JP3335015B2 - Positive photosensitive composition and method for producing positive photosensitive lithographic printing plate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photosensitive composition suitable for producing a lithographic printing plate, an IC circuit or a photomask and a method for producing a positive photosensitive lithographic printing plate.
More specifically, a positive-working photosensitive composition and a positive-working photosensitive lithographic printing plate having a good development latitude, comprising a positive-working photosensitive compound and a polymer compound having excellent abrasion resistance and chemical resistance. And a method for producing the same.

[0002]

2. Description of the Related Art A conventionally known positive planographic printing plate comprises a photosensitive composition using an o-naphthoquinonediazide compound as a photosensitive material and a novolak-type phenol resin as a binder. This lithographic printing plate, due to the nature of the novolak type phenolic resin in the photosensitive composition,
The poor adhesion to the substrate, the brittleness of the film and the poor abrasion resistance result in insufficient printing durability when used in a lithographic printing plate. Further, it is known that the chemical resistance is poor, and particularly when UV ink is used, the printing durability of the lithographic printing plate is extremely insufficient.

In order to solve these problems, various polymer compounds have been studied as binders. For example, Japanese Unexamined Patent Publication (Kokai) No. 2-866 discloses the above conventional problems,
In order to solve the printing durability of V ink, a photosensitive composition containing a polymer compound having a sulfonamide group as a binder is disclosed.

[0004]

However, the technology described in the above-mentioned Japanese Patent Application Laid-Open No. 2-866 has a tolerance (a so-called development latitude) with respect to fluctuations in development time, temperature and developer concentration. There is a problem such as narrow. An object of the present invention is to provide a method for producing a photosensitive lithographic printing plate which provides a lithographic printing plate having excellent chemical resistance and having a high printing durability even when printing with a UV ink without performing a burning treatment, and a photosensitive composition. It is to provide things.

It is a further object of the present invention to provide a method for producing a photosensitive lithographic printing plate having a good developing latitude and a photosensitive composition. Furthermore, the object of the present invention is excellent in abrasion resistance, good adhesion to the substrate, giving a flexible film,
An object of the present invention is to provide a method for producing a photosensitive lithographic printing plate that provides a lithographic printing plate having high printing durability, and a photosensitive composition.

[0006]

The object of the present invention can be achieved by the following constitutions (1) and (2). (1) A method for producing a positive photosensitive lithographic printing plate, comprising applying a coating solution containing the following (a) to (d) on a support and drying the coating solution. (A) a polymer compound having a sulfonamide group and being water-insoluble and soluble in an alkaline aqueous solution; (b) an alkali-soluble novolak resin; (c) a photosensitive compound acting positively; (d) a cyclic lactone; And (d).

(A) a polymer compound having a sulfonamide group and being water-insoluble and soluble in an alkaline aqueous solution; (b) an alkali-soluble novolak resin; (c) a photosensitive compound acting positively; and (d) a cyclic lactone.

That is, the present invention relates to the above components (a) to (d)
To solve traditional problems, especially UV
The development latitude can be improved in addition to the ink printing durability. The present invention achieves both the printing durability of UV ink, which is a feature of the polymer compound binder having a sulfonamide group, and the good development latitude, which is a feature of the effect of a novolak resin binder. However, the effect of the present invention is not exhibited only by using a polymer compound containing a sulfonamide group and a novolak resin in combination. By combining the constituent features of the present invention,
The development latitude is remarkably good, and a high UV ink printing durability is obtained.

Although the detailed mechanism is unknown, the solubility of the high molecular compound having a sulfonamide group of the cyclic lactone in the novolak resin is different from that of the cyclic lactone, and the cyclic lactone has a high boiling point. When dried,
It is considered that a change in the state in the photosensitive layer, for example, microscopic phase separation between resins occurs, and a photosensitive film in which the favorable properties of both binders are complementary can be obtained.

The (a) polymer compound having a sulfonamide group and being water-insoluble and soluble in an aqueous alkaline solution used in the present invention contains a --SO ₂ --NH-- bond in the side chain or main chain. A high molecular compound, preferably-
It is a polymer compound containing an SO ₂ —NH— bond. The (a) polymer compound having a sulfonamide group and being water-insoluble and soluble in an alkaline aqueous solution, which is used in the present invention, is a sulfone having at least one H atom bonded to one or more N atoms in one molecule. It can be obtained by polymerizing a low-molecular compound having an amide group and one or more polymerizable unsaturated bonds in a suitable solvent using a known polymerization initiator.

In the present invention, examples of such a low molecular weight compound that is more preferably used include a compound represented by the general formula (I) or (II).

[0012]

Embedded image

In the formula, X ¹ and X ² are each -O- or-
NR ⁷ -is shown. R ¹ and R ⁴ are each —H or —CH ₃
Is shown. R ² and R ⁵ each represent a C ₁ -C ₁₂ alkylene group, cycloalkylene group, arylene group or aralkylene group which may have a substituent. R ³ represents -H, alkyl group optionally C ₁ -C ₁₂ which may have a substituent, a cycloalkyl group, an aryl group, an aralkyl group, a. R ⁶ represents a C _{1 to} C ₁₂ alkyl group, cycloalkyl group, aryl group, or aralkyl group which may have a substituent. R ⁷ represents a hydrogen atom or a C _{1 to} C ₁₂ alkyl group, cycloalkyl group, aryl group or aralkyl group which may have a substituent.

Among the low molecular weight compounds represented by the general formula (I) or (II), those particularly preferably used in the present invention are those wherein R ² and R ⁵ are each an alkylene group of C ₂ -C ₆ , An alkylene group or a phenylene group or a naphthylene group which may have a substituent, wherein R ³ is H or C ₁ to
A C ₆ alkyl group, a cycloalkyl group or an optionally substituted phenyl group or a naphthyl group, wherein R ⁶ has a C ₁ -C ₆ alkyl group, a cycloalkyl group or a substituent; A phenyl group or a naphthyl group;
A compound in which ⁷ is a hydrogen atom.

