquinone sulfonic acid chlorides with phenol-formaldehyde resins described in US Pat. Nos. 3,046,120 and 3,188,210. Other useful o-naphthoquinonediazide compounds have been reported and known in numerous patents. For example, JP-A-47-5303 and JP-A-48-63802
Issue, Dosho 48-63803, Dosho 48-96575, Dosho 49-38701
Issue, Dosho 48-13354, Japanese Patent Publication No. 41-11222, Dosho 45-9610
No. 49-17481, U.S. Patent No. 2,797,213,
No. 3,454,400, No. 3,544,323, No. 3,573,917
No. 3,674,495, No. 3,785,825, British Patent No. 1,
227,602, 1,251,345, 1,267,005, and
1,329,888, 1,330,932, German Patent 854,890
The items described in each specification such as No. can be mentioned.

The amount of the o-quinonediazide compound acting on the positive type in the photosensitive composition of the present invention is 10 to 50% by weight,
It is more preferably 20 to 40% by weight.

(3) Negative-type diazonium compound As the diazonium compound used in the present invention, diazonium compounds described in US Pat. No. 3867147, US Pat.
Examples thereof include diazonium compounds described in Japanese Patent No. 632703, but diazo resins represented by a condensate of an aromatic diazonium salt and an active carbonyl-containing compound (for example, formaldehyde) are particularly 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 condensation product 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, benzenephosphinate), hydroxy group-containing compound salt (eg, 2,4-
Dihydroxybenzophenone salt, etc.), organic carboxylic acid salt, etc. are also preferable.

Further, 3-methoxy-4-diazo-diphenylamine as disclosed in JP-A-58-27141 is added to 4,4'-bis-
Those obtained by condensing with methoxy-methyl-diphenyl ether to give mesitylene sulfonate are also suitable.

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) Polymerizable Monomer / Photopolymerization Initiator The monomer that can be added to the photosensitive composition of the present invention is 1 in at least one molecule having a boiling point of 100 ° C. or higher at normal pressure.
It is a monomer or oligomer having a molecular weight of 10,000 or less, which has one, more preferably 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, trimethylolethane, etc. Those after adding ethylene oxide or propylene oxide (meth) acrylated polyhydric alcohols, JP-B-48
-41708, JP-B-50-6034, JP-A-51-37193, urethane acrylates as described in JP-A-48-64183, JP-B-49-43191, JP-B-52- Examples thereof include 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. 30490. Furthermore, Japan Adhesive Association magazine Vo1.
The materials introduced as photocurable monomers and oligomers on pages 20, No. 7, 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 5:95 to 70:30 by weight, more preferably 10:90 to 50:50.

The photopolymerization initiator that 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.
Α-carbonyl compounds disclosed in 661 and 2,367,670, acyloin ethers disclosed in U.S. Pat.No. 2,448,828, U.S. Pat.No. 2,722,512
.Alpha.-hydrocarbon substituted aromatic acyloin compounds disclosed in U.S. Pat. No. 3,046,127 and US Pat.
Multiple quinone compounds disclosed in 2,951,758, triarylimidazole dimer / p-aminophenyl ketone combinations disclosed in U.S. Pat.No. 3,549,367, disclosed in U.S. Pat.No. 3,870,524 Benzothiazole compounds, U.S. Pat.
Examples include acridine and phenazine compounds disclosed in US Pat. No. 259, oxadiazole compounds disclosed in US Pat. No. 4,212,970, and the like.

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

In the formula, R ₉ represents a substituted or unsubstituted aryl group or alkenyl group, and R ₈ represents R ₉ , —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 (V) include Wakabayashi et al., Bull. Chem. Soc. Japan, Vol. 42, page 2924 (1969).
), The compounds described in British Patent 1,388,492, West German Patent 2,718,259, and West German Patent 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)
-Yl) -4,6-bis (trichloromethyl) -S-triazine, 2- (4-styrylphenyl) -4,6-bis (trichloromethyl) -S-triazine and the like are included.

