JPH10312058A - Photosensitive composition and photosensitive lithographic printing plate - Google Patents

Abstract

(57) [Problem] To provide a photosensitive composition which gives a coating film having excellent solvent resistance and abrasion resistance, and a photosensitive lithographic printing plate having excellent printing durability. SOLUTION: A first structure is a polyurethane resin (A) having a macromer unit having an acidic hydrogen atom in a side chain.
And a photosensitive compound (B). A second configuration is a photosensitive lithographic printing plate characterized in that the photosensitive composition is provided on a metal support.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a lithographic printing plate, an IC,
The present invention relates to a photosensitive composition suitable for manufacturing circuits and photomasks. More specifically, the present invention relates to a photosensitive composition which provides a coating film having excellent solvent resistance and abrasion resistance, and a photosensitive lithographic printing plate having excellent printing durability.

[0002]

2. Description of the Related Art A photosensitive composition comprising an o-naphthoquinonediazide compound and a novolak-type phenol resin has been industrially used as a very excellent photosensitive composition for producing a lithographic printing plate or as a photoresist. However, due to the properties of the novolak type phenol 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 sufficient There was a point to be improved such as not being. Various binder resins have been studied to solve such a problem.

As a known polymer having excellent abrasion resistance, there is a polyurethane resin. Japanese Unexamined Patent Publication (KOKAI) Showa No. 63-124047 discloses a water-insoluble and alkali-soluble polyurethane resin.
A photosensitive composition comprising a naphthoquinonediazide compound is described.

On the other hand, JP-A-62-123452 describes a photosensitive composition characterized by containing a polyurethane resin having a carboxyl group in the main chain and a diazonium compound.

[0005] However, the coating films obtained from the photosensitive compositions containing the binder resins described in the above-mentioned publications all have the disadvantage that the solvent resistance is insufficient. In particular, there is a problem that resistance to a cleaning agent containing a solvent used in UV ink printing is poor, and as a result, printing durability is insufficient.

[0006]

An object of the present invention is to provide a photosensitive composition which gives a coating film having excellent solvent resistance and abrasion resistance and a photosensitive lithographic printing plate having excellent printing durability. is there.

[0007]

Means for Solving the Problems The present inventors synthesized various resins having an atomic group having a specific structure, prepared a photosensitive composition, and evaluated the physical properties. The photosensitive composition comprising a polyurethane resin having a macromer unit in a side chain and the photosensitive compound (B) as an essential component is compared with the photosensitive composition containing the above-mentioned known binder resin. As a result, the inventors have found that the solvent resistance and the printing durability are remarkably excellent, and have completed the present invention.

That is, a first constitution of the present invention is characterized by comprising (A) a polyurethane resin having a macromer unit having an acidic hydrogen atom in a side chain, and (B) a photosensitive compound as essential components. The present invention relates to a photosensitive composition.

Further, the present invention relates to a radical polymerizable resin having an acidic group in the presence of a mercaptan-based chain transfer agent having two or more hydroxyl groups and one mercapto group. The present invention relates to a photosensitive composition obtained by reacting a macromer obtained by radical polymerization of a monomer having an unsaturated bond as an essential component with a polyisocyanate as a polyol component.

[0010] The second structure of the present invention is the above-mentioned (A)
The present invention relates to a photosensitive lithographic printing plate characterized in that a photosensitive composition comprising a polyurethane resin having a macromer unit having an acidic hydrogen atom in a side chain and a photosensitive compound (B) is provided on a metal support.

The present invention also relates to a photosensitive lithographic printing plate wherein the photosensitive compound (B) is a positive photosensitive compound, and a photosensitive lithographic printing plate wherein the photosensitive compound (B) is a negative photosensitive compound. About.

Further, the present invention relates to a negative photosensitive lithographic printing plate wherein the negative photosensitive compound is a photosensitive diazonium compound.

Further, the present invention relates to a negative photosensitive lithographic printing plate wherein the negative photosensitive compound is a monomer or oligomer having at least two polymerizable ethylenically unsaturated groups and a photopolymerization initiator.

Further, the present invention provides the above-mentioned negative type photosensitive compound in which a photosensitive diazonium compound, a monomer or oligomer having at least two polymerizable ethylenically unsaturated groups, and a photopolymerization initiator are combined. The present invention relates to a negative photosensitive lithographic printing plate.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, (A) a polyurethane resin having a macromer unit having an acidic hydrogen atom in a side chain, which is used in the composition of the present invention and a method for producing the same,
(B) A photosensitive composition containing a photosensitive compound as an essential component and other components, a method for preparing a photosensitive composition used in the present invention, and a method for manufacturing a lithographic printing plate according to the present invention. This will be described in detail.

The methods for producing the macromer having an acidic hydrogen atom and the polyurethane resin used in the present invention are described, for example, in JP-A-4-178416 and JP-A-4-4-1.
78417 and the like.

The macromer having an acidic hydrogen atom used in the present invention includes, for example, vinyl polymer resins such as polyacrylates, polystyrenes, polyvinyl ethers and polyacrylonitriles, novolaks, polyesters and polyamides. Any resin obtained from such a condensation polymerization-based resin may be used, and can be suitably used in the present invention. Among them, the reaction using a vinyl polymer resin can be cited as an example of a macromer that can be particularly preferably used. Hereinafter, this system will be described as an example.

