JPH0519471A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain the photosensitive compsn. having a high sensitivity and excellent tone reproducibility by incorporating a specific photosensitive S triazine compd. therein. CONSTITUTION:This compsn. contains (a) a compd. having at least one piece of ethylenic unsatd. double bonds which can be addition polymerized and the compd. which is the photosensitive S-triazine compd. expressed by formula I and (b) the compd. in which both of R3 and R4 are a hydrogen atom, and (c) the compd. in which at least either of the R3 and R4 are a hydrogen atom and the weight ratio of (b) and (c) is in a 20/80 to 80/20 ratio. In the formula, R1, R2 may be the same or different from each other and denote a hydrogen atom, alkyl group, etc., or R1, R2 may form a heterocyclic ring consisting of a nonmetal atom together with the nitrogen atom to which these groups are bonded. R5 denotes an alkyl group, substd. alkyl group, etc.,' R<6>, R<7> may be the same or different from each other and denote a hydrogen atom, alkyl group, etc., R<3>, R<4> denote a hydrogen atom, halogen atom, etc.; X may be the same as or different from each other and denote a chlorine atom or bromine atom; (m), (n) denote 0, 1 or 2.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a photosensitive composition suitable for a photosensitive lithographic printing plate. More specifically, the present invention relates to a novel photosensitive composition containing two or more photosensitive S-triazine compounds to improve the relationship between sensitivity and tone reproducibility.

[0002]

2. Description of the Related Art Conventionally, a method of reproducing an image by a photographic method using a photosensitive composition containing a photopolymerization initiator is widely known. The photosensitive composition is, for example, a basic composition comprising an organic solvent-soluble polymer, an ethylenically unsaturated addition-polymerizable compound and a photopolymerization initiator as described in JP-B-46-32714, JP-B-4.
A composition in which an unsaturated double bond as described in JP-A-9-34041 is introduced into an organic solvent-soluble polymer to improve curing efficiency, JP-B-48-38403, and JP-B-53-53.
The composition using a novel photopolymerization initiator as described in JP-A 27605 and British Patent 1,388,492 is known, and some of them are put to practical use. Further, many halogen free radical generators have been proposed as photopolymerization initiators, and halogen free radical generators having a photosensitive wavelength range from near ultraviolet to visible light have been proposed. For example, U.S. Pat.Nos. 3,954,475, 3,987,037 and 4,1
There is a halomethyl-s-triazine compound group described in 89,323. Although these compounds have a photosensitive wavelength range from near-ultraviolet to visible light, the irradiated light is not effectively used and the sensitivity of photolysis is relatively low. Further, the photosensitive composition using these triazine compounds has a drawback that the triazine compound is crystallized during storage for a long period of time, resulting in a decrease in sensitivity.

A photosensitive composition using a novel S-triazine compound for the purpose of improving the storage stability and having high sensitivity to these problems is described in JP-A-63-153542. However, among the S-triazine compounds, compounds having high sensitivity have a drawback that tone reproducibility is deteriorated. In addition, a compound having a relatively good tone reproducibility had a defect that the sensitivity was insufficient. Therefore, a photosensitive composition which can satisfy both sensitivity and tone reproducibility has not been obtained so far.

[0004]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a photosensitive composition having high sensitivity and improved tone reproducibility.

[0005]

Means for Solving the Problems As a result of various investigations by the present inventors, the above-mentioned problems were (a) a compound having at least one ethylenically unsaturated double bond capable of addition polymerization, and the following general formula (I): A photosensitive S-triazine compound represented by: (b) a compound in which R ³ and R ⁴ are both hydrogen atoms, and (c) a compound in which at least one of R ³ and R ⁴ is a halogen atom (b) And (c) weight ratio is 20 / 80-8
The present invention has been found to be solved by a photosensitive composition containing 0/20.

[0006]

[Chemical 2]

In the general formula [I], R ¹ and R ² may be the same or different, and are a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, -COR ⁵ or -CO-NR. ⁶ R ⁷ is shown, or R ¹ and R ² may form a heterocyclic ring composed of a non-metal atom together with the nitrogen atom to which it is bonded. R ⁵ represents an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, and R ⁶ and R ⁷
May be the same or different from each other and represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group.

R ³ and R ⁴ represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. X and Y may be the same as or different from each other and each represents a chlorine atom or a bromine atom.
m and n represent 0, 1 or 2. The present invention will be described in more detail below. In the above general formula, R ^{1 to} R ⁷
It is preferable to use an alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group and isopropyl group, and an aryl group having 6 to 14 carbon atoms such as phenyl group and naphthyl group.