Examples of the compound represented by the general formula (VI) include compounds described in JP-A-54-74728, JP-A-55-77742, and JP-A-59-148784. Specifically, the following compounds are included.

That is, 2-styryl-5-trichloromethyl-1,3,4-
Oxadiazole, 2- (4-chlorostyryl) -5-
Trichloromethyl-1,3,4-oxadiazole, 2-
(4-methylstyryl) -5-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, an aromatic thiazole compound shown in JP-B-59-28328, a merocyanine dye shown in JP-A-54-151024, an aromatic thiopyrylium salt shown in JP-A-58-40302, and Examples thereof include aromatic pyrylium salts, other 9-phenylacridine, 5-nitroacenaphthene, and light absorbers such as ketocoumarins. Furthermore, a system in which a hydrogen donor such as N-phenylglycine, 2-menicatobenzothiazole, ethyl N, N'-dimethylaminobenzoate, or the like 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
The range of 0.01 to 20% by weight is sufficient with respect to the total amount of the photopolymerizable ethylenically unsaturated compound and the polyurethane resin of the present invention, and more preferably 0.5 to 10% by weight for good results. Become.

(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, Known alkali-soluble polymer compounds such as polyacetal resin, acrylic resin, methacrylic resin, etc. can be contained. Such an alkali-soluble polymer compound is 70% by weight of the total composition.
It is used in the following addition amounts.

In the composition of the present invention, a printing-out agent for obtaining a visible image immediately after exposure, a dye as an image colorant, a pigment, a stabilizer, a surfactant, a plasticizer, or other filler 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 1 to 15% by weight of these cyclic acid anhydrides in the total composition, the sensitivity can be increased up to about 3 times. As a printing-out agent for obtaining a visible image immediately after exposure, a combination of a photosensitive compound which releases an acid upon exposure and an organic dye capable of forming a salt can be mentioned as a representative example. Specifically, combinations of o-naphthoquinonediazide-4-sulfonic acid halogenide and salt-forming organic dyes described in JP-A-50-36209 and JP-A-53-8128, and JP-A-53- 36223, JP-A-54-7
The combination of the trihalomethyl compound and the salt-forming organic dye described in Japanese Patent No. 4728 can be mentioned. As the image colorant, dyes other than the above-mentioned salt-forming organic dyes can be used. Suitable dyes including salt-forming organic dyes include oil-soluble dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 130, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY,
Oil Black BS, Oil Black T-505 (above, manufactured by Orient Chemical Industry Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI42535), Rhodamine B (CI45170B), Malachite Green (CI42000), Methylene Blue ( CI520
15) and so on.

Further, when combined with a diazonium compound, stabilizers include phosphoric acid, phosphorous acid, oxalic acid, p-toluenesulfonic acid, dipicolinic acid, malic acid, tartaric acid, 2-methoxy-4-hydroxy-5-benzoyl-benzene. Examples thereof include sulfonic acid, butylnaphthalene sulfonic acid, p-hydroxybenzene sulfonic acid, and the like.

When a polymerizable monomer and a photopolymerization initiator are further combined, a small amount of a thermal polymerization inhibitor is added to prevent unnecessary thermal polymerization of the polymerizable ethylenically unsaturated compound during the production or storage of the photosensitive composition. Is preferably added. Suitable thermal polymerization inhibitors include hydroquinone and 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 composition of the present invention is dissolved in a solvent that dissolves each of the above components and applied onto a support. 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-propylacetate, N, N-dimethylformamide, tetrahydrofuran, dioxane, dimethylsulfoxide, toluene, ethyl acetate, etc., and these solvents are used alone or in combination. The concentration (solid content) in the above components is 2 to 50% by weight. Further, the coating amount varies depending on the use, but in the case of a photosensitive lithographic printing plate, for example, it is generally 0.5 to 3.0 gm ² as a solid component.
Is preferred. Although the photosensitivity increases as the coating amount decreases, the physical properties of the photosensitive film deteriorate.

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. Metal plates 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.