Examples of the monomer having a radical polymerizable unsaturated bond having an acidic hydrogen atom used in the production of the macromer of the present invention include N- (4-hydroxyphenyl) methacrylamide, monomethacryloylhydroquinone, and A vinyl polymerizable monomer having a phenolic hydroxyl group such as -hydroxystyrene, p-hydroxystyrene, p-isopropenylphenol and m-isopropenylphenol, and a vinyl polymerizable monomer having a carboxyl group such as acrylic acid and methacrylic acid Monomer having a sulfonamide group, such as N- (4-sulfamoylphenyl) methacrylamide, N-phenylsulfonylmethacrylamide, N-phenylsulfonylmaleimide, vinyl polymer monomer having an active imide group Monomer, JP-A-63-1 Such vinyl polymerization system active methylene group-containing resin of 7237 JP monomers and the like. These monomers having a radical polymerizable unsaturated bond having an acidic group can be used alone or as a mixture of a plurality of them. Further, it may be used as a mixture with a monomer having a radical polymerizable unsaturated bond containing no acidic group other than the above.

Examples of the monomer having a radical polymerizable unsaturated bond other than those used in the production of the macromer of the present invention include, for example, methyl acrylate, ethyl acrylate,
Propyl acrylate, butyl acrylate, amyl acrylate, ethyl hexyl acrylate, octyl acrylate, t-octyl acrylate, chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane mono Acrylates such as acrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, tetrahydroacrylate:

Aryl acrylates such as phenyl acrylate and furfuryl acrylate: methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 4-hydroxybutyl methacrylate Methacrylates such as, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate, furfuryl methacrylate and tetrahydrofurfuryl methacrylate:

Aryl methacrylates such as phenyl methacrylate, cresyl methacrylate and naphthyl methacrylate: acrylamide or its derivatives as N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, Nt-butylacrylamide N-alkylacrylamides such as N-heptylacrylamide, N-octylacrylamide, N-cyclohexylacrylamide, N-benzylacrylamide: N-phenylacrylamide, N-tolylacrylamide, N-nitrophenylacrylamide, N-naphthylacrylamide, N -N such as hydroxyphenylacrylamide
-Aryl acrylamides:

N, N-dimethylacrylamide, N, N
N, N-dialkylacrylamides such as diethylacrylamide, N, N-dibutylacrylamide, N, N-dibutylacrylamide, N, N-diisobutylacrylamide, N, N-diethylhexylacrylamide, N, N-dicyclohexylacrylamide: N −
N, N such as methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide
-Aryl acrylamides:

Examples of methacrylamide or a derivative thereof include N-methylmethacrylamide, N-ethylmethacrylamide, N-propylmethacrylamide, N-butylmethacrylamide, Nt-butylmethacrylamide,
N-alkyl methacrylamides such as -ethylhexyl methacrylamide, N-hydroxyethyl methacrylamide and N-cyclohexyl methacrylamide: N-aryl methacrylamides such as N-phenyl methacrylamide and N-naphthyl methacrylamide: N, N N, N-dialkyl methacrylamides such as diethyl methacrylamide, N, N-dipropyl methacrylamide, N, N-dibutyl methacrylamide:

N, N-diaryl methacrylamides such as N, N-diphenyl methacrylamide: N-hydroxyethyl-N-methyl methacrylamide, N-methyl-N-phenyl methacrylamide, N-ethyl-N-phenyl methacrylamide Methacrylamide derivatives such as amides: allyl compounds such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate and allyloxyethanol:

Hexyl vinyl ether, octyl vinyl ether, dodecyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol Vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether,
Vinyl ethers such as vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether and vinyl anthranyl ether:

Vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl phenyl acetate, vinyl aceto acetate, vinyl lactate , Vinyl-β-
Vinyl esters such as phenylbutyrate, vinylcyclohexylcarboxylate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate:

Methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene,
Isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, dodecylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, methoxystyrene, 4-methoxy-3
-Methylstyrene, dimethoxystyrene, chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, 2-bromo-4-trifluoromethylstyrene,
Styrenes such as 4-fluoro-3-trifluoromethylstyrene: butyl crotonate, hexyl crotonate,
Crotonic esters such as crotonic acid and glycerin monotonate:

Dialkyl itaconates such as dimethyl itaconate, diethyl itaconate and dibutyl itaconate: maleic acid or fumaric acid dialkyls such as dimethyl malate and dibutyl fumarate: maleimide, N-phenylmaleimide, N-2- Maleimides such as methylphenylmaleimide, N-2,6-diethylphenylmaleimide, N-2-chlorophenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N-hydroxyphenylmaleimide: other, N-vinylpyrrolidone, N- Vinyl pyridine, acrylonitrile, methacrylonitrile and the like can be mentioned.

Among these compounds having a polymerizable unsaturated bond, (meth) acrylic acids, (meth) acrylic esters, (meth) acrylamides, maleimides, (meth) ) Acrylonitrile.

