JP2911486B2 - Photosensitive composition - Google Patents

Description

The present invention relates to a photosensitive composition suitable for the production of a lithographic printing plate, an IC circuit or a photomask, and more particularly, to a positive composition. The present invention relates to a photosensitive composition having excellent abrasion resistance, chemical resistance, and development latitude.

[Conventional technology and problems to be solved]

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. As such an o-naphthoquinonediazide compound, an ester of a polyhydric phenol compound and 1,2-naphthoquinonediazidesulfonic acid chloride has been widely used. For example,
43-28403, esters of 1,2-naphthoquinonediazide sulfonic acid chloride and pyrogallol-acetone resin, U.S. Pat.Nos. 3,046,120 and 3,18
No. 8,210, esters of 1,2-naphthoquinonediazide sulfonic acid chloride and phenol-formaldehyde resin, and 2,3,4-trihydroxybenzophenone described in JP-B-38-12083. 1,2
-Esters with naphthoquinonediazidesulfonic acid chloride. When these compounds are used in combination with water-insoluble and alkaline water-soluble resins such as novolak-type phenolic resins and polyhydroxystyrene, the abrasion resistance is poor, and the printing durability when used in a lithographic printing plate is not sufficient. Further, there is a problem that the chemical resistance is poor, and especially when the UV ink is used, the printing durability is extremely insufficient. As a method of improving these performances, a burning process (exposure, development, and heat treatment) is generally used. However, when the burning process is performed, the low-molecular compound in the photosensitive layer adheres to the non-image area from the image area,
There is a problem that stains easily occur during printing.

In order to solve such a problem, various polymer compounds have been studied as binders. For example, Japanese Patent Publication No. 52-284
The acrylic polymer having a phenolic hydroxyl group as described in No. 01 publication has slightly improved printing durability and chemical resistance as compared with a novolak type phenol resin,
It was not satisfactory in practical use, and had problems such as deterioration of development latitude.

[Object of the invention]

Accordingly, an object of the present invention is to provide a photosensitive composition which is excellent in abrasion resistance, can be developed with an aqueous alkaline developer, and gives a lithographic printing plate having excellent printing durability.

Another object of the present invention is to provide a photosensitive composition which is excellent in chemical resistance and gives a lithographic printing plate having a large printing durability even when printing using UV ink without performing a burning treatment. is there.

Still another object is to provide a photosensitive composition having an excellent development latitude.

[Means for solving the problem]

The present inventors have result of intensive investigation to achieve the above object, in the photosensitive composition, -SO ₂ -NH- bond and / or The inventors have found that the above object can be achieved by including a condensation product of a compound having a bond and quinonediazide sulfonyl halide, and have reached the present invention.

 Hereinafter, the present invention will be described in detail.

-SO ₂ -NH- bond and / or for use in the present invention The compound having a bond is preferably-in a side chain or a main chain.
It is a polymer containing SO ₂ —NH— bonds and / or —CO—NH—CO— bonds.

-SO ₂ -NH- bonds and / or -CO-NH in the present invention
A preferred example of the compound having a -CO- bond is one in a molecule.
A compound having one or more —SO ₂ —NH— bonds and / or —CO—NH—CO— bonds and one or more polymerizable unsaturated bonds is prepared by using a known polymerization initiator in a suitable solvent. And polymerized by

Examples of the compound having an unsaturated bond suitably used in the present invention include the following general formulas (I) to (X).
Compounds represented by I) are mentioned.

^{Wherein, X 1, X 2, X} 3 are each -O- or -NR ²⁶ - shows the. R ^1, shows the ^{R 4, R 7, R 9} , R 12, R 14, R 16, R 18, R 20, R 22, R 24, R 25 each is -H or -CH _3. R ² , R ⁵ and R ¹⁰ each represent a C _{1 to} C ₁₂ alkylene group, cycloalkylene group, arylene group or aralkylene group which may have a substituent. R ³ and R ^{15 each} represent a hydrogen atom or a C _{1 to} C ₆ alkyl group, a cycloalkyl group or an aromatic group which may have a substituent. R ⁶ , R ⁸ , R ¹¹ , R ¹³ , R ¹⁷ , R ¹⁹ , R ²¹ , R ²³ may have a substituent, C _{1 to} C ₁₂ alkyl group, cycloalkyl group, aryl group, Represents an aralkyl group. Z represents a C _{1 to} C ₁₂ alkylene group which may have a substituent, a cycloalkylene group, or an aromatic ring group which may be substituted. Y ¹ , Y ²
Is Or -SO ₂ - shows a. Y ³ represents a single bond or —O—. And, R ₆ may be a hydrogen atom or a C ₁ ~ which may have a substituent.
C _{12 represents} an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group.

Among the compounds represented by the general formulas (I) to (XI), those particularly preferably used in the present invention include an alkylene group and a cycloalkylene group in which R ² , R ⁵ and R ¹⁰ are respectively C _{2 to} C _6. Or a phenylene group which may have a substituent, a naphthylene group, wherein R ³ and R ¹⁵ are a hydrogen atom or a C _{1 to} C ₃ alkyl group, and Z is a phenylene group which may have a substituent. And a naphthylene group, R ²⁶ is a hydrogen atom or a C ₁ -C ₄ alkyl group which may have a substituent.