Examples of the substituent of the substituted alkyl group and the substituted aryl group represented by R ¹ , R ² , R ⁵ , R ⁶ , and R ⁷ include aryl groups such as phenyl group and halogen atoms such as chlorine atom;
Alkoxy groups such as methoxy and ethoxy groups; carboxyl groups; carboalkoxy groups such as carbomethoxy groups and carboethoxy groups; carboaryloxy groups; cyano groups; acetyl groups; acyl groups such as benzoyl groups; nitro groups; dialkylamino groups; or the general formula (A) ~ (C): -SO 2 -Z 1 (A) -SO 2 -O-Z 1 (B) -SO 2 -NH-Z 1 (C) ( wherein Z ¹ is a hydrogen atom Or a sulfonyl derivative represented by an alkyl group or an aryl group).

The substituent of the substituted aryl group of R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ includes an alkyl group in addition to the above-mentioned substituents. When R ¹ and R ² form a heterocyclic ring composed of a non-metal atom together with the nitrogen atom to which it is bonded, examples of the heterocyclic ring include those shown in (D) to (H) below.

[0011]

[Chemical 3]

Particularly preferred substituents of the substituted alkyl group or substituted aryl group of R ¹ and R ² are a halogen atom, a carboxyl group, a carboalkoxy group, a cyano group,
An electron-withdrawing group such as an acyl group or a sulfonyl derivative,
Further, among the substituents of the substituted alkyl group and the substituted aryl group of R ⁵ , particularly preferable are electron-donating groups such as dialkylamino group and alkoxy.

Among the compounds represented by the general formula (I) as described above, particularly preferable compounds are those represented by the general formula (I):
R ¹ and R ² are a hydrogen atom, a carboalkoxymethyl group, a chloromethyl group, a chloroethyl group, a cyanomethyl group or a cyanoethyl group, and at least one of R ¹ and R ² is a group other than a hydrogen atom, or R ¹ and R ² and at _{-C 2 H 4 -SO 2 -C 2} H 4 - a composed group to form, R ³
And R ⁴ is a hydrogen atom, a halogen atom or an alkyl group.

The compound represented by the general formula [I] used in the photosensitive composition of the present invention is an aromatic nitrile compound represented by the general formula [II].

[0015]

[Chemical 4]

(Wherein R ¹ and R ⁴ have the same meanings as those in formula [I]), haloacetonitrile was used, and K. Wakabayashi et al., Bulletin of the Chemical Society of Japan, 4
2 , 2924-2930 (1960), and can be synthesized by cyclizing according to the method.

The following are examples of compounds useful as a free radical generator used in the present invention. However, it goes without saying that the present invention is not limited to the following compounds.

[0018]

[Chemical 5]

[0019]

[Chemical 6]

[0020]

[Chemical 7]

[0021]

[Chemical 8]

[0022]

[Chemical 9]

[0023]

[Chemical 10]

[0024]

[Chemical 11]

[0025]

[Chemical 12]

[0026]

[Chemical 13]

[0027]

[Chemical 14]

[0028]

[Chemical 15]

In the present invention, among the photopolymerization initiators represented by the general formula (I), (b) a compound in which R ³ and R ⁴ are both hydrogen atoms, and (c) at least R ³ and R ⁴ A compound in which one is a halogen atom is used in combination. Among these S-triazine compounds, (b) the compounds in which R ³ and R ⁴ are both hydrogen atoms have λmax in the relatively long wavelength measurement, and the tone reproducibility is relatively good, but the sensitivity is low. . On the other hand, the compound (c) in which at least one of R ³ and R ⁴ is a halogen atom has λmax on the relatively short wavelength side and has a relatively high sensitivity, but has the drawback of poor tone reproducibility. On the other hand, when (b) and (c) are used in combination, a good balance between sensitivity and tone reproducibility can be obtained. In the present invention, the difference in λ max between the S-triazine compounds (b) and (c) is 1 or less.
It is preferably 0 nm or more. If the difference is 10 nm or less, the effect of improving the balance between sensitivity and tone reproducibility is small. λ
Mixing two S-triazines having a large difference in max is particularly useful in a photosensitive composition containing a negative-working diazo resin. The combined amount of the S-triazine compounds (b) and (c) is 0.002 to 20% by weight based on the total amount of the photosensitive composition, and (b)
The weight ratio of (c) is preferably in the range of 20/80 to 80/20. If the amount of the S-triazine compound is less than 0.002% by weight, the sensitivity is insufficient, and the amount is 20% by weight.
When the amount is larger, the compatibility in the photosensitive composition is deteriorated or the sensitivity is lowered. Further, when the ratio of (b) or (c) to the total amount of (b) and (c) is 20% by weight or less, the effect of improving sensitivity and tone reproducibility is small.