In the present invention, when referred to as (meth) acrylate or (meth) acrylic acid, it includes not only acrylate but also methacrylate, and includes not only acrylic acid but also methacrylic acid. (Meth) acrylonitrile includes acrylonitrile and methacrylonitrile, and (meth) acrylamide includes acrylamide and methacrylamide.

The weight average molecular weight of the macromer thus obtained is not particularly limited, but is preferably 50
It is 0 or more and 20,000 or less.

As a solvent for producing the macromer of the present invention, for example, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl glycol, 2-methoxyethyl acetate, 1-methoxyethyl -2-propanol, 1
-Ethoxy-2-propanol, 1-methoxy-2-propyl acetate, 1-ethoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, N-methyl-
2-pyrrolidone, toluene, ethyl acetate, methyl lactate,
Ethyl lactate and the like. These solvents are used alone or in combination of two or more.

The mercaptan-based chain transfer agent having two or more hydroxyl groups and one mercapto group used in the production of the macromer used in the present invention includes, for example, 1-
Mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-
Propanediol, 2-mercapto-1,1-methanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2, 2-propanediol, 2-mercaptoethyl-2-methyl-1,3-
And propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol and the like.

The polyurethane resin having a macromer unit having an acidic hydrogen atom in the side chain used in the present reaction can be used, for example, in the presence of a mercaptan-based chain transfer agent having two or more hydroxyl groups and one mercapto group. Examples include those obtained by reacting a macromer obtained by radical polymerization with a monomer having a radical polymerizable unsaturated bond having an acidic hydrogen atom as an essential component as a polyol component and a polyisocyanate as a polyol component.

Further, the polyurethane composition of the present invention comprises:
Macromer obtained by radical polymerization of a monomer having a radical polymerizable unsaturated bond having an acidic hydrogen atom as an essential component in the presence of a mercaptan-based chain transfer agent having one or more hydrogen hydroxide atoms and one mercapto group In addition to the polyol component consisting of, a polyol having two or more groups that react with the polyisocyanate can be used in combination.

Examples of polyols having two or more groups reactive with polyisocyanate include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4
-Butylene glycol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, diethylene glycol, triethylene glycol, dipropylene Glycol, tripropylene glycol, cyclohexane-1,4-dimethanol, glycerin, trimethylolpropane, trimethylolethane,
A mixture of one or more low-molecular-weight polyols such as hexanetriol, pentaerythritriol, sorbitol, and methylglycoside;

Ethylenediamine, 1,3-propylenediamine, 1,2-propylenediamine, hexamethylenediamine, hydrazine, piperazine, N, N'-diaminopiperazine, 2-methylpiperazine, 4,4'-diaminodicyclohexylmethane, isophorone One of low molecular weight polyamines such as diamine, diaminobenzene, diphenylmethanediamine and methylenebisdichloroaniline
Succinic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimet Polyester polyols such as acids, phthalic anhydride, tetrahydrophthalic anhydride, glutaric anhydride, polybasic acids such as maleic acid, maleic anhydride, hexahydroisophthalic acid or condensates with one or more anhydrides ,

Ring-opening polymers such as γ-butyrolactone and ε-caprolactone using the above-mentioned polyol as initiator, polycarbonate diols such as poly (hexamethylene carbonate) diol, and one or more of the above-mentioned polyols and polyamines And polyether polyols such as ring-opening polymers such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, and tetrahydrofuran.

The polyisocyanate preferably used in the present invention includes, for example, aromatic diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate and phenylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate and isophorone diisocyanate. Aliphatic or alicyclic diisocyanates such as dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, triphenyl methane triisocyanate, polyphenyl polymethylene polyisocyanate, polyisocyanate having carbodiimide group, and poly having allophanate group Isocyanate isocyanate Polyisocyanate and the like having a rate group.

Specific examples of the polyurethane resin that can be particularly preferably used in the present invention include 3-mercapto-
Examples thereof include a reaction product of diphenylmethane diisocyanate and a macromer having two hydroxyl groups obtained by copolymerizing methacrylic acid, methyl methacrylate, and acrylonitrile using 1,2-propanediol as a chain transfer agent.

Solvents used for synthesizing the polyurethane resin include, for example, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl glycol, 2-methoxyethyl acetate, 1-methoxyethyl -2-propanol, 1-ethoxy-2-propanol, 1-methoxy-2-propyl acetate, 1-ethoxy-2-propyl acetate, N, N-dimethylformamide, N, N
-Dimethylacetamide, dimethylsulfoxide, N-
Examples thereof include methyl-2-pyrrolidone, toluene, ethyl acetate, methyl lactate, and ethyl lactate. These solvents are used alone or in combination of two or more.

The photosensitive compound (B) used in the photosensitive composition of the present invention may be appropriately selected from known ones, for example, depending on whether a positive or negative composition is prepared. Specifically, the following (1), (2),
A photosensitive compound selected from (3) or (4) can be used.