Examples of such low molecular weight compounds include N- (o-aminosulfonylphenyl) methacrylamide, N- (m-aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonylphenyl) methacrylamide, -(O-methylaminosulfonylphenyl) methacrylamide, N- (m-methylaminosulfonylphenyl) methacrylamide, N- (p-methylaminosulfonylphenyl) methacrylamide, N- (o
-Ethylaminosulfonylphenyl) methacrylamide, N- (m-ethylaminosulfonylphenyl) methacrylamide, N- (p-ethylaminosulfonylphenyl) methacrylamide, N- (on-propylaminosulfonylphenyl) methacrylamide, N- (m-
n-propylaminosulfonylphenyl) methacrylamide, N- (pn-propylaminosulfonylphenyl) methacrylamide, N- (oi-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- (p
-I-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-naphthylsulfonylaminoethyl) methacrylamide, N- (2
-Β-naphthylsulfonylaminoethyl) methacrylamides such as methacrylamide, acrylamides having the same substituents as 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, on -Propylaminosulfonylphenyl methacrylate, mn-propylaminosulfonylphenyl methacrylate , P-n-propyl-aminosulfonylphenyl methacrylate, o-i-propyl-aminosulfonylphenyl methacrylate, m-i-propyl-aminosulfonylphenyl methacrylate, o-n-butyl-aminosulfonylphenyl methacrylate, m-n-
Butylaminosulfonylphenyl methacrylate, p-
n-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-phenylaminosulfonylphenyl methacrylate, m- (α-naphthylaminosulfonyl) phenyl methacrylate, p
-(Α-naphthylaminosulfonyl) phenyl 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- Examples include methacrylates such as β-naphthylsulfonylaminoethyl methacrylate, and acrylates having the same substituents as described above.

In the present invention, another example of the low molecular weight compound having a sulfonamide group and a polymerizable unsaturated bond, which is preferably used for obtaining a polymer compound having a sulfonamide group, includes: The following general formula (III)
The compound represented by (V) is included.

[0017]

Embedded image

R ⁸ , R ¹⁰ and R ¹⁴ each represent a hydrogen atom,
It represents a halogen atom or a methyl group, and is preferably a hydrogen atom. R ⁹ represents an optionally substituted C ₁ -C ₁₂ alkylene group, cycloalkylene group, arylene group, aralkylene group, and preferably an optionally substituted methylene group, phenylene group, or naphthylene group .

R ¹¹ and R ¹⁵ each represent a single bond or an optionally substituted C ₁ -C ₁₂ alkylene group, cycloalkylene group, arylene group or aralkylene group, preferably a single bond or methylene group. . R ¹² and R ¹⁶ each represent an optionally substituted C ₁ -C ₁₂ alkylene group, cycloalkylene group, arylene group, or aralkylene group, preferably a C ₁ -C ₆ alkylene group or a substituted or unsubstituted alkylene group. Phenylene group and naphthylene group.

R ¹³ represents a hydrogen atom, an optionally substituted C ₁ -C ₁₂ alkyl group, cycloalkyl group, aryl group or aralkyl group, preferably a hydrogen atom or C
_{It represents} an alkyl group of ₁ to ₆ carbon atoms, a cycloalkyl group, a phenyl group which may be substituted, and a naphthyl group. R ¹⁷ is an alkyl group optionally C ₁ -C ₁₂ substituted, a cycloalkyl group, an aryl group, an aralkyl group, preferably C ₁
To C ₆ alkyl, cycloalkyl, optionally substituted phenyl, and naphthyl. Y ¹ , Y ²
Represents a single bond or —C (＝ O) —.

Specific examples of the compounds represented by the above general formulas (III) to (V) include 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, etc. is there.

The (a) polymer compound having a sulfonamide group preferably used in the present invention is a polymer compound having a sulfonamide group in which at least one H atom is bonded to N in the above molecule and a polymerizable unsaturated bond. Is a homopolymer or a copolymer of two or more low molecular compounds having a polymerizable unsaturated bond and a copolymer with one or more low molecular compounds having no sulfonamide group. Preferably, there is.

The compound containing such a polymerizable unsaturated bond and not containing a sulfonamide group includes
For example, polymerizable unsaturated selected from acrylic acid, methacrylic acid, acrylic esters, acrylamides, methacrylic esters, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotons, esters, and the like. It is a compound having a bond. Specifically, for example, acrylates, for example, alkyl (the alkyl group preferably has 1 to 10 carbon atoms) acrylate (for example, methyl acrylate,
Ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, ethylhexyl 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 acrylates (eg, phenyl acrylate): methacrylic acid esters, for example, alkyl (the alkyl group preferably has 1 to 10 carbon atoms) methacrylate (eg, 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 (eg, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.): acrylamides, for example Acrylamide, N-alkylacrylamide (the alkyl group having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group,
Examples include a heptyl group, an octyl group, a cyclohexyl group, a hydroxyethyl group and a benzyl group. ), N-arylacrylamides (for example, phenyl group, tolyl group, nitrophenyl group, naphthyl group, hydroxyphenyl group, etc.), N, N-dialkylacrylamide (for the alkyl group, carbon 1 atom
10 to, for example, a methyl group, an ethyl group, a butyl group,
Examples include an isobutyl group, an ethylhexyl group, and a cyclohexyl group. ), N, N-arylacrylamide (the aryl group includes, for example, a phenyl group),
N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide and the like: methacrylamides such as methacrylamide, N-alkylmethacrylamide (as the alkyl group Is a compound having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, t-
Examples include a butyl group, an ethylhexyl group, a hydroxyethyl group, and a cyclohexyl group. ), N-aryl methacrylamide (the aryl group includes a phenyl group and the like), N, N-dialkyl methacrylamide (the alkyl group includes an ethyl group, a propyl group and a butyl group), N, N-diaryl methacrylamide (the aryl group includes a phenyl group and the like), N-
Hydroxyethyl-N-methylmethacrylamide, N-
Methyl-N-phenylmethacrylamide, N-ethyl-
N-phenylmethacrylamide and the like: allyl compounds, for example, allyl esters (for example, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate,
Allyl acetoacetate, allyl lactate, etc., allyloxyethanol, etc .: vinyl ethers such as alkyl vinyl ethers (eg, 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 and the like, vinyl aryl ether (for example, Vini 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, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, and vinyl chloroacetate , Vinyl dichloroacetate, vinyl methoxyacetate, vinylbutoxyacetate, vinylphenylacetate, vinylacetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate, vinyl benzoate,
Vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, etc .: styrenes such as styrene, alkyl styrene (eg, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl Styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxy methyl styrene, acetoxy methyl styrene, etc., alkoxy styrene (for example, methoxy styrene,
4-methoxy-3-methylstyrene, dimethoxystyrene, etc.), halogen styrene (for example, 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 (for example, butyl crotonate, hexyl crotonate, glycerin monochrome) Dialkyl itaconate (eg, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.): dialkyl maleate or fumaric acid (eg, dimethyl maleate, dibutyl fumarate, etc.): acronitrile, methacryloyl There are nitriles and the like.