The photosensitive composition of the present invention further requires a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator represented by the general formula [I], and a binder if necessary. Then it is composed of a sensitizer. The polymerizable compound having an ethylenically unsaturated bond in the photosensitive composition of the present invention is a compound having at least one ethylenically unsaturated bond in its chemical structure, which is a monomer, a prepolymer, that is, It has a chemical form such as a dimer, a trimer and other oligomers, a mixture thereof and a copolymer thereof. Examples thereof include unsaturated carboxylic acids and salts thereof, esters of unsaturated carboxylic acids with aliphatic polyhydric alcohol compounds, and amides of unsaturated carboxylic acids with aliphatic polyhydric amine compounds.

Specific examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid and maleic acid. Salts of unsaturated carboxylic acids include the alkali metal salts of the aforementioned acids, such as sodium and potassium salts. Specific examples of the ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, Propylene glycol diacrylate, trimethylol propane triacrylate, trimethylol ethane triacrylate,
1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate,
Dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, polyester acrylate oligomer, etc. There is. As the methacrylic acid ester, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, pentaerythritol dimethacrylate, penta Erythritol trimethacrylate, dipentaerythritol dimethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis- [p- (3-methacryloxy-2-hydroxypropoxy) phenyl]
Examples include dimethyl methane and bis- [p- (methacryloxyethoxy) phenyl] dimethyl methane. As itaconic acid esters, ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate , Sorbitol tetri taconate, etc. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetracrotonate. Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocronate. Examples of the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate. Further, a mixture of the above-mentioned esters can also be mentioned.

Specific examples of the amide of an aliphatic polyvalent amine compound and an unsaturated carboxylic acid include methylenebis-acrylamide, methylenebis-methacrylamide, 1,6-hexamethylenebis-acrylamide and 1,6-hexamethylenebis-. Methacrylamide, diethylenetriamine tris acrylamide, xylylene bis acrylamide, xylylene bis methacrylamide and the like.

Another example is Japanese Examined Patent Publication No. 48-417.
No. 08, the polyisocyanate compound having two or more isocyanate groups in one molecule is added with a vinyl monomer having a hydroxyl group represented by the following general formula [III] in two molecules in one molecule. Examples thereof include vinyl urethane compounds containing a polymerizable vinyl group.

CH ₂ = C (R ⁸ ) COOCH ₂ CH (R ⁹ ) OH [II
I] (wherein R ⁸ and R ⁹ represent H or CH ₃ ) When the free radical generator represented by the general formula [I] is used as a photopolymerization initiator in the photosensitive composition, the photosensitive composition is A binder can be contained in the product, if necessary.

As the binder in the photosensitive composition of the present invention, the compatibility with the polymerizable ethylenically unsaturated compound and the photopolymerization initiator leads to the preparation of a coating solution of the composition, and the production of a photosensitive material which leads to coating and drying. It should be good enough not to cause demixing in all the steps, as a photosensitive layer or a resist layer, for example, it should be possible to carry out development treatment after image exposure, whether solution development or peeling development, as a photosensitive layer or a resist layer. Although it is required to have properties such as capable of forming a tough film, it is usually appropriately selected from linear organic high molecular polymers. Specific examples of the binder include chlorinated polyethylene, chlorinated polypropylene, polyacrylic acid alkyl ester (as the alkyl group, methyl group, ethyl group, n-butyl group, iso-butyl group, n
-Hexyl group, 2-ethylhexyl group, etc.), a copolymer of an acrylic acid alkyl ester (the alkyl group is the same as above) and at least one of acrylonitrile, vinyl chloride, vinylidene chloride, styrene, butadiene and the like,
Polyvinyl chloride, copolymer of vinyl chloride and acrylonitrile, polyvinylidene chloride, copolymer of vinylidene chloride and acrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyacrylonitrile, copolymer of acrylonitrile and styrene, acrylonitrile and butadiene And a copolymer with styrene, a polymethacrylic acid alkyl ester (as the alkyl group, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an iso-butyl group, an n-hexyl group, a cyclohexyl group, 2 -Ethylhexyl group, etc.), a copolymer of methacrylic acid alkyl ester (the alkyl group is the same as above) and at least one of monomers such as acrylonitrile, vinyl chloride, vinylidene chloride, styrene and butadiene, polystyrene, poly-α.
-Methylstyrene, polyamide (6-nylon, 6,6
-Nylon etc.), methyl cellulose, ethyl cellulose, acetyl cellulose, polyvinyl formal, polyvinyl butyral and the like.

Further, when a water or alkaline water-soluble organic high molecular polymer is used, water or alkaline water development is possible. Examples of such a high molecular weight polymer include an addition polymer having a carboxylic acid in a side chain, for example, a methacrylic acid copolymer (for example, a copolymer of methyl methacrylate and methacrylic acid, a copolymer of ethyl methacrylate and methacrylic acid). Polymers, copolymers of butyl methacrylate and methacrylic acid, copolymers of allyl methacrylate and methacrylic acid,
Copolymers of ethyl acrylate and methacrylic acid, copolymers of ethyl methacrylate and styrene and methacrylic acid, etc., acrylic acid copolymers (copolymers of ethyl acrylate and acrylic acid, butyl acrylate) There is a copolymer with acrylic acid, a copolymer of ethyl acrylate with styrene and acrylic acid, etc.), further itaconic acid copolymer, crotonic acid copolymer, partially esterified maleic acid copolymer, etc., Similarly, there is an acidic cellulose derivative having a carboxylic acid in the side chain.