Examples of such compounds represented by the general formulas (I) and (II) include N- (o-aminosulfonylphenyl) methacrylamide, N- (m-aminosulfonylphenyl) methacrylamide, N- (p-amino) Sulfonylphenyl) methacrylamide, N- (o-methylaminosulfonylphenyl) methacrylamide, N- (m-
Methylaminosulfonylphenyl) methacrylamide,
N- (p-methylaminosulfonylphenyl) methacrylamide, N- (o-ethylaminosulfonylphenyl) methacrylamide, N- (m-ethylaminosulfonylphenyl) methacrylamide, N- (p-ethylaminosulfonylphenyl) methacryl Amide, N- (o
-N-propylaminosulfonylphenyl) methacrylamide, N- (mn-propylaminosulfonylphenyl) methacrylamide, N- (pn-propylaminosulfonylphenyl) methacrylamide, N- (o-
i-propylaminosulfonylphenyl) methacrylamide, N- (mi-propylaminosulfonylphenyl) methacrylamide, N- (pi-propylaminosulfonylphenyl) methacrylamide, N- (on
-Butylaminosulfonylphenyl) methacrylamide, N- (mn-butylaminosulfonylphenyl)
Methacrylamide, N- (pn-butylaminosulfonylphenyl) methacrylamide, N- (oi-butylaminosulfonylphenyl) methacrylamide, N-
(Mi-butylaminosulfonylphenyl) methacrylamide, N- (pi-butylaminosulfonylphenyl) methacrylamide, N- (o-sec-butylaminosulfonylphenyl) methacrylamide, N- (m-
sec-butylaminosulfonylphenyl) methacrylamide, N- (p-sec-butylaminosulfonylphenyl) methacrylamide, N- (ot-butylaminosulfonylphenyl) methacrylamide, N- (mt-
Butylaminosulfonylphenyl) methacrylamide,
N- (pt-butylaminosulfonylphenyl) methacrylamide, N- (o-phenylaminosulfonylphenyl) methacrylamide, N- (m-phenylaminosulfonylphenyl) methacrylamide, N- (p-phenylaminosulfonylphenyl) ) Methacrylamide,
N- (o- (α-naphthylaminosulfonyl) phenyl) methacrylamide, N- (m- (α-naphthylaminosulfonyl) phenyl) methacrylamide, N- (p
-(Α-naphthylaminosulfonyl) phenyl) methacrylamide, N- (o- (β-naphthylaminosulfonyl) phenyl) methacrylamide, N- (m- (β-naphthylaminosulfonyl) phenyl) methacrylamide, N- ( p- (β-naphthylaminosulfonyl) phenyl) methacrylamide, N- (1- (3-aminosulfonyl) naphthyl) methacrylamide, N- (1- (3
-Methylaminosulfonyl) naphthyl) methacrylamide, N- (1- (3-ethylaminosulfonyl) naphthyl) methacrylamide, N- (o-methylsulfonylaminophenyl) methacrylamide, N- (m-methylsulfonylaminophenyl) Methacrylamide, N- (p
-Methylsulfonylaminophenyl) methacrylamide, N- (o-ethylsulfonylaminophenyl) methacrylamide, N- (m-ethylsulfonylaminophenyl) methacrylamide, N- (p-ethylsulfonylaminophenyl) methacrylamide, N- (O-phenylsulfonylaminophenyl) methacrylamide, N-
(M-phenylsulfonylaminophenyl) methacrylamide, N- (p-phenylsulfonylaminophenyl) methacrylamide, N- (o- (p-methylphenylsulfonylamino) phenyl) methacrylamide, N
-(M- (p-methylphenylsulfonylamino) phenyl) methacrylamide, N- (p- (p-methylphenylsulfonylamino) phenyl) methacrylamide,
N- (p- (α-naphthylsulfonylamino) phenyl methacrylamide, N- (p- (β-naphthylsulfonylamino) phenyl) methacrylamide, N- (2-methylsulfonylaminoethyl) methacrylamide, N-
(2-ethylsulfonylaminoethyl) methacrylamide, N- (2-phenylsulfonylaminoethyl) methacrylamide, N- (2-p-methylphenylsulfonylaminoethyl) methacrylamide, N- (2-α-naphthylsulfonylamino) Ethyl) methacrylamide, N
Methacrylamides such as-(2-β-naphthylsulfonylamino) ethyl methacrylamide, acrylamides having the same substituents as described above, o-aminosulfonylphenyl methacrylate, m-aminosulfonylphenyl methacrylate, p-aminosulfonylphenyl Methacrylate, o-methylaminosulfonylphenyl methacrylate, m-methylaminosulfonylphenyl methacrylate, p-methylaminosulfonylphenyl methacrylate, o-ethylaminosulfonylphenyl methacrylate, m-ethylaminosulfonylphenyl methacrylate, p-ethylaminosulfonylphenyl methacrylate, o-n-propylaminosulfonylphenyl methacrylate, mn-propylaminosulfonylphenyl methacrylate Rate, p-n-propyl-aminosulfonylphenyl methacrylate, o-i-propyl-aminosulfonylphenyl methacrylate, m-i-propyl-aminosulfonylphenyl methacrylate, o-n
-Butylaminosulfonylphenyl methacrylate, m
-N-butylaminosulfonylphenyl methacrylate, pn-butylaminosulfonylphenyl methacrylate, mi-butylaminosulfonylphenyl methacrylate, pi-butylaminosulfonylphenyl methacrylate, m-sec-butylaminosulfonylphenyl methacrylate, p -Sec-butylaminosulfonylphenyl methacrylate, mt-butylaminosulfonylphenyl methacrylate, pt-butylaminosulfonylphenyl methacrylate, o-phenylaminosulfonylphenyl methacrylate, m-phenylaminosulfonylphenyl methacrylate, p-phenylaminosulfonyl Phenyl methacrylate, m- (α
-Naphthylaminosulfonylphenyl) methacrylate, p- (α-naphthylaminosulfonylphenyl) methacrylate, m- (β-naphthylaminosulfonyl)
Phenyl methacrylate, p- (β-naphthylaminosulfonyl) phenyl methacrylate, 1- (3-aminosulfonyl) naphthyl methacrylate, 1- (3-methylaminosulfonyl) naphthyl methacrylate, 1-
(3-ethylaminosulfonyl) naphthyl methacrylate, o-methylsulfonylaminophenyl methacrylate, m-methylsulfonylaminophenyl methacrylate, p-methylsulfonylaminophenyl methacrylate, o-ethylsulfonylaminophenyl methacrylate, m-ethylsulfonylaminophenyl methacrylate, p-ethylsulfonylaminophenyl methacrylate, o-phenylsulfonylaminophenyl methacrylate, m-phenylsulfonylaminophenyl methacrylate, p-phenylsulfonylaminophenyl methacrylate, o- (p-methylphenylsulfonylamino) phenyl methacrylate, m- (p- Methylphenylsulfonylamino) phenyl methacrylate, p-
(P-methylphenylsulfonylamino) phenyl methacrylate, p- (α-naphthylsulfonylamino) phenyl methacrylate, p- (β-naphthylsulfonylamino) phenyl methacrylate, 2-methylsulfonylaminoethyl methacrylate, 2-ethylsulfonylaminoethyl methacrylate 2-phenylsulfonylaminoethyl methacrylate, 2-p-methylphenylsulfonylaminoethyl methacrylate, 2-α-naphthylsulfonylaminoethyl methacrylate, 2-β-
Examples include methacrylic acid esters such as naphthylsulfonylaminoethyl methacrylate, and acrylic acid esters having the same substituents as described above.

As the compound represented by the general formula (III), for example, N-methacryloylbenzenesulfonamide, N-
Methacryloyl-p-toluenesulfonamide, N-methacryloyl-m-toluenesulfonamide, N-methacryloyl-p-methoxyphenylsulfonamide, N
-Methacryloyl-p-butoxyphenylsulfonamide, N-methacryloyl-p-methoxyphenylsulfonamide, N-methacryloyl-α-naphthylsulfonamide, N-methacryloyl-o-butoxyphenylsulfonamide, N-acryloyl-benzenesulfonamide, N-acryloyl-p-toluenesulfonamide, N-acryloyl-o-toluenesulfonamide,
N-acryloyl-o-methoxyphenylsulfonamide, N-acryloyl-pi-amylphenylsulfonamide, N-acryloyl-o-methoxyphenylsulfonamide, N-acryloyl-α-naphthylsulfonamide, N-acryloyl-m -Butoxyphenylsulfonamide and the like.