Of these compounds having a polymerizable unsaturated bond, methacrylic esters, acrylic esters, methacrylamides, acrylamides, acrylonitrile, methacrylonitrile, methacrylic acid, acrylic Is an acid. One or more of these polymerizable unsaturated bond-containing compounds and one or more copolymers of a compound containing a sulfonamide group and having a polymerizable unsaturated bond may be a block, a random, or a graft. Etc. can be used.

In these copolymers, the constituent unit containing a sulfonamide group is preferably contained in an amount of at least 5 mol% based on all constituent units constituting the copolymer.
More preferably, the content is 0 to 90 mol%. Examples of the solvent used for synthesizing the polymer compound (a) having a sulfonamide group and being soluble in a water-insoluble and alkaline aqueous solution used in the present invention include, for example, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, Methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-
2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, toluene, ethyl acetate, methyl lactate, ethyl lactate and the like.

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

The (a) polymer compound having a sulfonamide group, which is preferably used in the present invention, and which is water-insoluble and can be converted into an alkaline aqueous solution, includes the following polyurethane resins in addition to the above-mentioned copolymers. . That is, the polyurethane resin suitably used in the present invention, a diisocyanate compound,
A polyurethane resin having, as a basic skeleton, a reaction product of a diol compound containing a sulfonamide group having at least one H atom bonded to N.

Specific examples of the diisocyanate compound suitably used in the present invention include the following.
That is, 2,4-tolylene diisocyanate, a dimer of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m
-Xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dimethylbiphenyl-4,4'-
Aromatic diisocyanate compound such as diisocyanate: fatty acid diisocyanate compound such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate, etc .: isophorone diisocyanate; 4,
Alicyclic diisocyanate compounds such as 4'-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, 1,3- (isocyanatomethyl) cyclohexane and the like:
Examples thereof include 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.

Examples of the diol compound containing a sulfonamide group having at least one H atom bonded to N include the following compounds. 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-
And toluenesulfonamide.

These diol compounds containing a sulfonamide group can be used alone or in combination of two or more.

Further, a diol compound which does not have a sulfonamide group and may have another substituent which does not react with isocyanate can be used in combination. Specific examples of such diol compounds include the following. That is, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, 1,3-butylene glycol, 1,6-hexanediol, and 2-butyl- 1,4
-Diol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-bis-β-hydroxyethoxycyclohexane, cyclohexanedimethanol, tricyclodecanedimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, An ethylene oxide adduct of bisphenol A, a propylene oxide adduct of bisphenol A, an ethylene oxide adduct of bisphenol F,
Propylene oxide adduct of bisphenol F, ethylene oxide adduct of hydrogenated bisphenol A, propylene oxide adduct of hydrogenated bisphenol A, hydroquinone dihydroxyethyl ether, p-xylylene glycol, dihydroxyethyl sulfone, bis (2-hydroxyethyl) -2,4-tolylene dicarbamate,
2,4-tolylene-bis (2-hydroxyethylcarbamide), bis (2-hydroxyethyl) -m-xylylenedicarbamate, bis (2-hydroxyethyl) inphthalate, 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 used in the present invention is synthesized by adding the above-mentioned diisocyanate compound and diol compound to an aprotic solvent, adding a known catalyst having an activity corresponding to the respective reactivity, and heating. The molar ratio of diisocyanate and diol compound used is preferably 0.8: 1 to 1.2: 1, more preferably 0.8: 1.
5: 1.1 to 1.1: 1, and when an isocyanate group remains at the terminal of the polymer, it is finally synthesized in a form in which no isocyanate group remains by treating with an alcohol or an amine. .

The molecular weight of the polymer (a) of the present invention having a sulfonamide group and being water-insoluble and soluble in an alkaline aqueous solution is preferably 2,000 or more by weight average, and 1,000 or more by number average. It is. More preferably, the weight average is in the range of 5,000 to 300,000, and the number average is 2,000.
The range is from 0 to 250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, and more preferably 1.1 to 10.

The (a) polymer compound having a sulfonamide group and having a water-insoluble property and being soluble in an alkaline aqueous solution used in the present invention may contain an unreacted monomer. In this case, the proportion of the monomer in the polymer compound is desirably 15% by weight or less. (A) used in the present invention
The polymer compound having a sulfonamide group and being insoluble in water and soluble in an alkaline aqueous solution may be used alone or in combination of two or more. The content of these high molecular compounds contained in the photosensitive composition is 3 to 95% by weight of the total composition, preferably 5 to 85% by weight .

The alkali-soluble novolak resin (b) used in the present invention includes, for example, phenol formaldehyde resin, m-cresol formaldehyde resin, p-form
Cresol formaldehyde resin, cresol formaldehyde resin such as m- / p-mixed cresol formaldehyde resin, phenol / cresol (m-, p- or m- / p-mixture) mixed formaldehyde resin, phenol-modified xylene resin And polyhydroxystyrene, polyhalogenated hydroxystyrene, and other known alkali-soluble polymer compounds. These alkali-soluble novolak resins are:
The weight average molecular weight is 500 to 20,000, and the number average molecular weight is 200 to 10,000.

The alkali-soluble novolak resin (b) is preferably used in an amount of 1 to 70% by weight of the total composition. More preferably, it is 3 to 60% by weight. Further, as described in U.S. Pat. No. 4,123,279, phenol having a C3-8 alkyl group as a substituent, such as t-butylphenol formaldehyde resin and octylphenol formaldehyde resin, and formaldehyde are used. It is preferable to use a condensate with the above in view of improving the oil sensitivity of the image.

The (c) positive-working photosensitive compound used in the present invention is specifically an o-naphthoquinonediazide compound. Examples of the o-naphthoquinonediazide compound used in the present invention include JP-B-43-2840.
An ester of 1,2-diazonaphthoquinonesulfonic acid chloride and a pyrogallol-acetone resin described in JP-A No. 3 is preferred. Other suitable orthoquinonediazide compounds include U.S. Pat.
There are esters of 1,2-diazonaphthoquinone sulfonic acid chloride and phenol-formaldehyde resin described in US Pat. Nos. 6,120 and 3,188,210. Other useful o-naphthoquinonediazide compounds have been reported in many patents and are known. For example, JP-A-47-5303 and JP-A-48-50
No.-63802, No. 48-63803, No. 48-
No. 96575, No. 49-38701, No. 48-1
No. 3354, Japanese Patent Publication No. 37-18015, 41-1
Nos. 1222, 45-9610 and 49-174
No. 81, U.S. Pat. Nos. 2,797,213, 3,454,400, 3,544,323, 3,573,917, and 3,674,495;
No. 3,785,825, British Patent No. 1,227,6
No. 02, No. 1,251,345, No. 1,267,
No. 005, No. 1,329,888, No. 1,33
No. 0,932, German Patent No. 854,890, and the like.