These high molecular weight polymers may be used alone as binders, but the mutual compatibility of two or more kinds may cause demixing during the manufacturing process from preparation of coating liquid to coating and drying. It is possible to use high molecular weight polymers which are not so good as a binder by mixing them in an appropriate ratio. The molecular weight of the high molecular weight polymer used as the binder can take a wide range of values depending on the type of the polymer, but in general, it is preferably in the range of 5,000 to 2,000,000, more preferably 10,000 to 1,000,000. is there.

When the photosensitive composition of the present invention further contains a sensitizer, the photopolymerization rate is increased by using it together with a free radical generator represented by the general formula [I], that is, a photopolymerization initiator. A sensitizer is selected. Specific examples of such a sensitizer include benzoin, benzoin methyl ether,
Benzoin ethyl ether, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, 2
-Ethyl-9-anthrone, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-
Butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2-methoxyxanthone, thioxanthone, benzyl, dibenzalacetone, p- (dimethylamino) phenylstyrylketone. , P- (dimethylamino) phenyl p-methylstyryl ketone, benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, benzanthrone and the like. Of these compounds, it is particularly preferable to use Michler's ketone.

Further, as a preferable sensitizer in the present invention, a compound represented by the general formula [IV] described in JP-B-51-48516 can be mentioned.

[0040]

[Chemical 16]

In the formula, R ¹⁰ is an alkyl group (eg, methyl group, ethyl group, propyl group, etc.) or a substituted alkyl group (eg, 2-hydroxyethyl group, 2-methoxyethyl group, carboxymethyl group, 2- Carboxyethyl group). R ¹¹ represents an alkyl group (eg, methyl group, ethyl group, etc.) or an aryl group (eg, phenyl group, p-hydroxyphenyl group, naphthyl group, thienyl group, etc.).

Z ² is a group of non-metal atoms necessary for forming a nitrogen-containing heterocyclic nucleus usually used in cyanine dyes, for example, benzothiazoles (benzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, etc.). ), Naphthothiazoles (α-naphthothiazole, β
-Naphthothiazole, etc.), benzoselenazoles (benzoselenazole, 5-chlorobenzoselenazole, 6
-Methoxybenzoselenazole etc.), naphthoselenazoles (α-naphthoselenazole, β-naphthoselenazole etc.), benzoxazoles (benzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole etc.), naphthoxazole It represents a class (α-naphthoxazole, β-naphthoxazole, etc.).

Specific examples of the compound represented by the general formula [IV] are those having a chemical structure in which Z ² , R ¹⁰ and R ¹¹ are combined, and many exist as known substances. Therefore, it can be appropriately selected and used from these known ones. Further, as a preferable sensitizer in the present invention, Japanese Patent Application No. 60-44027,
A merocyanine dye described in Japanese Patent Application No. 60-44029,
Moreover, the ketocoumarin type compound shown by the following general formula [V] can also be mentioned.

[0044]

[Chemical 17]

Here, R ¹² represents an alkyl group such as a methyl group or an ethyl group. Further, it is desirable to add a thermal polymerization inhibitor to prevent unnecessary thermal polymerization of the polymerizable compound having an ethylenically unsaturated bond during the production or storage of the composition of the present invention. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-
Examples include t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, cuprous chloride, phenothiazine, chloranil, naphthylamine, β-naphthol, nitrobenzene and dinitrobenzene.

In some cases, dyes or pigments such as methylene blue, crystal violet, rhodamine B, fuchsin, auramine, methyl violet, malachite green, parafuchsin, for the purpose of coloring,
Victoria Blue BH, Victoria Pure-Blue BOH, Victoria Pure-Blue BOH naphthalene sulfonate, Oil Blue # 603, Oil Pink # 312, Oil Red 5B, Oil Green # 502.
Dyes such as titanium oxide, carbon black, iron oxide,
Pigments such as phthalocyanine pigments and azo pigments may be added.

A negative-acting diazo resin, for example, a PF ₆ salt of a condensate of p-diazodiphenylamine and formaldehyde, is added in order to improve the adhesion to an aluminum support which has been anodized (sulfuric acid or phosphoric acid) and then treated with silicate. Good. In this case, a storage stabilizer for the diazo resin conventionally used in the negative diazo-based photosensitive composition, an antifouling agent,
For example, it is preferable to add compounds such as phosphoric acid, malic acid, dipicolinic acid, naphthalenesulfonic acid, polyvinylphosphonic acid and the like.