Examples of the compound represented by the general formula (IV) include N
-(P- (p-methylphenylsulfonylamino) sulfonylphenyl) methacrylamide, N- (p- (phenylisulfonylamino) sulfonylphenyl) methacrylamide, N- (m- (p-methoxyphenylsulfonylamino) sulfonyl Phenyl) methacrylamide, N
-(O- (o-methoxyphenylsulfonylamino) sulfonylphenyl) methacrylamide, N- (p- (p
-I-butylphenylsulfonylamino) sulfonylphenyl) methacrylamide, N- (p- (α-naphthylsulfonylamino) sulfonylphenyl) methacrylamide, N- (p- (β-naphthylsulfonylamino) sulfonylphenyl) methacrylamide, Methacrylamides, acrylamides having the same substituents as above, p- (p-methylphenylsulfonylamino) sulfonylphenyl methacrylate, m- (phenylsulfonylamino) sulfonylphenyl methacrylate, p-
(P-methoxyphenylsulfonylamino) sulfonylphenyl methacrylate, p- (α-naphthylsulfonylamino) sulfonylphenyl methacrylate, o-
Methacrylic acid esters such as (p-methylphenylsulfonylamino) sulfonylphenyl methacrylate, p- (mi-butylphenylsulfonylamino) sulfonylphenyl) methacrylate, p- (β-naphthylsulfonylamino) sulfonylphenyl methacrylate; And acrylates having the same substituents.

Examples of the compounds represented by the general formulas (V) to (XI) include, for example, p-aminosulfonylstyrene, p-aminosulfonyl-α-methylstyrene, p-aminosulfonylphenyl allyl ether, p- (N-methylaminosulfonyl) Phenyl allyl ether, methylsulfonylaminoacetic acid vinyl ester, phenylsulfonylaminoacetic acid vinyl ester, methylsulfonylaminoacetic acid allyl ester, phenylsulfonylaminoacetic acid allyl ester, p-methylsulfonylaminophenyl allyl ether, p- (N-acetylaminosulfonyl) styrene,
p-styrylmethylsulfonylamide, p-ethylsulfonylaminostyrene, p-styrylphenylimide,
Examples include p-styrylethylimide, maleimide, and methylmaleimide.

The compound having an —SO ₂ —NH— bond and / or a —CO—NH—CO— bond preferably used in the present invention includes one or more —SO ₂ —NH— bonds and / or —CO -NH-C
A homopolymer of a compound represented by the above general formulas (I) to (XI) or a copolymer of two or more compounds having an O-bond and one or more polymerizable unsaturated bonds; some, but preferably has one or more polymerizable unsaturated bond, and copolymers of one or more -SO ₂ -NH- bonds and / or -CO-NH-CO- contains no binding compound It is.

Examples of such a compound containing a polymerizable unsaturated bond and not containing a sulfonamide or a -CO-NH-CO- bond include acrylic acid, methacrylic acid, acrylates, acrylamides, and methacrylates. , Methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonic esters and the like, having a polymerizable unsaturated bond. Specifically, for example, acrylates such as alkyl (the alkyl group has 1 to 10 carbon atoms)
Acrylates (e.g., 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 monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc., aryl acrylate (for example, , Phenyl acrylate, etc.): methacrylic esters, for example, alkyl (alkyl having 1 to 10 carbon atoms) Preferably) methacrylate (e.g., methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 4-hydroxybutyl methacrylate, 5
-Hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.), aryl methacrylate (for example,
Phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.): acrylamides, for example, acrylamide, N-alkylacrylamide (the alkyl group having 1 to 1 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, t-butyl group, heptyl group, octyl group, cyclohexyl group, benzyl group, hydroxyethyl group, etc.), N-arylacrylamide (as the aryl group, for example, phenyl group, tolyl group, nitrophenyl group, naphthyl group) ,
And a hydroxyphenyl group. ), N, N-dialkylacrylamide (an alkyl group having 1 carbon atom
To 10 such as a methyl group, an ethyl group, a butyl group, an isobutyl group, an ethylhexyl group and a cyclohexyl group. ), N, N-diarylacrylamide (aryl groups include, for example, phenyl group), N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N -Acetylacrylamide and the like: methacrylamides, for example, methacrylamide, N-alkylmethacrylamide, (the alkyl group has 1 carbon atom
To 10, such as a methyl group, an ethyl group, a t-butyl group, an ethylhexyl group, a hydroxyethyl group, and a cyclohexyl group. ), N-arylmethacrylamide (an aryl group includes a phenyl group and the like),
N, N-dialkylmethacrylamide (an alkyl group includes an ethyl group, a propyl group, a butyl group, etc.),
N, N-diaryl methacrylamide (an aryl group includes a phenyl group, etc.), N-hydroxyethyl-N-methyl methacrylamide, N-methyl-N-phenyl methacrylamide, N-ethyl-N-phenyl methacryl Amides and the like: allyl compounds such as allyl esters (for example, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate,
Allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate), allyloxyethanol, etc .:
Vinyl ethers such as alkyl vinyl ethers (for example, hexyl vinyl ether, octyl vinyl ether, decyl 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, etc.), vinyl aryl ether (for example,
Vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthranyl ether, etc.): vinyl esters such as vinyl butyrate, vinyl isobutyrate, and vinyl trimethyl Acetate, vinyl diethyl acetate, vinyl barate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl phenyl acetate, vinyl aceto acetate, vinyl lactate,
Vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate and the like: styrenes such as styrene, alkyl styrene (for example, methyl styrene, Dimethylstyrene, trimethylstyrene, ethylstyrene,
Diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, p- (p-hydroxybenzoyloxymethyl) styrene, etc. ), Hydroxystyrene, alkoxystyrene (eg, methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.), halogenated styrene (eg, chlorostyrene, dichlorostyrene, trichlorostyrene,
Tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.): Crotonic esters,
For example, alkyl crotonates (eg, butyl crotonate, hexyl crotonate, glycerin monocrotonate, etc.): dialkyl itaconates (eg, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.): maleic acid or fumaric acid Dialkyls (for example, dimethyl maleate, dibutyl fumarate, etc.): Acronitrile, methacrylonitrile and the like.

Of these low molecular weight compounds having a polymerizable unsaturated bond, methacrylic esters, acrylates, methacrylamides, acrylamides, acrylotrile, methacrylonitrile, methacrylic acid, acrylic acid are preferably used. It is.

Copolymers of one or more of these compounds having a polymerizable unsaturated bond and one or more of compounds having a sulfonamide group and having a polymerizable unsaturated bond include a block form, a random form, and a graph form. And the body can be used.