The o-naphthoquinonediazide compound particularly preferred 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.
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
2-178562, JP-A-1-76047, JP-A-2-213847, U.S. Pat. No. 3,102,809
No. 3,126,281, No. 3,130,04
No. 7, No. 3,148,983, No. 3,184,3
No. 10, No. 3,188,210, No. 4,639,
Nos. 406 and the like, and those described in each publication or specification can be mentioned.

In synthesizing these o-naphthoquinonediazide compounds, it is preferable to react 0.2 to 1.2 equivalents of 1,2-diazonaphthoquinonesulfonic acid chloride with respect to the hydroxyl group of the polyhydroxy compound. It is preferable to react 0.3 to 1.0 equivalent. The obtained o-naphthoquinonediazide compound is 1,2-
A mixture of diazonaphthoquinonesulfonic 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 to 1,2-diazonaphthoquinonesulfonic acid ester in the mixture (complete esterification) 5 mol%)
It is preferably at least 20, more preferably 20 to 99.
Mol%.

Examples of the photosensitive compound which acts positively without using an o-naphthoquinonediazide compound include, for example, a polymer compound having an orthonitrocarbinol ester group described in JP-B-56-2696. Can also be used in the present invention. Further, a compound capable of generating an acid by photolysis and -CO- dissociated by the acid
A combination system with a compound having a C group or a -CO-Si group can also be used in the present invention.

For example, a combination of a compound capable of generating an acid by photolysis with an acetal or an O, N-acetal compound (Japanese Patent Application Laid-Open No. 48-89003) or a combination with an orthoester or amide acetal compound (Japanese Patent Application Laid-Open No. 51-120)
714), a combination with a polymer having an acetal or ketal group in the main chain (JP-A-53-133429),
Combination with enol ether compound (JP-A-55-12
No. 995), a combination with an N-acylimino carbon compound (JP-A-55-126236), a combination with a polymer having an orthoester group in the main chain (JP-A-56-173).
No. 45), a combination with a silyl ester compound (JP-A-6
No. 0-10247) and a combination with a silyl ether compound (JP-A-60-37549, JP-A-60-1214).
No. 46).

The amount of these (c) positive-acting photosensitive compounds (including the above combinations) in the photosensitive composition of the present invention is 10 to 50% by weight, more preferably 15 to 50% by weight. 40% by weight. The cyclic lactone (d) used in the present invention also functions as a solvent for dissolving other components. Examples of such a cyclic lactone include α-butyrolactone, β-propiolactone, δ-valerolactone and the like.

The amount of the cyclic lactone (d) in the coating solvent is as follows:
The amount is not particularly limited as long as the effect of the present invention is sufficient. (D) Since the cyclic lactone has a high boiling point, a trace amount usually remains in the photosensitive layer after the coating solution is applied and dried. The residual amount can be measured by gas chromatography.

The composition of the present invention may contain 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. it can. Cyclic acid anhydride include U.S. Pat phthalic anhydride as described in 4,115,128 Pat, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-oxy - [delta ⁴ - tetrahydrophthalic anhydride Examples include phthalic acid, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, and pyromellitic anhydride. By containing these cyclic acid anhydrides in an amount of 1 to 15% by weight in the total composition, the sensitivity can be increased up to about three times. 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. More specifically, o- is disclosed in JP-A-50-36209 and JP-A-53-8128.
Combinations of naphthoquinonediazide-4-sulfonic acid halogenides and salt-forming organic dyes, JP-A-53-36223,
Nos. 54-74728, 60-3626, 61-
No. 143748, No. 61-151644, No. 63-5
The combination of a trihalomethyl compound and a salt-forming organic dye described in JP-A-8440 can be mentioned. 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 # 60
3. Oil black BY, oil black BS, oil black T-505 (all manufactured by Orient Chemical Industries, Ltd.), Victoria Pure Blue, crystal violet (C142555), methyl violet (C14)
2535), rhodamine B (C145170B), malachite green (C142000), methylene blue (C152015) and the like. Also,
Dyes described in JP-A-62-293247 are particularly preferred.

The composition of the present invention is dissolved in a solvent capable of dissolving the above-mentioned components, and coated on a support. Solvents that can be used in combination other than the cyclic lactone used in the present invention include:
Ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol,
-Methoxy-2-propyl acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethylacetamide, dimethylformamide, water, N-methylpyrrolidone, tetrahydrofurfuryl alcohol, acetone, diacetone alcohol, methanol, ethanol, isopropanol, diethylene glycol There are dimethyl ether and the like, and these solvents are used alone or as a mixture of two or more.

The solid concentration in the coating solution is 2 to 5
0% by weight. The amount of application varies depending on the application, but for example, in the case of a photosensitive lithographic printing plate, the solid content is generally preferably 0.5 to 3.0 g / m ² . 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 0.0% of the entire photosensitive composition.
The content is 1 to 1% by weight, more preferably 0.05 to 0.5% by weight.

The surface of the photosensitive layer provided as described above is preferably matted in order to reduce the time for evacuation and prevent blurring during close contact exposure using a vacuum frame. Specifically, JP-A-50-125805,
A method of providing a mat layer as described in JP-B-57-6582 and JP-A-61-28986, and a method of thermally fusing a solid powder as described in JP-B-62-62337. And the like.

When a lithographic printing plate is produced using the photosensitive composition of the present invention, an aluminum plate is preferred as a support. Aluminum plates include pure aluminum and aluminum alloy plates. 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, or 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, it is preferable that a back surface treatment such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate or the like, or anodizing treatment is performed. Also, as described in U.S. Pat. No. 2,714,066, an aluminum plate grained and then immersed in an aqueous solution of sodium silicate is disclosed in U.S. Pat. No. 3,181,461. As described above, 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 electrolytic solution of an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, boric acid, or an organic acid such as oxalic acid or sulfamic acid or an aqueous solution or a non-aqueous solution of a salt thereof alone or in combination of two or more. It is carried out by passing a current through an aluminum plate as an anode.