Further, a plasticizer may be added to the photosensitive composition of the present invention, if necessary. Examples of plasticizers include phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, dimethyl glycol phthalate, ethyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, etc. And glycol esters, tricresyl phosphate, triphenyl phosphate and other phosphoric acid esters, diisobutyl adipate, dioctyl adipate, dibutyl sebacate, dibutyl malate and other aliphatic dibasic acid esters.

Further, in the photosensitive composition of the present invention, if necessary, a fluorine-containing surfactant for improving the surface quality of the coating, for example, JP-A-62-170950 and JP-A-62-170950.
-226143, a fluorine-containing copolymer, higher fatty acids and higher fatty acid amides for reducing the influence of oxygen, various additions such as fine particles of silica or the like for reducing adhesiveness or improving vacuum adhesion You may add an agent.

The photosensitive composition of the present invention is used by dissolving the above-mentioned various constituents in a solvent and coating it on a suitable support by a known method. Next, the preferable ratio of the various constituents in this case is expressed in parts by weight relative to 100 parts by weight of the polymerizable compound having an ethylenically unsaturated bond. Preferred range Particularly preferred range Free radical generator represented by general formula [I] 0.01 to 100 parts by weight 0.1 to 30 parts by weight Binder 0 to 1000 〃 0 to 500 〃 Sensitizer 0 to 100 〃 0 〜 20 〃 Thermal polymerization inhibitor 0 〜 10 〃 0 〜 5 〃 Dye or pigment 0 〜 50 〃 0 〜 20 〃 Plasticizer 0 〜 200 〃 0 〜 50 〃 Used when applying the photosensitive composition of the present invention As the solvent to be used, ethylene dichloride, cyclohexanone, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve acetate, methyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, methanol, monochlorobenzene, toluene, ethyl acetate, Lactic acid methyl And the like.
These solvents may be used alone or as a mixture, and a small amount of water may be added depending on the case.

The photosensitive composition of the present invention is suitable as a photosensitive layer of a photosensitive lithographic printing plate. When manufacturing a photosensitive lithographic printing plate, the coating amount is generally 0.1 to 1.0 g as solid content.
/ M ² is suitable, and particularly preferably 0.5 to 5.0 g / m ² . This coating layer may be overcoated with polyvinyl alcohol, for example, as an oxygen barrier layer. Further, a conventionally known mat layer for improving vacuum adhesion, for example, a method described in JP-B-61-28986 may be applied.

As the support suitable for the photosensitive lithographic printing plate, a dimensionally stable plate-like material is used, and those which have been used as the support of the printing plate so far are included. Examples of such a support include paper, paper laminated with plastics (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate such as aluminum (including aluminum alloy), zinc, iron, copper, etc. Cellulose acetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene,
Films of plastics such as polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc., paper or plastic films laminated or vapor-deposited with the above metals are included,
An aluminum plate is particularly preferable. Aluminum plates include pure aluminum and aluminum alloy plates. Various aluminum alloys can be used, such as silicon, copper, manganese, magnesium, chromium, zinc, lead,
An alloy of aluminum with a metal such as bismuth or nickel is used. These compositions include some iron and titanium, as well as other negligible amounts of impurities.

The support is surface-treated if necessary.
For example, in the case of a photosensitive lithographic printing plate, on the surface of the support,
Hydrophilization treatment is performed. There are various hydrophilic treatments. For example, in the case of a support having a plastic surface, chemical treatment, discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment,
So-called surface treatment methods such as laser treatment (for example, US Pat. Nos. 2,764,520, 3,497,407 and 3,145,242,
No. 3,376,208, No. 3,072,483, No. 3,475,193, No.
No. 3,360,448, British Patent No. 788,365, etc.), and those subjected to surface treatment once and then coated with an undercoat layer on the plastic.

Various methods have been devised as a coating method. The first layer is a multi-layered structure in which plastic is adhered and a hydrophobic resin layer having good adhesiveness is applied, and a hydrophilic resin layer is applied as a second layer. And a single layer method in which a layer of a resin containing a hydrophobic group and a hydrophilic group is applied in the same polymer. In the case of a support having a surface of metal, particularly aluminum, surface treatment such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, etc., or anodization treatment is performed. It is preferable. Also, as described in U.S. Pat.No. 2,714,066, an aluminum plate that has been grained and then immersed in an aqueous solution of sodium silicate, and an anodized aluminum plate as described in U.S. Pat. Those obtained by immersing in an aqueous solution of alkali metal silicate after the treatment are also suitably used. The anodizing treatment is, for example, an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, boric acid,
Alternatively, it is carried out by passing a current through an aluminum plate as an anode in an electrolytic solution of an organic acid such as oxalic acid, sulfamic acid or the like, or an aqueous solution or a non-aqueous solution of a salt thereof, or a combination of two or more kinds.