In these copolymers, sulfonamide or CO-NH-
The compound (structural unit) containing a CO-bond is 5 mol% based on all the compounds (structural units) constituting the copolymer.
The content is preferably as described above, and more preferably from 10 to 90 mol%.

As a solvent used when synthesizing such a copolymer, for example, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxyethyl acetate Methoxy-2-propanol, 1-
Methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate, ethyl lactate and the like.

These solvents are used alone or in combination of two or more.

Also, -SO ₂ -NH- or -CO-NH-CO in the present invention
As the compound containing a bond, a polyurethane resin and a polystyrene resin are preferably used.

Such a polyurethane resin is preferably a polyurethane resin having, as a basic skeleton, a reaction product of a diisocyanate compound and a diol compound containing a sulfonamide or a -CONHCO- bond having at least one H atom bonded to N. is there.

Specific examples of the diisocyanate compound suitably used in the present invention include the following.

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,
Aromatic diisocyanate compounds such as 3,3'-dimethylbiphenyl-4,4'-diisocyanate; hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate, etc. Aliphatic diisocyanate compounds such as
Alicyclic diisocyanates such as isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, and 1,3- (isocyanatomethyl) cyclohexane; Isocyanate compounds; diisocyanate compounds which are reaction products of diols and diisocyanates, such as adducts of 1 mol of 1,3-butylene glycol and 2 mol of tolylene diisocyanate, and the like.

On the other hand, specific examples of the diol compound containing a sulfonamide or a -CONHCO- bond in which at least one H atom is bonded to N include those shown below.

That is, p- (1,1-dihydroxymethylethylcarbonylamino) benzenesulfonamide, N-ethyl form of p- (1,1-dihydroxymethylethylcarbonylamino) benzenesulfonamide, N- (m-methylsulfonylaminophenyl) ) -2,2-Dihydroxymethylpropanamide, N- (p-methylsulfonylaminophenyl) -2,2-dihydroxymethylpropanamide, N-
(M-ethylsulfonylaminophenyl) -2,2-dihydroxymethylpropanamide, N- (P-ethylsulfonylaminophenyl) -2,2-dihydroxymethylpropanamide, N- (2,2- (dihydroxyethylaminocarbonyl) ) Ethyl) methanesulfonamide, N-
(2,2- (dihydroxyethylaminocarbonyl) ethylbenzenesulfonamide, N- (2,2- (dihydroxyethylaminocarbonyl) ethyl-p-toluenesulfonamide, etc.).

These sulfonamides or diol compounds containing -CONHCO- bonds can be used alone or in combination of two or more.

Further, without a sulfonamide or -CONHCO- bond,
A diol compound which may have another substituent which does not react with the isocyanate may be used in combination.

As such a diol compound, specifically, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, 1,3-butylene glycol, 1,6-hexanediol, 2-butene-1,4-diol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-bis-β-hydroxyethoxycyclohexane, cyclohexanedimethanol, tricyclo Decane 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-
Xylylenedicarbamate, bis (2-hydroxyethyl) isophthalate, 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 and the like can be mentioned.

The polyurethane resin is synthesized by adding the known diisocyanate compound and the diol compound to an aprotic solvent, adding a known catalyst having an activity corresponding to the respective reactivity, and heating. The molar ratio of the diisocyanate and the diol compound used is preferably 0.8: 1 to 1.2: 1, and when the isocyanate group remains at the polymer terminal, the isocyanate is finally treated with an alcohol or an amine to obtain an isocyanate group. It is synthesized in a form in which no naat group remains.

In the present invention, the —SO ₂ —NH— bond and / or The molecular weight of the compound having a bond is preferably a weight average.
It is 1,000 or more, and the number average is 500 or more. Preferably, the weight average is in the range of 2,000 to 300,000, and the number average is 1,000 to
The range is 250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, and particularly preferably 1.1 to 1
It is in the range of 0.

Also, -SO ₂ -NH- bond and / or in the present invention When the compound having a bond is a polymer compound, it may contain an unreacted monomer. In this case, the proportion of the monomer in the polymer compound is desirably 15% by weight or less.

The quinodiazide sulfonyl halide used in the present invention is preferably 1,2-naphthoquinone-2-diazide-5.
-(Or -4-) sulfonyl chloride.

—SO ₂ —NH— bonds and / or The compound having a bond can be used as one component of the photosensitive composition of the present invention by subjecting it to a condensation reaction with quinonediazidosulfonyl chloride. Such a condensation reaction can be performed by performing a dehydrochlorination condensation reaction in the presence of a dehydrochlorination agent. This reaction proceeds in an aqueous solvent or an organic solvent as long as it is in the presence of a dehydrochlorinating agent. In an aqueous solvent, lithium hydroxide, sodium hydroxide, potassium hydroxide,
Sodium carbonate, potassium carbonate and the like are preferred. When the reaction is carried out in an organic solvent, examples of the organic solvent having no OH group, for example, diethyl ether, diisopropyl ether, acetone, dichloromethane, chloroform,
Preferred are carbon chloride, tetrahydrofuran, dioxane, ethyl acetate, benzene, toluene, acetonitrile and the like.

Pyridine, diethylamine,
Preferred are triethylamine, N, N-dimethylaniline, N, N-diethylaniline, p- (N, N-dimethylamino) pyridine and the like.

Condensation reaction, -SO ₂ -NH- bond and / or Quinonediazidesulfonic acid chloride is added in an amount of 0.1 equivalent to 1 equivalent of the group that undergoes a condensation reaction contained in the compound containing a bond.
It is preferable to use 05 to 1.5 equivalents and 0.2 to 3 equivalents of a dehydrochlorinating agent, and the reaction temperature is preferably 10 to 40 ° C.

Incidentally, -SO ₂ -NH- bond and / or in the present invention When a compound having a bond, in which the quinonediazide sulfonic acid chloride is a condensation reaction, the former reactive group -SO ₂ -NH-
And Not limited to For example, if a phenolic hydroxyl group is present in the former compound, the compound of the present invention may be synthesized by a condensation reaction between the group and quinonediazidesulfonic acid chloride. Further, the obtained quinonediazide compound has a quinonediazide group introduction rate (—SO ₂ —NH—, The quinonediazidesulfonic acid chloride condensation rate with respect to an acidic group such as phenolic -OH) is preferably at least 3 mol%, particularly preferably from 15 mol% to
99 mol%.

The condensation reaction product (quinonediazide compound) of the present invention may be used alone or as a mixture. The content of these quinonediazide compounds contained in the photosensitive composition is about 5 to 95% by weight, preferably about 10 to 85% by weight.
%, Particularly preferred is 30 to 60% by weight.