Electrodeposition of a silicate as described in US Pat. No. 3,658,662 is also 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 trichlene, 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 the mechanical method include a ball polishing method, a plast polishing method, and a brush polishing method in which an aqueous dispersion slurry of an abrasive such as pumice is rubbed with a nylon brush, and the chemical method is disclosed in JP-A-54-31187. A method of immersing in a saturated aqueous solution of an aluminum salt of a mineral acid as described in the official gazette is suitable, and as an electrochemical method, a method of alternating current electrolysis in an acidic electrolyte such as hydrochloric acid, nitric acid or a combination thereof is used. Is preferred. Among such surface roughening methods, particularly, a surface roughening method combining mechanical surface roughening and electrochemical surface roughening as described in Japanese Patent Application Laid-Open No. 55-137993, Is preferred because of its strong adhesion to the support.

[0053] graining according to the above-described method, 0.3 center line surface roughness of the surface of the aluminum plate (H _a) is
It is preferable that the coating be performed within a range of 1.0 μm.
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 preferable because they form unnecessary films on the etched surface.

These etching agents are used so that the dissolution rate of the aluminum or alloy to be used is from 0.3 g to 40 g / m ² per one minute of immersion time when the concentration and temperature are set. Most preferred,
It can be higher or lower than this. Etching is performed by immersing the aluminum plate in the above-mentioned etching solution, or by applying an etching plate to the aluminum plate, and the amount of etching is 0.5 to 10 g.
/ M ² .

As the above-mentioned 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, fluoric acid, hydrofluoric acid, or the like is 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, sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid or the like or a combination of two or more thereof in an aqueous solution or a non-aqueous solution when a DC or AC current is passed through aluminum,
An anodic oxide film can be formed on the surface of the aluminum support.

Anodizing treatment conditions vary depending on the electrolytic solution used and cannot be unconditionally determined. However, in general, the concentration of the electrolytic solution is 1 to 80% by weight, and the liquid temperature is 5 to 70%.
° C, current density 0.5-60 amps / dm ² , voltage 1 ~
A range of 100 V and an electrolysis time of 30 seconds to 5 minutes is appropriate.
Among these anodizing treatments, in particular, British Patent No. 1,
No. 412,768, a method of anodizing at high current density in sulfuric acid, U.S. Pat. No. 4,211,6.
Anodizing in low concentrations of sulfuric acid as described in U.S. Patent No. 3,511,661.
The method of anodizing phosphoric acid as an electrolytic bath described in the specification is preferred.

The aluminum plate which has been roughened and anodized as described above may be subjected to a hydrophilizing treatment, if necessary. A preferred example is US Pat.
No. 066 and 3,181,461, such as an alkali metal silicate, for example, an aqueous solution of sodium silicate or potassium fluoride zirconate disclosed in JP-B-36-22063 and U.S. Pat. There is a method of treating with polyvinyl sulfonic acid as disclosed in 153,461.

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, if necessary, subjected to a hydrophilization treatment. An example of such a water-soluble compound is disclosed in
No. 3,511,661, a combination of a water-soluble metal salt and hydrophilic cellulose (for example, zinc chloride and carboxymethyl cellulose, magnesium chloride and hydroxyethyl cellulose) disclosed in US Pat.
Disclosed in Japanese Patent Publication No. 46-35885, polyvinyl phosphonic acid disclosed in JP-B-46-35885, amino acids disclosed in JP-A-60-1499491, and salts thereof (Na salt, K salt) Alkali metal salts, ammonium salts, hydrochlorides, sulfates, acetates, phosphates, etc.), and amines having a hydroxyl group and their salts (hydrochloride, sulfuric acid) disclosed in JP-A-60-232998. Salts, phosphates, etc.), JP-A-62-194
No. 94, the phosphate disclosed in JP-A-59-1.
Polymer compounds containing a monomer having a sulfo group as a repeating unit disclosed in 01651, a compound described in JP-A-4-282637, and the like.
Among them, amino acids and salts thereof, and amines having a hydroxyl group and salts thereof are particularly preferable. Such water-soluble primer layer compounds preferably provided in the range of 1mg / m ² ~80mg / m ² in solid content.

On the back side of the support of the photosensitive lithographic printing plate used in the present invention, a polymer for suppressing the elution of the anodic oxide film of aluminum during development and for preventing the photosensitive layer from being damaged when superposed. A back coat layer made of a compound may be provided. As the material of the back coat,
A polymer compound insoluble in an alkaline developer as described in JP-A-2271 is suitable.

As a developer for the photosensitive composition of the present invention, sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium phosphate tribasic, sodium phosphate dibasic, phosphate tribasic Aqueous solutions of inorganic alkali agents such as ammonium, dibasic ammonium phosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc., having a concentration of 0.1 to 1 are suitable.
0% by weight, preferably 0.5 to 5% by weight.

Further, an organic solvent such as a surfactant or alcohol can be added to the alkaline aqueous solution, if necessary. 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 photosensitive lithographic printing plate of the present invention is disclosed in JP-A-54-8002 and JP-A-55-1.
Plate making may be performed by the methods described in JP-A-15045 and JP-A-59-58431. That is, after the development treatment, the substrate may be subjected to desensitization treatment after washing with water or as it is, or after treatment with an aqueous solution containing an acid. Furthermore, in the development process of this type of photosensitive lithographic printing plate,
The alkaline aqueous solution is consumed depending on the amount of processing to reduce the alkali concentration, or the processing time is reduced because the alkali concentration is reduced by air when the automatic developing solution is operated for a long time. The processing capacity may be restored by using a replenisher as described in Japanese Patent Application Laid-Open Publication No. H11-209,036. In this case, it is preferable to supplement by the method described in US Pat. No. 4,882,246. The plate making process described above is described in JP-A-2-7054,
It is preferably carried out by an automatic developing machine as described in JP-A-2-32357.

In the case where unnecessary image portions are erased after the development of the photosensitive lithographic printing plate of the present invention, the so-called non-polluting erasing method described in Japanese Patent Publication No. 13293/1990. Liquid (not including hydrofluoric acid, a powerful drug) can be used. Further, as a desensitized gum applied as desired in the final step of the plate making process, Japanese Patent Publication No. Sho 62-16
No. 834, No. 62-25118, No. 63-52600
No., JP-A-62-7595, JP-A-62-11693,
What is described in each gazette of the said 62-83194 is preferable.

Further, the photosensitive lithographic printing plate of the present invention is suitable for a burning treatment when high printing durability is desired. If you are burning, before burning, the Japanese Patent Publication No. 61-2
Nos. 518 and 55-28062, JP-A-62-318
It is preferable to carry out treatment with a surface-regulating liquid as described in JP-A Nos. 59 and 61-159655.

[0064]

EXAMPLES The present invention will be described in more detail with reference to Synthesis Examples and Examples, which should not be construed as limiting the scope of the present invention.