Further, in the case of a support having a surface of a metal, particularly aluminum, surface treatment such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate or the like, or anodization treatment is performed. Preferably. In addition, as described in U.S. Pat.No. 2,714,066, an aluminum plate immersed in an aqueous solution of sodium silicate, and after anodizing the aluminum plate as described in Japanese Patent Publication No. 47-5125. An aluminum support treated by immersion in an aqueous solution of an alkali metal silicate, and an aluminum support treated by a combination of opportunistic roughening and electrolytic roughening as described in US Pat. No. 4,476,006 are also preferably used. . The anodizing treatment is, for example, phosphoric acid, chromic acid, sulfuric acid, an inorganic acid such as boric acid, or
It is carried out by applying an electric current using an aluminum plate as an anode in an electrolytic solution of an acid, an organic acid such as sulfamic acid or the like, or an aqueous solution or a non-aqueous solution of a salt thereof, or a combination of two or more kinds.

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

Further, silicate electrodeposition as described in US Pat. No. 3,658,662 is also effective.

The photosensitive composition of the present invention coated on a support has a line image,
Exposure through a transparent original having a halftone image and the like followed by 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, metal halide lamps and the like.

〔The invention's effect〕

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

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

Synthesis Example 1 125 g of 4,4'-diphenylmethane diisocyanate in a 500 ml three-necked round bottom flask equipped with a condenser and a stirrer.
(0.50 mol) and 67 g (0.50 mol) of 2,2-bis (hydroxymethyl) propionic acid were added and dissolved in 290 ml of dioxane. 1 g of N, N-diethylaniline was added as a catalyst, and the mixture was heated under reflux for 6 hours with stirring. Then, the reaction solution was poured into a solution of 4 l of water and 40 ml of acetic acid while stirring to precipitate a white polymer. The polymer was filtered off, washed with water, and dried under vacuum to obtain 185 g of polymer.

Weight average (polystyrene standard) when molecular weight was measured by gel permeation chromatography (GPC)
It was 28.000. Further, the carboxyl group content measured by titration was 2.47 meq / g.

Furthermore, 40g of this polymer was equipped with a condenser and stirrer.
It was put in a 3-necked round-bottomed flask of 00 ml and dissolved in 200 ml of DMF. To this solution was added 2.6 g (0.026 mol) of triethylamine, and after heating to 80 ° C, 1H, 1H, 7H-dodecafluoro-1-
10.3 g (0.026 mol) of heptyl bromide was added. Then, stirring was continued for 2 hours.

After completion of the reaction, the reaction solution was poured into a solution of water (4 l) and acetic acid (200 ml) with stirring to precipitate a white polymer. This polymer was separated by filtration, washed with water, and dried under vacuum to obtain 44 g of a polymer.

It was confirmed by NMR measurement that the 1H, 1H, 7H-dodecafluoro-1-heptyl group had been introduced, and the acid value was further measured by titration to find that it was 1.70 meq / g [polyurethane used in the present invention. (A)].

Synthesis Example 2 m-xylylene diisocyanate 94 g (0.50 mol) and N- (1,1-bis (hydroxymethyl) propyl) pentafluorobenzenesulfonamide were placed in a 500 ml three-necked round flask equipped with a condenser and a stirrer. And 2,2-bis (hydroxymethyl) propionic acid 47g
(0.35 mol) was added and dissolved in 330 ml of dioxane. As a catalyst, 1 g of N, N-diethylaniline was added, and the mixture was heated under reflux for 6 hours with stirring. Then, the reaction solution was mixed with 4 L of water and acetic acid.
It was poured into 40 ml of the solution with stirring to precipitate a white polymer. This polymer was separated by filtration, washed with water, and then dried under vacuum to obtain 180 g of a polymer.

When the molecular weight was measured by GPC, the weight average (polystyrene standard) was 24,000. Further, when the acid value was measured by titration, it was 1.72 meq / g. (Polyurethane (b) used in the present invention).

Synthesis Examples 3 to 14 Polyurethane resins used in the present invention were synthesized in the same manner as in Synthesis Example 1 or Synthesis Example 2 using the diisocyanates and diol compounds shown in Table 1. The molecular weight was measured by GPC, and the acid value was measured by titration. The acid values measured are shown in Table 1.