In the photosensitive composition of the present invention, a known o-naphthoquinonediazide compound can be used in addition to the compound of the present invention as the photosensitive compound acting in a positive manner.

As the known o-naphthoquinonediazide compound used in the present invention, an ester of 1,2-diazonaphthoquinonesulfonic acid chloride and a pyrogallol-acetone resin described in JP-B-43-28403 is preferable. Other suitable o-quinonediazide compounds include the esters of 1,2-diazonaphthoquinonesulfonic acid chloride and phenol-formaldehyde resin described in U.S. Pat. Nos. 3,046,120 and 3,188,210. Other useful o-naphthoquinonediazide compounds have been reported and are known in numerous patents. For example, JP-A-47-5303, JP-A-48-63802, JP-A-48-63803
No. 48-96575, No. 49-38701, No. 48-13354
No., Japanese Patent Publication No. 37-18015, No. 41-11222, No. 45-9610
No. 49-17481, U.S. Pat.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,
No. 602, No. 1,251,345, No. 1,267,005, No. 1,32
No. 9,888, No. 1,330,932, German Patent No. 854,890 and the like can be mentioned.

A particularly preferred known o-naphthoquinonediazide compound in the present invention is a compound 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, JP-A-58-150948,
No. 58-203434, No. 59-165053, No. 60-121445, No. 60-
134235, 60-163043, 61-118744, 62-10645
No. 62-10646, No. 62-153950, No. 62-178562, Japanese Patent Application No. 62-233292, U.S. Pat.No. 3,102,809, No. 3,126,
No. 281, 3,130,047, 3,148,983, 3,18
Nos. 4,310, 3,188,210, and 4,639,406, etc., and those described in each gazette or specification can be mentioned.

When synthesizing these o-naphthoquinonediazide compounds, 1,2-diazonaphthoquinonesulfonic acid chloride is used in an amount of 0.2 to 0.2 to the hydroxyl group of the polyhydroxy compound.
The reaction is preferably carried out at 1.2 equivalents, more preferably at 0.3 to 1.0 equivalent.

The resulting o-naphthoquinonediazide compound is 1,2-
A mixture of diazonaphthoquinone sulfonic acid ester groups having various positions and introduced amounts is different, and the ratio of the compound in which all the hydroxyl groups are converted by 1,2-diazonaphthoquinone sulfonic acid ester to the mixture (esterification ratio) Is preferably 5 mol% or more, and more preferably 20 to 99 mol%.

Examples of known positive-acting photosensitive compounds other than o-naphthoquinonediazide compounds include, for example,
Polymers having orthonitrocarbinol ester groups described in US Pat. No. 2,696 can also be used in the present invention.

Further, a combination of a compound generating an acid by photolysis and a compound having a -CO-C group or a -CO-Si group dissociated by the acid can also be used in the present invention.

For example, a combination of a compound capable of generating an acid by photolysis and an acetal or an O, N-acetal compound (JP-A-48-8900)
No. 3), a combination with an orthoester or amide acetal compound (JP-A-51-120714), and a combination with a polymer having an acetal or ketal group in the main chain (JP-A-53-120).
-133429,), a combination with an enol ether compound (JP-A-55-12995), a combination with an N-acylimino carbon compound (JP-A-55-126236), a polymer having an orthoester group in the main chain (JP-A-56-17345)
No.), a combination with a silyl ester compound (JP-A-60-102)
No. 47) and a combination with a silyl ether compound (JP-A No.
60-37549) and JP-A-60-121446).

The positive-working photosensitive component in the photosensitive composition of the present invention includes the above-mentioned condensation reaction product of the present invention and the above-mentioned known positive-working photosensitive compound (including the combination system as described above). 5) to 95% by weight, preferably 10 to 85% by weight, particularly preferably 30 to 60% by weight, based on the total amount of the positive photosensitive component. The amount is comprised between 10 and 90% by weight, preferably between 30 and 70% by weight.

In the compositions of the present invention, -SO ₂ -NH- in the present invention
Binding and / or The compound having a bond itself can be contained. In particular, the compound is preferably a polymer having a weight average molecular weight of 1,000 or more, more preferably 3,000 or more.

In the photosensitive composition of the present invention, phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin, phenol / cresol (m-, p) -Or m- / p-
A known alkali-soluble polymer compound such as a cresol formaldehyde resin such as a mixed formaldehyde resin, a phenol-modified xylene resin, polyhydroxystyrene, and polyhalogenated hydroxystyrene can be contained. These alkali-soluble polymer compounds preferably have a weight average molecular weight of 500 to 20,000 and a number average molecular weight of 200 to 60,000.

Such an alkaline water-soluble polymer compound is used in the total composition.
It is used in an addition amount of 70% by weight or less.

Further, as described in U.S. Pat. No. 4,123,279, a condensate of formaldehyde with a phenol having an alkyl group having 3 to 8 carbon atoms as a substituent, such as a t-butylphenol formaldehyde resin or an octylphenol formaldehyde resin. It is preferable to use in combination from the viewpoint of improving the oil sensitivity of the image.

In the photosensitive composition of the present invention, a cyclic acid anhydride for enhancing sensitivity, a printing-out agent for obtaining a visible image immediately after exposure, and a dye or other filler as an image coloring agent can be added. . U.S. Patent No.
4,115,128 Pat phthalic anhydride as described in, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-oxy - [delta ⁴ - tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloro Maleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride and the like can be mentioned. Sensitivity can be increased up to about three times by including these cyclic acid anhydrides in an amount of 1 to 15% by weight in the total composition.

As a printing-out agent for obtaining a visible image immediately after exposure, a combination of a photosensitive compound that releases an acid upon exposure and an organic dye capable of forming a salt can be exemplified. Specifically, a combination of o-naphthoquinonediazide-4-sulfonic acid halogenide and a salt-forming organic dye described in JP-A-50-36209 and JP-A-53-8128, -36223, 54-74728, 60-3626, 61-1437
Combinations of trihalomethyl compounds and salt-forming organic dyes described in Nos. 48, 61-151644 and 63-58440 can be exemplified. Other dyes besides the above-mentioned salt-forming organic dyes can be used as image coloring agents. 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 (all manufactured by Orient Chemical Co., Ltd.), Victoria Pure Blue, crystal violet (CI142555), methyl Violet (CI42535),
Rhodamine B (CI45170B), Malachite green (CI42
000), methylene blue (CI52015) and the like. Dyes described in JP-A-62-293247 are particularly preferred.

In the photosensitive composition of the present invention, acids having a pKa of 3.0 or less, for example, sulfonic acids, so as to enhance the developability and to prevent additives such as a dye in the photosensitive composition from remaining in the exposed portion after development.
Sulfinic acids, alkyl sulfates, phosphonic acids, and phosphinic acids can be added.