Synthesis Example 1 p-Aminobenzenesulfonamide was placed in a one-liter three-necked flask equipped with a stirrer, a condenser, and a dropping funnel.
2 g (1.0 mole) and 700 ml of tetrahydrofuran
And stirred under ice-water bath. To this mixture, 52.3 g (0.5 mole) of methacrylic acid chloride was dropped by a dropping funnel over about 1 hour. After completion of the dropwise addition, the ice-water bath was removed, and the mixture was stirred at room temperature for 30 minutes, and further stirred for 1 hour while heating to 60 ° C. using an oil bath. After the reaction,
This reaction mixture was poured into 3 liters of water with stirring, stirred for 30 minutes, and then filtered to obtain a white solid of N- (p-aminosulfonylphenyl) methacrylamide. This white solid could be purified by recrystallization from a mixed solvent of water-acetone (yield 39.3).
g).

The thus obtained N- (p-aminosulfonylphenyl) methacrylamide (9.72 g, 0.02 g) was obtained.
408 mole) and 7.93 g of methyl methacrylate (0.
0792 mole), N, N-dimethylformamide 50 m
was placed in a 200 ml three-necked flask equipped with a stirrer and a condenser, and stirred while heating to 64 ° C. in a hot water bath.
0.246 g of α, α'-azobisisobutyronitrile was added to the 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 to obtain 16 g of a white solid. The weight average molecular weight (polystyrene standard) of this polymer compound was measured by gel permeation chromatography and found to be 490.
00. (Polymer compound (i) of the present invention)

Synthesis Example 2 31.0 g (0.36 mole) of methacrylic acid was placed in a 500 ml three-necked flask equipped with a stirrer, a condenser, and a dropping funnel.
39.1 g (0.36 mole) of ethyl chloroformate and 200 ml of acetonitrile were added, and the mixture was stirred in an ice-water bath. 36.4 g (0.36 mole) of triethylamine was added to this mixture.
Was dropped by a dropping funnel over about 1 hour. After completion of the dropwise addition, the ice water bath was removed, and the mixture was stirred at room temperature for 30 minutes, and an oil bath was attached.

To the reaction mixture was added 51.7 g (0.30 mole) of p-aminobenzenesulfonamide, and the mixture was stirred for 1 hour while warming to 70 ° C. in an oil bath. After the reaction,
This mixture was poured into 1 liter of water under stirring and stirred for 30 minutes. The solid was collected by filtration and further 500 m of water
After reslurrying to 1 l, filtration and drying
A white solid of (p-aminosulfonylphenyl) methacrylamide was obtained. (Yield 46.9 g).

Next, 4.61 g (0.019 g) of N- (p-aminosulfonylphenyl) methacrylamide was placed in a 20 ml three-necked flask equipped with a stirrer, a condenser and a dropping funnel.
2 mol), 2.94 g (0.025 g) of ethyl methacrylate
8mol), 0.80g of acrylonitrile (0.015mo
le) and 20 g of N, N-dimethylacetamide,
The mixture was stirred while being heated to 65 ° C. by a hot water bath. 0.15 g of V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) was added to this mixture, and 6
The mixture was stirred for 2 hours under a nitrogen stream while maintaining the temperature at 5 ° C. The reaction mixture is further added with N- (p-aminosulfonylphenyl)
1.61 g of methacrylamide, ethyl methacrylate
A mixture of 94 g, acrylonitrile 0.80 g, N, N-dimethylacetamide and V-65 0.15 g was added to 2
The solution was dropped with a dropping funnel over time. After completion of the dropwise addition, the mixture was further stirred at 65 ° C. for 2 hours. After completion of the reaction, methanol 40
g, cooled and poured into 2 liters of water with stirring.
After stirring for 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 (ii) of the present invention)

Synthesis Examples 3 to 5 Polymer compounds (iii) to (v) 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.

[0071]

[Table 1]

Synthesis Example 6 2,2-dihydroxymethylpropionic acid 4 was added to a 500 ml three-necked flask equipped with a stirrer, a condenser, and a dropping funnel.
0 g (0.298 mole) and 100 ml of acetic anhydride were added and stirred in an ice-water bath. 100 m of pyridine was added to this mixture.
1 was dropped by a dropping funnel over about 30 minutes. After dropping, remove the ice-water bath and remove the mixture with an oil bath.
The mixture was stirred for 2 hours while heating to 0 ° C. After completion of the reaction, hydrochloric acid was added to make the mixture acidic, and the mixture was extracted with chloroform using a separating funnel. After washing the chloroform layer with water,
It was dehydrated with anhydrous sodium sulfate. The solution was distilled off under reduced pressure with this chloroform solution to obtain 57 g of 2,2-diacetoxymethylpropionic acid as a white solid.

Next, 30 g (0.137 mole) of 2,2-diacetoxymethylpropionic acid and 20 m of thionyl chloride were used.
was placed in a 300 ml three-necked flask equipped with a stirrer, a condenser, and a dropping funnel, and stirred for 2 hours while heating to 80 ° C. After completion of the reaction, unreacted thionyl chloride and the like were sufficiently removed by distillation under reduced pressure, and the reaction product was sufficiently cooled by placing an ice-water bath. To this reaction product, a mixture of 46.6 g (0.274 mole) of p-aminobenzenesulfonamide and 150 ml of tetrahydrofuran was dropped by a dropping funnel over about 1 hour. After dripping, 6 in an oil bath
The mixture was stirred for 2 hours while heating to 0 ° C. After completion of the reaction, the reaction mixture was poured into 2 liters of water with stirring, stirred for 30 minutes, and filtered to obtain a white solid of p- (1,1-diacetoxymethylethylcarbonylamino) benzenesulfonamide. . This white solid could be purified by recrystallization from ethanol. (Yield 26 g).

Next, 22 g of p- (1,1-diacetoxymethylethylcarbonylamino) benzenesulfonamide
(0.06 mole) and 4.8 g of sodium hydroxide (0.
12 mol), 50 ml of ethanol and 50 ml of water are put into a 300 ml three-necked flask equipped with a stirrer and a condenser,
The mixture was heated under reflux for 2 hours. The reaction mixture was poured into 1 liter of water with stirring, stirred for 30 minutes, and then filtered to obtain a white solid of p- (1,1-dihydroxymethylethylcarbonylamino) benzenesulfonamide.
This white solid could be purified by recrystallization from ethanol (yield 11 g).