Further, silicate electrodeposition as described in US Pat. No. 3,658,662 is also effective. These hydrophilization treatments are performed to make the surface of the support hydrophilic, in addition to prevent harmful reaction with the photosensitive composition provided thereon and to improve the adhesion to the photosensitive layer. It is given to improve.

Prior to graining the aluminum plate, if necessary, the rolling oil on the surface may be removed, and the surface of the aluminum plate may be pretreated in order to expose a clean aluminum surface. For the former, solvents such as trichlene and surfactants 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. Mechanical methods include a ball polishing method, a plast polishing method, and a brush polishing method in which a water-dispersed slurry of an abrasive such as pumice is rubbed with a nylon brush. As a chemical method, JP-A-54-31187 is used. The method of immersing in a saturated aqueous solution of an aluminum salt of a mineral acid as described in the publication is suitable, and the electrochemical method is a method of alternating current electrolysis in an acidic electrolytic solution such as hydrochloric acid, nitric acid or a combination thereof. Is preferred. Among such surface roughening methods, a surface roughening method combining mechanical surface roughening and electrochemical surface roughening as described in JP-A-55-137993 is particularly preferable.
It is preferable because the adhesion of the oil-sensitive image to the support is strong.

In the graining by the above method, the center line surface roughness (Ha) of the surface of the aluminum plate is 0.2 to 1.0 μm.
It is preferable that the treatment is performed in such a range that The grained aluminum plate is washed with water and chemically etched as required. The etching treatment liquid is usually selected from an aqueous solution of a base or an acid that dissolves aluminum. In this case, the etched surface must not form a coating different from aluminum derived from the etching solution component. Examples of preferable etching agents include sodium hydroxide, potassium hydroxide, trisodium phosphate, disodium phosphate, tripotassium phosphate, dipotassium phosphate as basic substances; sulfuric acid, persulfuric acid, phosphoric acid, hydrochloric acid as acidic substances. Further, salts such as salts thereof, which have a lower ionization tendency than aluminum, for example, salts of zinc, chromium, cobalt, nickel, copper, etc. form an unnecessary film on the etching surface and are not preferred.

These etching agents are most preferably used so that the dissolution rate of the aluminum or alloy to be used is 0.3 to 40 g / m ² per 1 minute of immersion time, when the use concentration and temperature are set. However, it does not matter if it exceeds or falls below this. Etching is performed by immersing an aluminum plate in the above-mentioned etching solution or by applying an etching solution to the aluminum plate, and the etching amount may be treated in the range of 0.5 to 10 g / m ^2. preferable.

As the above-mentioned etching agent, it is desirable to use an aqueous solution of a base because of its high etching rate. In this case, a smut is generated, and thus it is usually desmutted. As the acid used for the desmutting treatment, nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, borofluoric acid, or the like is used. If necessary, the etched aluminum plate is washed with water and anodized. Anodization can be performed by a method conventionally used in this field. Specifically, when a direct current or an alternating current is applied to aluminum in sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, etc., or an aqueous solution or a non-aqueous solution in which two or more of them are combined, aluminum is supported. An anodized film can be formed on the body surface.

The treatment conditions for the anodic oxidation cannot be unconditionally determined because they vary depending on the electrolytic solution used, but generally the concentration of the electrolytic solution is 1 to 80% by weight, and the liquid temperature is 5 to 70%.
℃, current density 0.5-60 amperes / dm ² , voltage 1-10
A range of 0 V and electrolysis time of 30 seconds to 50 minutes is suitable. Among these anodizing treatments, particularly British Patent No. 1,412,76
The method of anodizing in sulfuric acid at a high current density described in U.S. Pat. No. 8,819,058 and the method of anodizing phosphoric acid as an electrolytic bath described in U.S. Pat. No. 3,511,661 are preferable.

The aluminum plate which has been surface-roughened and anodized as described above may be subjected to a hydrophilic treatment if necessary, and preferred examples thereof are disclosed in US Pat. Nos. 2,714,066 and 3,181,461. Alkali metal silicates, such as aqueous sodium silicate or potassium fluorozirconate disclosed in Japanese Patent Publication No. Sho 36-22063 and polyvinylphosphonic acid as disclosed in US Pat. No. 4,153,461. There is a way to handle.

Prior to coating the photosensitive composition of the present invention on the support thus treated, if necessary, it is possible to improve the hydrophilicity and to prevent harmful effects to the photosensitive composition. Various compounds such as polyvinylphosphonic acid, phenylphosphonic acid, sulfonic acid-containing polymer, and carboxylic acid for the purpose of preventing reaction, improving the adhesion to the photosensitive layer, and absorbing halation light from the support. You may coat a containing polymer, a yellow dye, etc.