Specific examples include naphthalene-2-sulfonic acid,
Naphthalene-1-sulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, mesitylenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, m-benzenedisulfonic acid, cyclohexylsulfamic acid, p-toluidine-2- Sulfonic acid, pyridine-3-sulfonic acid, phenyl J acid, p-toluenesulfinic acid, benzylsulfinic acid, methanesulfinic acid, phenylphosphonic acid, methylphosphonic acid, chloromethylphosphonic acid, dimethylphosphinic acid, diphenyl phosphate, phosphorous acid Examples include diphenyl and ethyl sulfate. In addition, trifluoroacetic acid, trichloroacetic acid, 2,
Carboxylic acids with low pKa, such as 6-dichlorobenzoic acid and picric acid, and phenols can also be used. These acids are used alone or as a mixture of two or more, and are used in an amount of 0.05 to 5% by weight, preferably 0.2 to
It is used in the range of ２2% by weight.

The photosensitive composition of the present invention is dissolved in a solvent that dissolves each of the above components to form a coating solution, and is coated on a support. As the solvent used here, ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, toluene , Ethyl acetate, methyl lactate, ethyl lactate, dimethylsulfoxide, dimethylacetamide, dimethylformamide, water, N-methylpyrrolidone, tetrahydrofurfuryl alcohol, acetone, diacetone alcohol, methanol, ethanol, isopropanol, diethylene glycol dimethyl ether, and the like. Are used alone or as a mixture.

The concentration of the photosensitive composition in the coating solution is 2 to 50% by weight. In addition, the amount of application varies depending on the application, for example, generally speaking about a photosensitive lithographic printing plate as a solid content of 0.5 to
3.0 g / m ² is preferred. As the amount of coating decreases, the photosensitivity increases, but the physical properties of the photosensitive film deteriorate.

In the composition of the present invention, a surfactant for improving coating properties, for example, a fluorine-based surfactant described in JP-A-62-170950 can be added.
A preferable addition amount is 0.001 to 1% by weight, more preferably 0.05 to 0.5% by weight of the whole photosensitive composition.

When a lithographic printing plate is produced using the photosensitive composition of the present invention, the support is preferably an aluminum plate. The aluminum plate includes a pure aluminum plate and an aluminum alloy plate. Various aluminum alloys can be used, and for example, an alloy of aluminum with a metal such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, and nickel is used. These compositions also contain some negligible amount of impurities in addition to some iron and titanium.

The aluminum plate is subjected to a surface treatment as required. For example, surface treatment such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, or the like, or anodic oxidation treatment is preferably performed. Further, as described in British Patent No. 851,819, an aluminum plate which is grained and then immersed in an aqueous solution of sodium silicate, US Pat. No. 3,181,461
As described in the specification, an aluminum plate that has been subjected to anodizing treatment and then immersed in an aqueous solution of an alkali metal silicate is also preferably used. The anodizing treatment is, for example, an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, or boric acid, or oxalic acid, an organic acid such as sulfamic acid, or an aqueous or non-aqueous solution of a salt thereof alone or in combination of two or more. This is carried out by flowing a current in an electric field solution using an aluminum plate as an anode.

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

These hydrophilic treatments are performed not only to make the surface of the support hydrophilic, but also to prevent harmful reactions with the photosensitive composition provided thereon and to improve the adhesion with the photosensitive layer. It is done to improve.

Prior to graining the aluminum plate, if necessary, the surface may be subjected to a pretreatment to remove rolling oil on the surface and to expose a clean aluminum surface. For the former, solvents such as trichloroethylene, surfactants and the like are used. For the latter, a method using an alkali etching agent such as sodium hydroxide or potassium hydroxide is widely used.

As the graining method, any of mechanical, chemical and electrochemical methods is effective. Examples of mechanical methods include a ball polishing method, a plus and polishing method, and a brush polishing method in which an aqueous dispersion of an abrasive such as pumice is rubbed with a nylon brush.
A method of immersing in a saturated aqueous solution of an aluminum salt of a mineral acid as described in JP-31187 is suitable, and as an electrochemical method, an alternating current in an acidic electrolyte such as hydrochloric acid, nitric acid or a combination thereof is used. Electrolysis is preferred. Among such surface roughening methods, in particular, a surface roughening method combining mechanical surface roughening and electrochemical surface roughening as described in Japanese Patent Application Laid-Open No. 55-137993, It is preferable because the adhesive strength to the support is strong.

The graining by the above-described method is preferably performed in a range where the center line surface roughness (Ha) of the surface of the aluminum plate is 0.3 to 1.0 μ.

The aluminum plate thus grained is washed with water and chemically etched as required.

The etching solution is usually selected from aqueous solutions of bases or acids that dissolve aluminum. In this case, a film different from aluminum derived from the etchant component must not be formed on the etched surface. Preferred examples of the etching agent include sodium hydroxide, potassium hydroxide, trisodium phosphate, disodium phosphate, tripotassium phosphate, and dipotassium phosphate as basic substances; and sulfuric acid and persulfuric acid as acidic substances. , Phosphoric acid, hydrochloric acid, and salts thereof. Metals having a lower ionization tendency than aluminum, such as salts of zinc, chromium, cobalt, nickel, and copper, are not preferred because they form unnecessary coatings on the etched surface.

It is most preferable that these etching agents are used so that the dissolution rate of the aluminum or alloy to be used is 0.3 to 40 g / m ² per one minute of immersion time, at the setting of the working concentration and the temperature, but more than this Or it may be lower.

The etching is performed by immersing the aluminum plate in the above-mentioned etching solution or by applying the etching solution to the aluminum plate, and is preferably processed so that the etching amount is in the range of 0.5 to 10 g / m ² .

As the etching agent, it is preferable to use an aqueous solution of a base because of its high etching rate. In this case, since a smut is generated, a normal desmutting process is performed. As the acid used for the desmut treatment, nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, borofluoric acid and the like are used.

The etched aluminum plate is optionally washed with water and anodized. The anodic oxidation can be performed by a method conventionally used in this field. Specifically, when a direct current or an alternating current is passed through aluminum in an aqueous solution or non-aqueous solution in which sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, or the like or a combination of two or more thereof, aluminum An anodized film can be formed on the surface of the support.

Anodizing treatment conditions vary depending on the electrolytic solution used, and thus cannot be unconditionally determined. Generally, however, the concentration of the electrolytic solution is 1 to 80% by weight, the liquid temperature is 5 to 70 ° C, and the current density is 0%. .
5-60 amps / dm ² , voltage 1-100V, electrolysis time 30 seconds-50
A range of minutes is appropriate.

Among these anodizing treatments, in particular, British Patent No. 1,41
U.S. Pat.No. 2,768,047, U.S. Pat.No. 4,211,619, U.S. Pat. The method of anodizing phosphoric acid as an electrolytic bath described in the specification is preferable.