All molecular weights are weight average (polystyrene standard)
It was 11,000 to 36,000.

Examples 1 to 5 An aluminum plate having a thickness of 0.30 mm was grained on its surface with a nylon brush and an aqueous suspension of 400 mesh pumice, and then washed thoroughly with water. It was immersed in 10% sodium hydroxide at 70 ° C. for 60 seconds for etching, washed with running water, neutralized with 20% nitric acid, and washed with water. This was subjected to electrolytic surface-roughening treatment in an aqueous 1% nitric acid solution at an anodic electricity of 160 clones / dm ² using a sinusoidal alternating current under the condition of V _A = 12.7V. The surface roughness was measured and found to be 0.6 μ (Ra
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 of the following photosensitive solution [A], five kinds of photosensitive solutions [A] -1 to [A]
-5 was prepared, and this photosensitive solution was applied on an anodized aluminum plate and dried at 100 ° C. for 2 minutes to prepare photosensitive lithographic printing plates [A] -1 to [A] -5. . The coating amount at this time was 2.5 g / m ² in dry weight.

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

Photosensitive solution [A] Next, as a comparative example, the following photosensitive solution [B] was applied in the same manner as the photosensitive solution [A] to prepare a photosensitive lithographic printing plate [B]. The coating weight after drying was 2.5 g / m ² .

Photosensitive liquid [B] 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 [5] and [B] and exposed at a distance of 70 cm with a carbon arc lamp of 30 amperes.

Exposed photosensitive lithographic printing plates [A] -1 to 5 and [B]
Was immersed and developed in an 8 times diluted aqueous solution of DP-4 (trade name: manufactured by Fuji Photo Film Co., Ltd.) at 25 ° C. for 60 seconds.

The planographic printing plates [A] -1 to 5 and [B] thus obtained were used to print on high-quality paper with a commercially available ink using a KOR type printer manufactured by Heidelberg. Planographic printing plates [A] -1 to 5 and [B]
When the final number of printed sheets was examined, it was as shown in Table 2.

As can be seen from Table 2, the planographic printing plates [A] -1 to 5 (Examples 1 to 5) 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.

Instead of the resin of the present invention in the photosensitive solution [A], a commercially available polyurethane resin having no carboxyl group was used as Estane # 5715 (Estane # 5715, manufactured by BF Goodrich Co.).
When coating, exposure and development were carried out in the same manner as above, development failure occurred and a clear image could not be obtained. From this, it can be seen that the resin of the present invention has very excellent developability in an aqueous alkaline developer as compared with a polyurethane resin having no carboxyl group.

Examples 6 to 10 An aluminum plate having a thickness of 0.24 mm was grained on its surface with a nylon brush and an aqueous suspension of 400 mesh pumice and then thoroughly washed with water. This was immersed in a 10% aqueous sodium hydroxide solution at 70 ° C. for 60 seconds for etching, then washed with running water, neutralized with 20% nitric acid, and then washed with the light of the prior art.
Electrochemical surface roughening method described in JP 07, namely V _A = 12.7 V, V
Using a sinusoidal alternating waveform current of _C = 9.1 V, electrolytic surface roughening treatment was performed in a 1% aqueous nitric acid solution at an anode electricity of 160 clones / dm ² . Continue to soak in 30% sulfuric acid aqueous solution at 55 ℃
After desmutting for 2 minutes, it was anodized in a 7% sulfuric acid aqueous solution so that the coating amount of aluminum oxide was 2.0 g / m ² . Then, it was immersed in a 3% aqueous solution of sodium silicate at 70 ° C. for 1 minute, washed with water and dried. On the aluminum plate obtained as described above, the photosensitive liquid [C] -1 to
[C] -5 was applied using a wheeler and dried at 80 ° C for 2 minutes. The dry weight was 2.0 g / m ² .

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

Photosensitive liquid [C] Next, as a comparative example, a photosensitive solution [D] using the following polymer instead of the polyurethane resin used in the present invention in the above photosensitive solution was similarly applied and dried. The dry weight was 2.0 g / m ² .