Next, p- (1,1-dihydroxymethylethylcarbonylamino) benzenesulfonamide
73 g (0.02 mole) and 5.26 g (0.021 mole) of 4,4'-diphenylmethane diisocyanate;
18 g of N, N-dimethylacetamide was placed in a 100 ml three-necked flask equipped with a stirrer and a condenser, and stirred for 2 hours while heating to 100 ° C. After completion of the reaction, the reaction mixture was poured into 500 ml of water with stirring, and stirred for 30 minutes. The precipitate was filtered and dried to obtain 10 g of a white solid. By gel permeation chromatography, the weight average molecular weight of this polymer compound (polystyrene standard)
Was 32000. (Polymer compound (vi) of the present invention).

Examples 1 to 6 and Comparative Examples 1 to 10 An aluminum plate having a thickness of 0.30 mm was grained with a nylon brush and an aqueous suspension of pumicestone of 400 mesh, and washed thoroughly with water. . After etching by dipping in 10% sodium hydroxide at 70 ° C. for 60 seconds, the substrate was washed with running water, then neutralized with 20% HNO ₃ , and washed with water. This was converted to 160 clones / d in a 1% aqueous nitric acid solution using a sinusoidal alternating current under the condition of _VA = 12.7V.
The electrolytic surface-roughening treatment was performed with an anode electricity amount of m ² . When the surface roughness was measured, it was 0.6 μ (Ra display). Then immersed in 30% H ₂ SO ₄ aqueous solution
After desmutting at 5 ° C. for 2 minutes, a thickness of 2.7 g / m ² at a current density of 2 A / dm ² in a 20% H ₂ SO ₄ aqueous solution.
Anodized so that

Next, six kinds of photosensitive solutions [A] -1 to [A] -6 were prepared by changing the kind of the polymer compound of the present invention in the following photosensitive solution [A] as shown in Table 2. These photosensitive liquids are applied on an anodized aluminum plate, dried at 100 ° C. for 2 minutes, and dried to form a photosensitive lithographic printing plate [A] -1.
To [A] -6 (Examples 1 to 6). The coating amount at this time was 2.5 g / m ² in terms of dry weight.

[Photosensitive Solution A (Invention)] Esterified product of naphthoquinone-1,2-diazide-5-sulfonyl chloride and 0.45 g pyrogallol-acetone resin (as described in Example 1 of US Pat. No. 3,635,709) ) High molecular compound (Table 2) 0.50 g Cresol-formaldehyde novolak resin 0.6 g (m-; 60%, p-; 40%) 2- (p-methoxyphenyl) -4,6-bis 0.02 g ( Trichloromethyl) -S-triazine Oil Blue # 603 (Orient Chemical Co., Ltd.) 0.01 g γ-butyrolactone (γ-BL) 8 g Methyl ethyl ketone 12 g

Next, the kind of the high molecular compound of the present invention in the following photosensitive solution [B] was changed as shown in Table 2, and instead of γ-butyrolactone (γ-BL) used in the photosensitive solution [A], methylcellosolve was used. And 6 types of photosensitive solutions [B] -1 to [B]
-6 was adjusted. These photosensitive solutions were used in the above photosensitive solution [A]-
In the same manner as in 1 to [A] -6, a photosensitive lithographic printing plate [B]
-1 to [B] -6 (Examples 1 to 6) were prepared.

[Photosensitive Solution B (Comparative Example)] Esterified product of naphthoquinone-1,2-diazide-5-sulfonyl chloride and 0.45 g pyrogallol-acetone resin (as described in Example 1 of US Pat. No. 3,635,709) ) High molecular compound (Table 2) 0.50 g Cresol-formaldehyde novolak resin 0.6 g (m-; 60%, p-; 40%) 2- (p-methoxyphenyl) -4,6-bis 0.02 g ( Trichloromethyl) -S-triazine Oil Blue # 603 (Orient Chemical Co., Ltd.) 0.01 g Methyl cellosolve 8 g Methyl ethyl ketone 12 g

Next, the following photosensitive solutions [C] to [F] were prepared in the same manner as the photosensitive solutions A or B except that the following photosensitive solutions were changed as follows. In the same manner as the photosensitive solution [A] and the photosensitive solution [B], these photosensitive solutions are used as photosensitive lithographic printing plates [C], [D], [E],
[F] was prepared.

[Photosensitive solution C (Comparative Example 7)] In the photosensitive solution A, 1.1 g of the polymer compound (ii) alone was used instead of the polymer compound (ii) and the cresol formaldehyde novolak resin.

[Photosensitive solution D (Comparative Example 8)] In photosensitive solution B, 1.1 g of the polymer compound (ii) alone was used instead of the polymer compound (ii) and the cresol formaldehyde novolak resin.

[Photosensitive solution E (Comparative example 9)] In photosensitive solution A, 1.1 g of cresol formaldehyde novolak resin alone was used instead of polymer compound (ii) and cresol formaldehyde novolak resin.

[Photosensitive solution F (Comparative Example 10)] In photosensitive solution B, 1.1 g of cresol formaldehyde novolak resin alone was used instead of polymer compound (ii) and cresol formaldehyde novolak resin.

Photosensitive planographic printing plates [A] -1 to 6, [B]
-1 to 6, and a positive transparent original of a line image and a halftone dot image were adhered on the respective photosensitive layers of [C], [D], [E] and [F], and a distance of 70 cm with a 30-amp carbon arc lamp. Was exposed. The exposed photosensitive lithographic printing plates [A] -1 to 6, [B] -1 to 6, [C], [D],
Each of [E] and [F] was immersed and developed at 25 ° C. for 60 seconds in an 8-fold diluted aqueous solution of DP-4 (trade name: manufactured by Fuji Photo Film Co., Ltd.).

The obtained lithographic printing plates [A] -1 to 6
Each of [B] -1 to 6, [C], [D], [E] and [F] was printed on high quality paper using UV ink with a KOR type printer manufactured by Heidelberg. Lithographic printing plates [A] -1 to 6, [B] -1 to 6, [C], [D],
The final printed number of each of [E] and [F] was examined, and the results are as shown in Table 2.

The developing latitude was obtained by diluting DP-4 to 1: 8, processing at 25 ° C. for 30 seconds and 5 minutes, and adjusting the density difference to 0.15.
Of the number of solid gray scale steps (number of processing steps for 5 minutes-
The results are shown in Table 2 according to the number of processing stages for 30 seconds). The greater the number of prints, the better the printing durability, and the smaller the number of steps evaluated for development latitude, the better the development latitude.