The aluminum plate which has been roughened as described above and further anodized may be subjected to a hydrophilization treatment if necessary. Preferred examples thereof are U.S. Pat. Nos. 2,714,066 and 3,1.
Alkali metal silicates such as those disclosed in U.S. Patent No. 81,461, such as aqueous sodium silicate or potassium fluorozirconate disclosed in JP-B-36-22063 and as disclosed in U.S. Patent No. 4,153,461. There is a method of treating with polyvinyl phosphonic acid.

Further, an undercoat layer made of a water-soluble compound can be provided on the aluminum plate which has been roughened as described above, anodized, and further subjected to a hydrophilic treatment as required. Examples of such water-soluble compounds include a combination of a water-soluble metal salt and hydrophilic cellulose (for example, zinc chloride and carboxymethyl cellulose, magnesium chloride and hydroxyethyl cellulose, etc.) disclosed in JP-B-57-16349, US Polyacrylamide disclosed in Japanese Patent No. 3,511,661, polyvinylphosphonic acid disclosed in Japanese Patent Publication No. 46-35685, amino acids disclosed in JP-A-60-149491, and salts thereof (Na salt) , K salts and other alkali metal salts, ammonium salts, hydrochlorides, oxalates, acetates, phosphates, etc.), and amines having hydroxyl groups and their salts disclosed in JP-A-60-232998. Hydrochloride, oxalate, phosphate, etc.), among which amino acids and salts thereof, amines having a hydroxyl group and salts thereof are particularly preferred. Subbing layer of compound is preferably provided in the range of 1mg / m ² ~80mg / m ² in solid content.

Examples of the developer for the photosensitive composition of the present invention include sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, and tertiary ammonium phosphate. ,
Aqueous solutions of inorganic alkaline agents, such as ammonium diphosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc., are suitable, and their concentration should be 0.1 to 10% by weight, preferably 0.5 to 5% by weight. Is added to

In addition, an organic solvent such as a surfactant or alcohol can be added to the alkaline aqueous solution as needed.

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

〔The invention's effect〕

The photosensitive composition of the present invention has excellent developability when the exposed portion is used with an aqueous alkaline developer after coating, drying and image exposure, and has a wide latitude. The resulting relief image has good abrasion resistance, adhesion to the support, and treatment chemical resistance.
When used as a printing plate, many good prints are obtained.

Further, even when printing using UV ink is performed, a large number of 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 present invention is not limited thereto.

Synthesis Example 1 170.2 g (1.0%) of p-aminobenzenesulfonamide was placed in a three-necked flask equipped with a stirrer, a condenser, and a dropping funnel.
Mol) and 700 ml of tetrahydrofuran, and the mixture was stirred in an ice-water bath. 52.3 g of methacrylic acid chloride is added to this mixture.
(0.5 mol) was dropped by a dropping funnel over about 1 hour. After dropping, remove the ice-water bath, stir for 30 minutes at room temperature, and further heat to 60 ° C using an oil bath.
Stirred for hours. After completion of the reaction, the reaction mixture was poured into 3 l of water with stirring, stirred for 30 minutes, and then filtered,
A white solid of N- (p-aminosulfonylphenyl) methacrylamide was obtained. This white solid could be purified by recrystallization from a mixed solvent of water-acetone (yield: 39.3 g).

9.72 g (0.0408 mol) of N- (p-aminosulfonylphenyl) methacrylamide thus obtained, 7.93 g (0.0792 mol) of methyl methacrylate, and 50 ml of N, N-dimethylformamide were equipped with a stirrer and a condenser. The mixture was placed in a 200-m three-necked flask and stirred while being heated to 64 ° C. in a hot water bath. 0.246 g of α, α'-azobisisobutyronitrile was added to this mixture, and the mixture was stirred for 5 hours under a nitrogen stream while maintaining the temperature at 64 ° C. After completion of the reaction, the reaction mixture was poured into 2 liters of water with stirring, stirred for 30 minutes, and then filtered and dried.
16 g of a white solid was obtained. The weight average molecular weight (polystyrene standard) of this polymer compound was measured by gel permeation chromatography and found to be 49,000 (polymer compound (a) in Table 1 below).

13.7 g of polymer compound (a) and 1,2-naphthoquinone-2
N, N-dimethylacetamide (100 ml) was added to diazide-5-sulfonyl chloride (9.1 g), and the reaction mixture was stirred for 3 hours.
While cooling so that it does not reach 0 ° C or higher, triethylamine
A solution of 4.0 g dissolved in 20 ml of N, N-dimethylacetamide was added dropwise over 30 minutes. After further reacting at 20-30 ° C. for 1 hour, the reaction solution was poured into 300 ml of water, and the precipitate was collected by filtration.
This was dried to obtain 16 g of a condensation product (A).

Synthesis Example 2 31.0 g (0.36 mol) of methacrylic acid, 39.1 g (0.36 mol) of ethyl chloroformate and 200 ml of acetonitrile were put into a 500 ml three-necked flask equipped with a stirrer, a condenser and a dropping funnel, and stirred in an ice water bath. Triethylamine is added to this mixture.
36.4 g (0.36 mol) was dropped by a dropping funnel over about 1 hour. After the addition, the ice-water bath was removed, and the mixture was stirred at room temperature for minutes, and an oil bath was attached.

To this reaction mixture was added 51.7 g (0.30 mol) of p-aminobenzenesulfonamide, and the mixture was stirred for 1 hour while warming to 70 ° C in an oil bath. After completion of the reaction, this mixture was poured into water 1 with stirring, and stirred for 30 minutes. The solid was collected by filtration, slurried in 500 ml of water, filtered and dried to obtain a white solid of N- (p-aminosulfonylphenyl) methacrylamide (yield 46.9 g).

Next, 4.61 g (0.0192 mol) of N- (p-aminosulfonylphenyl) methacrylamide, 2.94 g (0.0258 mol) of ethyl methacrylate, 0.80 g of acrylonitrile were placed in a 200 ml three-necked flask equipped with a stirrer, a condenser, and a dropping funnel. (0.
015 mol) and 20 g of N, N-dimethylacetamide.
The mixture was stirred while being heated to 65 ° C. by a hot water bath. V-65 [2,2'-azobis- (2,4-dimethylvalero)
Nitrile] (manufactured by Wako Pure Chemical Industries, Ltd.) (0.15 g) was added, and the mixture was stirred under a nitrogen stream for 2 hours while maintaining the temperature at 65 ° C. The reaction mixture was further charged with N- (p-aminosulfonylphenyl) methacrylamide 4.61 g, ethyl methacrylate 2.94 g, acrylonitrile 0.80 g, N, N-dimethylacetamide and V-65.
0.15 g of the mixture was added dropwise from the dropping funnel over 2 hours. After completion of the dropwise addition, the mixture was further stirred at 65 ° C. for 2 hours. After the completion of the reaction, 40 g of methanol was added, and the mixture was cooled.
After stirring for 15 minutes, the mixture was filtered and dried to obtain 15 g of a white solid. The weight average molecular weight of this polymer compound (polystyrene standard) was measured by gel permeation chromatography and found to be 53,000 (polymer compound (b) in Table 1). Next, the polymer compound (b) was reacted with 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride in the same manner as in Synthesis Example 1 to obtain a condensation product (B).