(1) o-naphthoquinonediazide compound (2) photosensitive diazonium compound (3) combination of a photopolymerization initiator with a monomer or oligomer having at least two polymerizable ethylenically unsaturated groups (4) photosensitive diazonium Compound, monomer or oligomer having at least two polymerizable ethylenically unsaturated groups and combination of photopolymerization initiator

Specific examples of the positive photosensitive compound include o-naphthoquinonediazide compounds. The o-naphthoquinonediazide compound used in the present invention is preferably an ester of 1,2-diazonaphthoquinonesulfonic acid chloride and pyrogallol-acetone resin described in JP-B-43-28403.

Other suitable orthoquinonediazide compounds include the compounds described in US Pat. Nos. 3,046,120 and 3,188,210.
There are esters of 2-diazonaphthoquinone sulfonic acid chloride with phenol-formaldehyde resin.

Other useful o-naphthoquinonediazide compounds are described and known in numerous patents. For example, JP-A-47-5303 and JP-A-48-63
Nos. 802, 48-63803, 48-965
No. 75, No. 49-38701, No. 48-1335
No. 4, Japanese Patent Publication No. 37-18015, and No. 41-1122
No. 2, No. 45-9610, and No. 49-17481, and the like.

Particularly preferred o-naphthoquinonediazide compounds in the present invention are compounds obtained by reacting a polyhydroxy compound having a molecular weight of 1,000 or less with 1,2-diazonaphthoquinonesulfonic acid chloride. Specific examples of such compounds are described in JP-A-51-139402.
No. 58-150948, No. 58-203434
No., 59-165053, 60-12445
No. 60-134235, No. 60-16343
No. 61-118744, No. 62-10645,
No. 62-10646, No. 62-153950, No. 6
Examples described in the specification such as 2-178562 can be given.

When synthesizing these o-naphthoquinonediazide compounds, it is preferable to react 0.2-1.2 equivalents of 1,2-diazonaphthoquinonesulfonic acid chloride with respect to the hydroxyl group of the polyhydroxy compound. More preferably, the reaction is carried out in an amount of from 3 to 1.0 equivalent.

The resulting o-naphthoquinonediazide compound is a mixture of various 1,2-diazonaphthoquinonesulfonic acid ester groups having different positions and introduced amounts. The ratio of the compound converted in the above to the mixture (content of the completely esterified compound) is preferably 5 mol% or more, more preferably 20 to 100 mol%.

Examples of positive photosensitive compounds other than o-naphthoquinonediazide compounds include, for example, JP-B-56
-2696, JP-A-48-89003, JP-A-51
JP-A-120714, JP-A-53-133429, JP-A-55-12995, JP-A-55-126236,
JP-A-56-17345, JP-A-60-10247
JP-A-60-37549, JP-A-60-1214
No. 46 and the like.

The photosensitive compounds used in the negative photosensitive composition include the compounds (2) to (4) described above, and specific examples thereof include the following.

As the photosensitive diazonium compound, for example, there is a diazo resin represented by a salt of a condensate of a diazodiarylamine and an active carbonyl compound, and a photosensitive, water-insoluble and organic solvent-soluble compound is preferred.

Particularly preferred diazo resins are, for example, 4-diazodiphenylamine, 4-diazo-3-methyldiphenylamine, 4-diazo-4'-methyldiphenylamine, 4-diazo-3'-methyldiphenylamine,
Diazo-4'-methoxydiphenylamine, 4-diazo-3-methyl-4'-ethoxydiphenylamine, 4-
Condensation of at least one compound selected from diazo-3-methoxydiphenylamine and at least one compound selected from formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, 4,4'-bis-methoxymethyldiphenyl ether and the like Organic or inorganic acid salts.

Examples of the organic acid include methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, mesitylenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, propylnaphthalenesulfonic acid, 1-naphthol-5- Sulfonic acid, 2
-Nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2,4-dihydroxybenzophenone, benzenephosphinic acid, and the like.Examples of inorganic acids include hexafluorophosphoric acid, Examples include tetrafluoroboric acid and thiocyanic acid.

Further, a diazo resin having a main chain of a polyester group described in JP-A-54-30121;
A diazo resin obtained by reacting a polymer having a carboxylic anhydride residue described in JP-A 1-273538 with a diazo compound having a hydroxyl group; a diazo resin obtained by reacting a polyisocyanate compound with a diazo compound having a hydroxyl group : A diazo resin having a carboxyl group: a diazo resin having a phenolic hydroxyl group or the like can also be used.

The use amount of these diazo resins is preferably in the range of 0.1 to 40% by weight based on the solid content of the composition.
If necessary, two or more diazo resins may be used in combination.

Examples of the compound having an ethylenically unsaturated group include monomers having a boiling point of 100 ° C. or more at normal pressure and having at least one, preferably two or more addition-polymerizable ethylenically unsaturated groups per molecule. Or an oligomer.
Examples of such a monomer or oligomer include, for example,
Polyethylene glycol mono (meth) acrylate [Hereinafter, methacrylate and acrylate are collectively referred to as (meth) acrylate. Monofunctional (meth) acrylates such as polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane 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) isocyanurate (Meth) acrylates of polyhydric alcohol / alkylene oxide adducts and (meth) acrylates of polyhydric phenol / alkylene oxide adducts Relate, JP-B-48-41708, JP-B-50-603
4, urethane acrylates described in JP-B-51-37193 and JP-A-48-64183.
No., JP-B-49-43191, JP-B-52-3049
Polyfunctional (meth) acrylates such as polyester acrylates and epoxy acrylates obtained by adding an epoxy resin and (meth) acrylic acid described in each of JP-A No. 0 can be exemplified.