When the photosensitive composition of the present invention is used for producing a proof plate for printing, a film for an overhead projector, and a film for a second original drawing, polyethylene terephthalate film, cellulose triacetate film, etc. are suitable as a support for these. Examples thereof include transparent films and those obtained by chemically or physically matting the surfaces of these plastic films.

When the photosensitive composition of the present invention is used for producing a film for a photomask, a suitable support is a polyethylene terephthalate film vapor-deposited with aluminum, an aluminum alloy or chromium, or a polyethylene terephthalate film provided with a coloring layer. Can be mentioned. When the composition of the present invention is used as a photoresist, various materials such as a copper plate, a copper plated plate, a stainless plate and a glass plate can be used as a support.

[0066]

[Composition of Photosensitive Solution]

Copolymer of allyl methacrylate / methacrylic acid 3 g (copolymerization molar ratio 85/15) Dipentaerythritol pentaacrylate 1 g PF ₆ salt of a condensate of P-diazodiphenylamine and formaldehyde 0.15 g Photoinitiator (shown in Table 1 ) Dipicolinic acid 0.1 g Behenic acid 0.05 g Behenic acid amide 0.1 g Victoria Pure Blue BOH 0.07 g Megafac F-177 (Dainippon Ink and Chemicals, Inc. 0.05 g Fluorosurfactant) Methyl lactate 10 g Propylene glycol monomethyl ether 35 g Methyl ethyl ketone 25 g Methanol 10 g Water 3.5 g On the photosensitive layer of the photosensitive lithographic printing plate thus obtained, Fuji PS Step Guide manufactured by Fuji Photo Film Co., Ltd. (ΔD =
Gray scale in which the transmission density changes discontinuously at 0.15)
And an EG chart film manufactured by the same company for checking the tone reproducibility were brought into close contact with each other, and exposure was performed for 1 minute from a distance of 70 cm with a 10-amp metal halide lamp. The development was performed with a developer having the following composition described in JP-B-56-42860, and the unexposed portion was removed.

Sodium sulfite 3 g Benzyl alcohol 30 g Triethanolamine 20 g Monoethanolamine 5 g Perex NBL (sodium butylnaphthalene sulfonate: manufactured by Kao Atlas Co., Ltd.) 30 g Water 1000 g The results are shown in Table 1. Note that λmax was measured with an ethanol solution.

Table 1 ─────────────────────────────────── Example Compound (1) Example Compound (12) Sensitivity Tone Solid / tail Reproducibility (λmax = 386nm) (λmax = 372nm) ───────────────────────────────── ─── Example 1 0.1 g 0.25 g 3.0 / 10.0 8-10 μm Example 2 0.175 g 0.175 g 3.0 / 10.0 8 μm Example 3 0.25 g 0.1 g 2.5 / 9.5 6-8 μm ──── ─────────────────────────────── Comparative Example 1 0.35 g −2.0 / 9.0 8 μm Comparative Example 2 0.30 g 0. 05g 2.0 / 9.0 6 to 8 μm Comparative Example 3 0.05 g 0.30 g 3.0 / 10.0 12 μm Comparative Example 4-0.35 g 3.0 / 10.0 12 μm ──────────────────── ──────────────── Sensitivity is a step guide It is used to read of solid / tail.

The tone reproducibility is obtained by reading the minimum thin line width reproduced without thin lines being broken in the EG chart. Conventionally known Comparative Example 1 has good tone reproducibility but low sensitivity. Comparative Example 4 has high sensitivity but poor tone reproducibility. On the other hand, Examples 1 to 3 of the present invention have good results in both sensitivity and tone reproducibility.

However, Comparative Example 2 in which the combined ratio was insufficient
And Comparative Example 3 is insufficient for improving the sensitivity and tone reproducibility. Examples 4 to 10 and Comparative Examples 5 to 12 An aluminum plate (material 1050) having a thickness of 0.30 mm was grained on its surface using a nylon brush and a water suspension of 400 mesh pumice stone, and then well watered. Washed.
It was immersed in 10% sodium hydroxide at 70 ° C. for 60 seconds for etching, washed with running water, neutralized with 20% HNO ₃ , and then washed with water. This was subjected to 1 V in a 1% aqueous nitric acid solution using a sinusoidal alternating current under the condition of V _A = 12.7V.
The electrolytic surface-roughening treatment was carried out with the amount of electricity at the anode of 60 coulomb / dm ² . When the surface roughness was measured, it was 0.6 μ (Ra display). Then, after soaking in 30% H ₂ SO ₄ aqueous solution and desmutting at 50 ° C for 2 minutes, 20% H ₂ SO ₄ was added.
In an aqueous solution, the thickness is 2.7 g / at a current density of 2 A / dm ² .
Anodizing treatment was performed so as to obtain m ² . Then, it was immersed in a 2.5% aqueous solution of sodium silicate at 70 ° C. for 1 minute, washed with water and dried.