Synthesis Examples 3 and 4 Polymer compounds (c) and (d) shown in Table 1 were synthesized in the same manner as in Synthesis Example 1 or 2. The weight average molecular weight (polystyrene standard) of these polymer compounds was 9,000 to 80,000. Using these polymer compounds (c) and (d), 1,2 was prepared in the same manner as in Synthesis Example 1.
-Naphthoquinone-2-diazide-4-sulfonyl chloride to give condensation products (C) and (D), respectively.

Synthesis Example 5 N-methacrylbenzenesulfonamide 10.0 g (0.044
Mol), 4.46 g (0.044 mol) of methyl methacrylate
In 22 ml of methoxyethanol, copolymerization was carried out using 0.0213 g of V-65 [2,2'-azobis- (2,4-dimethylvalero) nitrile] as an initiator. After stirring at 60 ° C for 7 hours, 60 ml of 2-methoxyethanol was added, and the mixture was reprecipitated in 2 l of water. 100 ml of the obtained polymer in tetrahydrofuran
And then reprecipitated in 1.5 l of methanol to obtain 10.2 g of a polymer compound (e) shown in Table 1 (w = 2
00,000, 70% yield). The constituent molar ratio was determined from ¹ H-NMR.

Next, using this polymer compound (e), 1,2-naphthoquinone-2-diazide-5 was prepared in the same manner as in Synthesis Example 1.
Reaction with sulfonyl chloride gave condensation product (E).

In addition, the condensation products (A)-shown in Synthesis Examples 1 to 5
(E) shows that the rate of introduction of the naphthoquinonediazide group was -SO ₂ NH ₂ group or-
CONH-SO ₂ - it ranged all 40% to 80% with respect to the base.

Examples 1 to 5 and Comparative Examples 1 to 4 An aluminum plate having a thickness of 0.24 mm was
The surface was grained using a pumicestone-water suspension of a mesh, and then thoroughly washed with water to prepare a substrate [I]. The substrate [I] was immersed in 10% sodium hydroxide at 70 ° C. for 20 seconds, etched, washed with running water, neutralized and washed with 20% HNO ₃ , washed with water, and subjected to sine wave at 12.7 V. The substrate was subjected to electrolytic surface roughening treatment in a 0.7% nitric acid aqueous solution at an electric quantity of 400 coulomb / dm ² using the alternating waveform current, and then washed with water to prepare a substrate [II].

The substrate [II] was treated in a 10% aqueous sodium hydroxide solution such that the amount of the surface dissolved was 0.9 g / m ² . 20% after washing with water
After neutralizing in a nitric acid solution, washing and desmutting,
Anodization was performed in an 18% aqueous sulfuric acid solution so that the amount of the oxide film was 3 g / m ² .

Next, in a photosensitive solution [A] having the following composition,
As shown in the table, five kinds of photosensitive solutions [A] -1 to 5 in which the kind of the quinonediazide compound (condensation product) of the present invention was changed.
[A] -5 was prepared. As a comparative example, photosensitive solution [A]
In place of the quinonediazide compound of the present invention, 2,3,4
-Trihydroxybenzophenone and naphthoquinone-1,2
Photosensitive solution [A] -6 using an esterified product with -diazide-5-sulfonyl chloride (esterification ratio; 60 mol%)
Photosensitive solution [A] -7 and [A] -8 using polymer compound (a) and polymer compound (e) shown in Table 1 in place of quinonediazide compound of the present invention; quinonediazide of the present invention A photosensitive solution [A] -9 using an m-cresol-formaldehyde resin (weight average molecular weight 4,000) instead of the compound was prepared. These photosensitive solutions are applied to a substrate [I
I] and dried at 100 ° C. for 2 minutes to produce photosensitive lithographic printing plates [A] -1 to [A] -9. The coating amount was 2.3 g / m ² in dry weight.

Photosensitive solution [A]-Esterified product of 2,3,4-trihydroxybenzophenone and naphthoquinone-1,2-diazido-5-sulfonyl chloride (esterification rate: 60 mol) 0.45 g-Quinone diazide compound of the present invention (Condensation product: Table 2) 0.60 g m-cresol-formaldehyde resin (weight average molecular weight: 4,000) 0.40 g Naphthalene-1-sulfonic acid 0.01 g 2- (p-methoxyphenyl) -4,6- Bis (trichloromethyl) -s-triazine 0.02 g ・ Naphthoquinone-1,2-diazide-4-sulfonyl chloride 0.01 g ・ Victoria Pure-BOH (dye manufactured by Hodogaya Chemical Co., Ltd.) 0.015 g ・ MegaFac F-177 (Fluorinated surfactant manufactured by Dainippon Ink and Chemicals, Inc.) 0.004 g ・ Dimethylacetamide 4 g ・ 1-Methoxy-2-propanol 9 g ・ Methyl ethyl ketone 7 g Photosensitivity On the photosensitive layers of the lithographic printing plates [A] -1 to [A] -9, a positive transparent original image of a line image and a halftone image was adhered, and exposure was performed from a distance of 1 m with a 2 kW metal halide lamp.
The exposed printing plate was immersed and developed in a developer A having the following composition at 25 ° C. for 60 seconds.

Composition: · Si ₂ / Na ₂ O to examine the (molar ratio 1.1) of sodium silicate 2 g · sodium ethylenediaminetetraacetate · 4H ₂ O 0.1g · Water 97.9g printing durability, and printing using UV ink, The comparison was made by examining the number of prints on which normal prints could be printed. The chemical resistance was evaluated by immersion in a chemical and examining the erosion of the image area.

Further, in order to examine the development latitude, development was performed while changing the temperature of the developer, and the easiness of the change in the number of solid steps of the step wedge was examined. Table 2 shows the results.

As is evident from Table 2, the photosensitive lithographic printing plate using the photosensitive composition of the present invention had extremely good UV ink printing durability, chemical resistance and development latitude.

Continuation of the front page (56) References JP-A-63-226441 (JP, A) JP-A-64-4672 (JP, A) JP-A-64-4671 (JP, A) JP-A-63-80254 (JP) , A)

Claims (1)

(57) [Claims] 1. A photosensitive composition comprising a condensation reaction product of a polymer compound having a —SO ₂ —NH— bond in a side chain and quinonediazide sulfonyl halide.