The polyurethane resin (A) having a macromer unit having an acidic hydrogen atom in the side chain is particularly suitable in combination with the above-mentioned compound having an ethylenically unsaturated group, alone or in combination with a photopolymerization initiator. When a photosensitive diazonium compound is further combined, the adhesiveness to a substrate is further improved, and a negative photosensitive lithographic printing plate having excellent printing durability can be obtained.

The amount of the compound having an ethylenically unsaturated group capable of undergoing addition polymerization is preferably in the range of 5 to 70% by weight based on the solid content of the composition.

Examples of the photopolymerization initiator include α-carbonyl compounds described in US Pat. No. 2,367,661, acyloin ethers described in US Pat. No. 2,448,828, and US Pat. No. 27225.
No. 12, α-hydrocarbon-substituted aromatic acyloin compounds, polycyclic quinone compounds described in U.S. Pat. No. 3,046,127, and U.S. Pat. No. 3,549,367. A combination of triarylbiimidazole / p-aminophenyl ketone,
Trihalomethyl-s-triazine compounds described in U.S. Pat. No. 4,239,850, U.S. Pat.
Oxadiazole compounds described in U.S. Pat. No. 221970, acridine and phenazine compounds described in U.S. Pat. No. 3,751,259,
Examples thereof include benzothiazole compounds described in JP-A-1-48516, and the amount thereof is preferably in the range of 0.5 to 20% by weight based on the solid content of the composition.

The photosensitive composition of the present invention can be used as a positive type lithographic printing plate or a negative type lithographic printing plate by coating it on an aluminum support.

In the case of a positive planographic printing plate, various additives can be added according to the purpose. For example, a surfactant for improving coating properties, a plasticizer for improving physical properties of a coating film, a sensitizing agent having a hydrophobic group for increasing ink inking property of an image area, and for increasing sensitivity. To a cyclic acid anhydride,
Immediately after exposure, a printing-out agent for obtaining a visible image and a dye or other filler as an image coloring agent can be added.

In the case of a negative type lithographic printing plate, an organic polymer binder can be used in addition to the negative type photosensitive compound and the alkali-soluble resin. As such an organic polymer binder, for example, acrylic resin, polyamide resin,
Examples include polyurethane resin, phenoxy resin, epoxy resin, polyacetal resin, polystyrene resin, and novolak resin. Further, known additives such as a thermal polymerization inhibitor, a dye, a surfactant, a plasticizer, and a stability improver can be added to improve the performance.

As the surfactant, JP-A-62-366
No. 57, JP-A-62-226143, and the like. Examples of the plasticizer include diethyl phthalate, dibutyl phthalate, dioctyl phthalate, tributyl phosphate, trioctyl phosphate, tricresyl phosphate, tri (2-chloroethyl) phosphate, and tributyl citrate.

Examples of the sensitizer include novolak resins having a hydrophobic group such as p-octylphenol novolak and pt-butylphenol novolak. As cyclic acid anhydrides, US Pat.
As described in US Pat. No. 5,128, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-endooxy- 無水 4-tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride Acid, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride and the like. These cyclic anhydrides are used in an amount of 1 to 15% by weight in the total photosensitive composition.
By containing it, the sensitivity can be increased up to about three times.

As a printing-out agent for obtaining a visible image immediately after exposure, for example, a combination of a photosensitive compound which releases an acid upon exposure and an organic dye which can form a salt can be mentioned. More specifically, ο described in JP-A-50-36209 and JP-A-53-8128.
A combination of -naphthoquinonediazide-4-sulfonic acid halogenide with a salt-forming organic dye or JP-A-53-36223;
Nos. 54-74728, 60-3626, 6
1-1143748, 61-151644, 63
Combinations of a trihalomethyl compound and a salt-forming organic dye described in JP-A-58440 can be exemplified.

As the colorant for the image, other dyes can be used in addition to the above-mentioned salt-forming organic dyes. Suitable dyes including salt-forming organic dyes include oil-soluble dyes and basic dyes. Specifically, Oil Yellow #
101, oil yellow # 130, oil pink # 31
2. Oil green BG, oil blue BOS, oil blue # 603, oil black BY, oil black BS, oil black T-505 (all manufactured by Orient Chemical Co., Ltd.), Victoria Pure Blue, crystal violet (CI42555), methyl Violet (CI42535), Rhodamine B (CI4517)
OB), malachite green (CI42000), methylene blue (CI52015) and the like.

Known stability improvers include, for example, phosphoric acid, phosphorous acid, oxalic acid, tartaric acid, malic acid, citric acid,
Dipicolinic acid, polyacrylic acid, benzenesulfonic acid,
Toluenesulfonic acid and the like can be mentioned.

The amounts of these various additives vary depending on the purpose, but generally, the amount of the solids in the photosensitive composition is from 0 to 0%.
A range of 30% by weight is preferred.