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

The weight average molecular weight (polystyrene standard) is 55,000.
Met.

Each of the photosensitive lithographic printing plates [C] -1 to 5 and [D] obtained by using the photosensitizing liquids [C] -1 to 5 and [D] was adjusted to 1 m with a PS light manufactured by Fuji Photo Film Co., Ltd. Imagewise exposed from a distance for 1 minute, immersed in a developing solution at room temperature for 1 minute, lightly rubbed the surface with absorbent cotton to remove the unexposed area, and then a bright blue image lithographic printing plate [C] -1. ~ 5 and [D]
Got

(Developer) Each of the printing plates was used to print on high-quality paper with a commercially available ink using a KOR type printer manufactured by Heidelberg. Planographic printing plate [C]
When the final number of printed sheets of -1 to 5 and [D] was examined, it was as shown in Table 3.

As can be seen from Table 3, the planographic printing plates [C] -1 to 5 (Examples 6 to 10) using the photosensitive composition of the present invention produced a larger number of printed sheets than the comparative example [D]. The printing durability is very good.

Examples 11 to 14 The aluminum plate obtained in Example 6 was provided with the following photosensitive solution [E].
Apply [1]-[E] -4 using a wheeler and apply 2 at 80 ℃.
Dry for minutes. The dry weight was 2.0 g / m ² .

The polyurethane resins used in the present invention used in the photosensitive liquids [E] -1 to [E] -4 are shown in Table 4.

Photosensitive liquid [E] Then, as a comparative example, a benzyl methacrylate-methacrylic acid (molar ratio 73/27) copolymer (polymerization average molecular weight of 45,00) was used in place of the polyurethane resin used in the present invention in the above-mentioned photosensitive solution.
Similarly, a photosensitive solution [F] using 0 (polystyrene standard) was applied and dried. The dry weight was 2.0 g / m ² .

Each of the photosensitive lithographic printing plates [E] -1 to 4 and [F] obtained by using the photosensitizing liquids [E] -1 to 4 and [F] was adjusted to 1 m with a PS light manufactured by Fuji Photo Film Co., Ltd. After image exposure for 1 minute from a distance and immersion 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 portion, and a lithographic printing plate with a bright blue image [E ] -1 to 4 and [F] were obtained.

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

As can be seen from Table 4, the lithographic printing plates [E] -1 to 4 (Examples 11 to 14) using the photosensitive composition of the present invention had a larger number of printed sheets than the comparative example [F], It has excellent printability.

Examples 15 to 16 The following photosensitive liquid [G] was added to the aluminum plate obtained in Example 6.
Apply -1 to [G] -2 with a wheeler and apply 2 at 80 ℃.
Dry for minutes. The dry weight was 2.0 g / m ² .

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

Photosensitive liquid [G] Next, as a comparative example, a methyl methacrylate-methacrylic acid (molar ratio 80/20) copolymer (weight average molecular weight of 52,000) was used in place of the polyurethane resin used in the present invention in the photosensitive solution.
(Polystyrene standard)) was similarly applied and dried. The dry weight was 2.0 g / m ² .

A photosensitive lithographic printing plate [G] -1-2 and [H] obtained by using the photosensitizing liquids [G] -1 and 2 and [H] was used, and a distance of 1 m was obtained using a PS light manufactured by Fuji Photo Film Co., Ltd. Image-exposed for 1 minute, immersed in the developer used in Example 6 at room temperature for 1 minute, and then lightly rubbed the surface with absorbent cotton to remove the unexposed portion, and then a bright blue image lithographic printing plate [G] -1 and 2 and [H] were obtained.

Each of the printing plates was used to print on high-quality paper with a commercially available ink using a KOR type printer manufactured by Heidelberg. Planographic printing plate [G]
When the final number of printed sheets of -1 to 2 and [H] was examined, it was as shown in Table 5.

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

〔The invention's effect〕

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

Claims (1)

[Claims] 1. A photosensitive composition comprising a polyurethane resin having a carboxyl group and a fluorine-substituted hydrocarbon group.