[0089]

[Table 2]

As can be seen from Table 2, a polymer compound having a sulfonamide group, a novolak resin, and a γ-BL
Printing plate [A] -1 using a photosensitive composition containing
To 6 (Examples 1 to 6) are lithographic printing plates [B] -1 to 6
(Comparative Examples 1 to 6), planographic printing plate [C] (Comparative Example 7), planographic printing plate [D] (Comparative Example 8), planographic printing plate [E] (Comparative Example 9), planographic printing plate [F] Compared with (Comparative Example 10), the printing durability of UV ink and the development latitude were very excellent.

Examples 7 to 12 and Comparative Examples 11 to 20 An aluminum plate having a thickness of 0.24 mm was grained with a nylon brush and an aqueous suspension of 400 mesh pamistone, and then washed thoroughly with water. Thus, a substrate [I] was prepared. Substrate [I] is immersed in 10% sodium hydroxide at 70 ° C. for 20 seconds, etched, washed with running water, and then etched.
% HNO ₃ , washed with water, and subjected to electrolytic surface roughening treatment in a 0.7% nitric acid aqueous solution at 400 clones / dm ^{2 in} a 0.7% nitric acid aqueous solution using a sine wave alternating waveform current at 12.7 V. Then, the substrate was washed with water to prepare a substrate [II].

The substrate [II] was treated in a 10% aqueous sodium hydroxide solution so that the amount of the surface dissolved was 0.9 g / m ² . After washing with water, neutralization and washing were performed in a 20% nitric acid solution to perform desmutting, followed by anodic oxidation in an 18% aqueous sulfuric acid solution so that the oxide film amount was 3 g / m ² . On the aluminum plate thus obtained, six types of photosensitive solutions [G] -1 to 6 (present invention) in which the kind of the polymer compound of the present invention was changed with the following photosensitive solution [G] were applied. . 100 ℃
And dried for 2 minutes each, and each photosensitive lithographic printing plate [G]-
1 to 6 (Examples 7 to 12) were prepared.

Further, the following photosensitive solutions [H] -1 to 6;
[I], [J], [K] and [L] (Comparative Example) were adjusted, and coated and dried in the same manner as [G] -1 to 6 to obtain a photosensitive lithographic printing plate [H] -1 to 6, [I], [J], [K] and [L] (Comparative Examples 11 to 20) were prepared. The coated amount of these photosensitive lithographic printing plates after drying was 2.5 g / m ² .

The photosensitive solutions [G] -1 to 6 and [H] -1
Table 3 shows the high molecular compounds used in [I], [J], [K] and [L].

[Photosensitive solution G] Esterified product of 2,3,4-trihydroxybenzophenone and 0.45 g naphthoquinone-1,2-diazide-5-sulfonyl chloride (esterification ratio: 90 mol%) Polymer compound (Table 3) 0.77 g cresol formaldehyde novolak resin 0.33 g (meta 60%, para 40%) 4- (p-hydroxybenzoyl) amino-2,6-0.02 g bis (trichloromethyl) -S-triazine Victoria Pure- BOH 0.05 g (Hodogaya Chemical) Megafac F-177 0.004 g (Dainippon Ink fluorinated surfactant) γ-butyrolactone (γ-BL) 4 g 1-methoxy-2-propanol 9 g Methyl ethyl ketone 7 g

[Photosensitive Solution H (Comparative Example)] Esterified product of 2,3,4-trihydroxybenzophenone and 0.45 g naphthoquinone-1,2-diazido-5-sulfonyl chloride (esterification ratio: 90 mol%) Molecular compound (Table 3) 0.77 g cresol formaldehyde novolak resin 0.33 g (60% meta, 40% para) 4- (p-hydroxybenzoyl) amino-2,6-0.02 g bis (trichloromethyl) -S- Triamine Victoria Pure-BOH 0.05 g (Hodogaya Chemical) Megafac F-177 0.004 g (Dainippon Ink Fluorinated Surfactant) Dimethylformamide 4 g 1-Methoxy-2-propanol 9 g Methyl ethyl ketone 7 g

The following photosensitive solutions [I] to [L] are the same as the photosensitive solutions [G] and [H] except that the photosensitive solution [G] or [H] is changed as follows.

[Sensitivity Liquid I (Comparative Example 17)] In Sensitive Solution G, 1.1 g of the high molecular compound (ii) alone was used in place of the high molecular compound (ii) and the cresol formaldehyde novolak resin.

[Photosensitive solution J (Comparative Example 18)] In the photosensitive solution H, 1.1 g of the polymer compound (ii) alone was used in place of the polymer compound (ii) and the cresol formaldehyde novolak resin.

[Photosensitive solution K (Comparative Example 19)] In the photosensitive solution G, 1.1 g of cresol formaldehyde novolak resin alone was used instead of the polymer compound (ii) and the cresol formaldehyde novolak resin.

[Photosensitive solution L (Comparative Example 20)] In photosensitive solution H, only 1.1 g of cresol formaldehyde novolak resin was used in place of polymer compound (ii) and cresol formaldehyde novolak resin.

[0102]

[Table 3]

Photosensitive planographic printing plates [G] -1 to 6 (Examples 7 to 12), [H] -1 to 6, [I], [J], [K]
And [L] (Comparative Examples 11 to 20) were evaluated for performance in the same manner as in Examples 1 to 6 and Comparative Examples 1 to 10, and the results were as shown in Table 3. As can be seen from Table 3, lithographic printing plates [G] -1 to 6 using the polymer compound of the present invention, a novolak resin, and a photosensitive composition containing γ-BL.
(Examples 7 to 12) are planographic printing plates [H] -1 to 6,
[I], [J], [K] and [L] (Comparative Examples 11 and 2)
Compared with 0), the printing durability of the UV ink and the development latitude are very good.

[0104]

The present invention has excellent coating properties when coated on a support, and has excellent development latitude when the exposed portion is used with an aqueous alkaline developer after coating, drying and image exposure. The resulting relief image has good abrasion resistance and good adhesion to the support, and when used as a printing plate, many good printed matter can be obtained.

Further, even when printing using UV ink is performed, a large number of good printed matters can be obtained.

Claims (2)

(57) [Claims] 1. A method for producing a positive photosensitive lithographic printing plate, comprising applying a coating solution containing the following (a) to (d) on a support and drying it. (A) a polymer compound having a sulfonamide group and being water-insoluble and soluble in an alkaline aqueous solution; (b) an alkali-soluble novolak resin; (c) a photosensitive compound acting positively; (d) a cyclic lactone 2. A positive photosensitive composition comprising the following (a) to (d). (A) a polymer compound having a sulfonamide group and being water-insoluble and soluble in an alkaline aqueous solution; (b) an alkali-soluble novolak resin; (c) a photosensitive compound acting positively; (d) a cyclic lactone