The above-mentioned photosensitive composition can be dissolved in various solvents as necessary and applied onto a support. As the solvent, for example, halogen-based solvents such as methylene chloride, chloroform, dichloroethane, trichloroethane, trichloroethylene, monochlorobenzene, dichlorobenzene, and carbon tetrachloride: hexane, heptane, cyclohesan,
Aliphatic or alicyclic or aromatic hydrocarbon solvents such as benzene, toluene and xylene: tetrahydrofuran,
Ether solvents such as dioxane and diethyl ether:
Ester solvents such as methyl acetate, butyl acetate, ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate:

A ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, butanol, benzyl alcohol, diacetone alcohol, methyl cellosolve,
Alcohol-based solvents such as ethyl cellosolve and cyclohexanol: Nitrogen-containing solvents such as acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone: dimethyl sulfoxide, etc. Two or more kinds may be used as a mixture, and in some cases, a mixed solvent with water may be used.

The photosensitive composition thus produced can be used, for example, by dip coating, curtain coating, roll coating,
It is applied to the support by a well-known application method such as spray application, wheeler application, spinner application, air knife application, doctor knife application and the like.

As the support, for example, aluminum,
Metal plate of zinc, copper, stainless steel, iron, etc .: Plastic film of polyethylene terephthalate, polycarbonate, polyvinyl acetal, polyethylene, etc .: Vapor deposition and lamination of a metal layer on paper or plastic film with synthetic resin melt coated or synthetic resin solution coated Composite materials provided by techniques such as those described above: and other various materials used as a support for a printing plate.

Further, in the case of a support having a metal surface, particularly an aluminum surface, it is preferable that a surface treatment such as graining treatment, anodizing treatment, and hydrophilizing treatment is performed. The coating amount of the photosensitive composition is usually about 0.5 to 5 g / m ² by dry weight.

After coating, the resultant is dried by a known method to obtain a photosensitive lithographic printing plate having a photosensitive layer provided on a support.

The photosensitive lithographic printing plate thus obtained can be used by a known method. For example, a positive type film is brought into close contact with this photosensitive lithographic printing plate, exposed with an ultra-high pressure mercury lamp, a metal halide lamp, etc., and developed with an aqueous alkali solution such as sodium metasilicate, potassium metasilicate, sodium phosphate, caustic soda, and the like. Used as

When the lithographic printing plate thus obtained is subjected to a thermosetting treatment (called a burning treatment or a baking treatment), the printing durability is further improved and the non-image area is hardly stained. There is also an effect.

[0078]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist.

(Synthesis Example 1) Macromer polymer-1 31.0 g of methyl ethyl ketone was placed in a 200 ml four-necked flask equipped with a nitrogen inlet tube, a thermometer and a stirrer, and heated to 80 ° C. While blowing in nitrogen gas, 8.0 g of methyl methacrylate, 24.0 g of methacrylic acid, 8.0 g of acrylonitrile, 4.0 g of 3-mercapto-1,2-propanediol, and 2,2′-azobis (2,
A monomer solution obtained by dissolving 0.06 g of 4-dimethylvaleronitrile in 3.0 g of methyl ethyl ketone was added dropwise over 2 hours. The reaction solution was kept at 80 ° C.
After an hour, 0.14 g of 2,2'-azobis (2,4-dimethylvaleronitrile) was added, and the mixture was further stirred for 1 hour. After completion of the polymerization reaction, the reaction solution was cooled to room temperature, and the reaction solution was dropped into 1 liter of hexane to precipitate a polymer.
After washing and drying, macromer polymer-1 was obtained.

(Synthesis Example 2) Polymer-2 N, N-dimethylacetamide was placed in a 200 ml four-necked flask equipped with a nitrogen inlet tube, a thermometer and a stirrer.
Add 0 g and heat to 80 ° C. While blowing in nitrogen gas, 15.0 g of diphenylmethane diisocyanate, 40.0 g of polymer-1 macromer, and 0.04 g of dibutyltin dilaurate were added. The reaction solution was kept at 80 ° C., and stirring was continued for another 5 hours. After stopping the introduction of nitrogen and adding 3.0 g of methanol to terminate the reaction, the reaction solution was cooled to room temperature, and the reaction solution was dropped into 2 liters of methanol to precipitate a polymer, which was filtered, washed, and dried to obtain a polymer. 2 (polyurethane resin) was obtained.

(Comparative Synthesis Example 1) Comparative Polymer-1 In a 500 ml three-necked flask equipped with a condenser and a stirrer, 125 g of diphenylmethane diisocyanate and 67 of 2,2-bis (hydroxymethyl) propionic acid were placed.
g was added and dissolved in 290 ml of dioxane. 1 g of N, N-diethylaniline was added as a catalyst and heated at 80 ° C. for 6 hours with stirring. Thereafter, 41 ml of water was added to the reaction solution,
The solution was charged into a solution of acetic acid (40 ml) with stirring to obtain Comparative Polymer-1 (polymer described in JP-A-63-124047).

With respect to Example 1 and Comparative Example 1, photosensitive solutions (photosensitive compositions) having the composition ratios shown in Table 1 below were prepared, respectively, and the printing plate was prepared according to the procedures described below, and the solvent resistance and printing durability test were performed. Was carried out.

[0083]

[Table 1]

Each (note) in Table 1 shows the following. (Note 1): Esterification rate 90% (Note 2): m-cresol (100 g), p-cresol (66.8 g), phenol (36.0 g), 37%
An aqueous formaldehyde solution (105 g) and oxalic acid (2.5
The mixture of g) was heated and stirred at 105 ° C. for 3 hours. Thereafter, the temperature was raised to 175 ° C. to distill off water, and 200 ° C./10
The residual monomer was distilled off at 0 mmHg. The weight average molecular weight of the cresol-formaldehyde resin obtained by the above-mentioned production method was 4000. (Note 3): Basic oil-soluble dye manufactured by Hodogaya Chemical Industry Co., Ltd.

(Preparation of Printing Plate, Solvent Resistance Test and Printing Durability Test) An aluminum plate having a thickness of 0.24 mm was degreased with an aqueous sodium hydroxide solution and subjected to electrolytic polishing in a 20% hydrochloric acid bath. Thus, a grained board having a center line average roughness (Ra) of 0.6 μm was obtained. Then, in a 20% sulfuric acid bath, the current density was 2 A /
Anodizing treatment was performed at dm ² to form an oxide film of 2.7 g / m ² , followed by washing and drying to obtain an aluminum support. The photosensitive solution (photosensitive composition) having the above composition was applied to the thus obtained aluminum support using a roll coater and dried at 100 ° C. for 3 minutes to obtain a photosensitive lithographic printing plate. The dry coating amount was 2.0 g / m ² .

An image film was brought into close contact with each of the obtained positive photosensitive lithographic printing plates, and exposed from a distance of 1 m with a 3 kW metal halide lamp. This was subjected to a development process at 30 ° C. for 12 seconds using a developing solution PD-1 (9-fold dilution) manufactured by Polychrome Japan Co., Ltd. using an automatic developing machine PD-912 manufactured by Dainippon Screen Co., Ltd. .

The lithographic printing plate thus prepared was evaluated for solvent resistance and printing durability. The solvent resistance was evaluated by immersing the lithographic printing plate exposed by the above apparatus in the following various solvents for 30 minutes, and evaluating the degree of erosion of the photosensitive layer.

The printing durability was measured by mounting a lithographic printing plate on a Roland Fabolit printing machine, using a UV ink “Dicure Scepter Boku” (manufactured by Dainippon Ink and Chemicals, Inc.).
Printing was performed using a 100-fold diluted solution of dampening solution "NA-108W" (manufactured by Dainippon Ink and Chemicals, Inc.), and the evaluation was made based on the final number of printed sheets on which an appropriate printed matter was obtained. Table 2 shows the results.

A and B in the solvent resistance column of Table 2 represent the following mixed solvents, respectively. A: light oil (60%) + butyl cellosolve (40%) B: xylene (30%) + light oil (50%) + butyl cellosolve (20%) The evaluation criteria are as follows.

：: no erosion, Δ: slight erosion, ×: completely eroded

[0091]

[Table 2]

(Synthesis Example 3) Macromer polymer-3 31.0 g of methyl ethyl ketone was placed in a 200 ml four-necked flask equipped with a nitrogen inlet tube, a thermometer and a stirrer, and heated to 80 ° C. While blowing in nitrogen gas, 24.0 g of methyl methacrylate, 8.0 g of methacrylic acid, 8.0 g of acrylonitrile, 4.0 g of 3-mercapto-1,2-propanediol, 2,2′-azobis (2,
A monomer solution obtained by dissolving 0.06 g of 4-dimethylvaleronitrile in 3.0 g of methyl ethyl ketone was added dropwise over 2 hours. The reaction solution was kept at 80 ° C.
After an hour, 0.14 g of 2,2'-azobis (2,4-dimethylvaleronitrile) was added, and the mixture was further stirred for 1 hour. After completion of the polymerization reaction, the reaction solution was cooled to room temperature, and the reaction solution was dropped into 1 liter of hexane to precipitate a polymer.
After washing and drying, a macromer polymer-3 was obtained.

(Synthesis Example 4) Polymer-4 N, N-dimethylacetamide was placed in a 200 ml four-necked flask equipped with a nitrogen inlet tube, a thermometer and a stirrer.
Add 0 g and heat to 80 ° C. While blowing in nitrogen gas, 15.0 g of diphenylmethane diisocyanate 40.0 g of macromer of polymer-3 and 0.04 g of dibutyltin dilaurate were added. The reaction solution was kept at 80 ° C., and stirring was continued for another 5 hours. After the introduction of nitrogen was stopped and 3.0 g of methanol was added to terminate the reaction, the reaction solution was cooled to room temperature, and the reaction solution was dropped into 2 liters of methanol to precipitate a polymer. 4 (polyurethane resin) was obtained.

(Comparative Synthesis Example 2) Comparative Polymer-2 125 g of diphenylmethane diisocyanate and 67 g of 2,2-bis (hydroxymethyl) propionic acid were placed in a 500 ml three-necked flask equipped with a condenser and a stirrer.
Was added and dissolved in 290 ml of dioxane. 1 g of N, N-diethylaniline was added as a catalyst, and the mixture was refluxed under heating for 6 hours with stirring. Thereafter, 41 ml of water and acetic acid 4
Introduced into 0 ml of the solution with stirring, the comparative polymer-2
(Polymer described in JP-A-62-123452) was obtained.

For Examples 2, 3, 4 and Comparative Example 2,
Photosensitive liquids (photosensitive compositions) having the composition ratios shown in Table 3 below were prepared, and a printing plate was prepared, and a solvent resistance and a printing durability test were performed according to the procedures described below.

[0096]

[Table 3]

(Preparation of printing plate, solvent resistance and printing durability test) An aluminum plate having a thickness of 0.24 mm was degreased with an aqueous sodium hydroxide solution, and subjected to electrolytic polishing in a 20% hydrochloric acid bath. A grained board having a center line average roughness (Ra) of 0.6 μm was obtained. Then, in a 20% sulfuric acid bath, the current density was 2 A / d.
and anodized m ^2, and the formed oxide film of 2.7 g / m ^2, washed with water dried, to obtain an aluminum support. The photosensitive solution (photosensitive composition) having the above composition was applied on the thus obtained aluminum support using a roll coater and dried at 100 ° C. for 3 minutes to obtain a photosensitive lithographic printing plate. The dry coating amount was 2.0 g / m ² .

An image film was brought into close contact with each of the resulting negative photosensitive lithographic printing plates, and exposed from a distance of 1 m with a 3 kW metal halide lamp. This was subjected to a developing treatment at 30 ° C. for 19 seconds using a developing solution ND-1 (4-fold dilution) manufactured by Polychrome Japan Co., Ltd. using an automatic developing machine PD-912 manufactured by Dainippon Screen Co., Ltd. .

The lithographic printing plate thus prepared was evaluated for solvent resistance and printing durability. The evaluation method is the same as in Example 1 and Comparative Example 1. The evaluation results are shown in Table 4 below.

[0100]

[Table 4]

Example 1 showed better solvent resistance than Comparative Example 1, and also had excellent printing durability. On the other hand, the negative-type photosensitive lithographic printing plate used in combination with the photosensitive diazonium compound (Example 2) exhibited better solvent resistance and printing durability as compared with Comparative Example 2, and exhibited stability over time and safety light resistance. Was also excellent.

When the resin of the present invention is combined with a photopolymerization initiator and a monomer having an ethylenically unsaturated group (Example 3), a photosensitive diazonium compound, a photopolymerization initiator, an ethylenically unsaturated When a monomer having a group was combined (Example 4), more excellent solvent resistance and printing durability were obtained, and a highly sensitive negative photosensitive lithographic printing plate was obtained.

[0103]

The coating film obtained from the photosensitive resin composition of the present invention has excellent solvent resistance and good developing characteristics.
When used as a lithographic printing plate, it exhibited excellent solvent resistance and printing durability, and in particular, exhibited excellent printing durability due to its excellent solvent resistance in UV ink printing.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/038 G03F 7/038 7/039 7/039 H01L 21/027 H01L 21/30 502R (72) Inventor Koji Koe Saitama 5-90 Higashima, Kitamoto-shi Sun apartment 2-505 Kitamoto (72) Inventor Yasuhiro Matsumoto 58-3 Minamikidocho, Nara City, Nara Prefecture

Claims (8)

[Claims] 1. A photosensitive composition comprising: (A) a polyurethane resin having a macromer unit having an acidic hydrogen atom in a side chain; and (B) a photosensitive compound. 2. The polyurethane resin (A) having a macromer unit having an acidic hydrogen atom in the side chain has an acidic group in the presence of a mercaptan-based chain transfer agent having two or more hydroxyl groups and one mercapto group. The photosensitive composition according to claim 1, which is a polyurethane resin obtained by reacting a macromer obtained by radical polymerization of a monomer having a radical polymerizable unsaturated bond as an essential component with a polyisocyanate as a polyol component. 3. A metal support comprising: (A) a polyurethane resin having a macromer unit having an acidic hydrogen atom in a side chain thereof; and (B) a photosensitive composition comprising a photosensitive compound. Photosensitive lithographic printing plate. 4. The photosensitive lithographic printing plate according to claim 3, wherein the photosensitive compound (B) is a positive photosensitive compound. 5. The photosensitive lithographic printing plate according to claim 3, wherein the photosensitive compound (B) is a negative photosensitive compound. 6. The photosensitive lithographic printing plate according to claim 5, wherein the negative photosensitive compound is a photosensitive diazonium compound. 7. The photosensitive lithographic printing plate according to claim 5, wherein the negative photosensitive compound is a monomer or oligomer having at least two polymerizable ethylenically unsaturated groups and a photopolymerization initiator. 8. The method according to claim 5, wherein the negative photosensitive compound is a combination of a photosensitive diazonium compound, a monomer or oligomer having at least two polymerizable ethylenically unsaturated groups, and a photopolymerization initiator. The photosensitive lithographic printing plate described in the above.