On the aluminum plate thus treated, a photosensitive solution having the following composition was applied so that the dry coating weight was 1.8 g / m ^2, and dried at 100 ° C. for 2 minutes to give a photosensitive lithographic printing plate. Obtained. The photopolymerization initiator used and the amount used in the photosensitive solution are shown in Table 2. [Composition of Photosensitive Solution] Copolymer of allyl methacrylate / methacrylic acid 3 g (copolymerization molar ratio 85/15) Dipentaerythritol hexaacrylate 1 g PF ₆ salt of a condensate of P-diazodiphenylamine and formaldehyde 0.2 g Photopolymerization initiation Agents (shown in Table 2) Malic acid 0.05 g Dipicolinic acid 0.05 g Behenic acid 0.07 g Behenic acid amide 0.07 g Victoria pure blue naphthalene sulfonate 0.1 g Megafac F-177 (Dainippon Ink ) 0.05 g Fluorine surfactant) Ethylene glycol monomethyl ether 20 g Propylene glycol monomethyl ether 25 g Methyl ethyl ketone 35 g Water 4 g The photosensitive lithographic printing plate thus obtained was treated in the same manner as in Examples 1-3.

The results are shown in Table 2. λmax was measured with an ethanol solution. Table 2 ─────────────────────────────────── Photoinitiator Sensitivity Tone reproducibility Solid / tail ─ ────────────────────────────────── Example 4 Exemplified Compound (1) Exemplified Compound (13) 3.0 / 10.0 10 μm [λmax 0.175 g [λmax 0.175 g 386 nm] 374 nm] Example 5 Exemplified compound (1) Exemplified compound (18) 3.0 / 100.0 8 to 10 μm [386 nm] 0.175 g [373 nm] 0.175 g Example 6 Exemplified compound (1) Exemplified compound (19) 3.0 / 10.0 10 μm [386 nm] 0.175 g [375 nm] 0.175 g Example 7 Exemplified compound (2) Exemplified compound (12) 3.0 / 10.0 8-10 μm [393 nm] 0.175 g [372 nm] 0.175 g Example 8 Exemplified compound (2) Exemplified compound (13) 3.0 / 10.0 8 to 10 μm [393 nm] 0.175 g [374 nm] 0.175 g Example 9 Exemplified compound (2) Exemplified compound (18) 3.0 / 10.0 10 μm [393 nm] 0.175 g [ 373 nm] 0.175 g Example 10 Exemplified compound (2) Exemplified compound (19) 3.0 / 10.0 8-10 μm [393nm] 0.175g [375nm] 0.175g ──────────────────────────────── Comparative Example 5 Exemplified Compound (1) ─── 2.0 / 9.0 8-10 μm [386 nm] 0.35 g Comparative Example 6 Exemplified Compound (2) ─── 2.0 / 8.5 8-10 μm [393 nm] 0.35 g Comparative Example 7 Exemplified compound (12) ─── 3.0 / 10.0 14 μm [372 nm] 0.35 g Comparative example 8 Exemplified compound (13) ─── 3.0 / 10.0 14 μm [374 nm] 0.35 g Comparative example 9 Exemplified compound (14) ─── 3.0 /10.0 14 μm [373 nm] 0.35 g Comparative Example 10 Exemplified Compound (15) ─── 3.0 / 10.0 14 μm [375 nm] 0.35 g Comparative Example 11 Exemplified Compound (1) Exemplified Compound (2) 2.0 / 9.0 8-10 μm [386 nm] 0.175 g [393 nm] 0.175 g Comparative Example 12 Exemplified Compound (12) Exemplified Compound (19) 3.0 / 10.0 14 μm [372 nm] 0.175 g [375 nm] 0.175 g ──────────────── ─────────────────── Comparative example of known technology In Nos. 5 and 6, tone reproducibility is good, but sensitivity is low. Comparative Examples 7 to 10 have high sensitivity but poor tone reproducibility.
In contrast, Examples 4 to 10 of the present invention have good results in both sensitivity and tone reproducibility.

However, in Comparative Examples 11 to 12 in which the combination method is different from that of the present invention, no effect is recognized for improvement in sensitivity and tone reproducibility.

Claims (2)

[Claims] 1. A compound (a) having at least one ethylenically unsaturated double bond capable of addition polymerization, and a photosensitive S-triazine compound represented by the following general formula (I), wherein (b) R A compound in which ³ and R ⁴ are both hydrogen atoms and (c) a compound in which at least one of R ³ and R ⁴ is a halogen atom have a weight ratio of (b) and (c) of 20/80 to 8
A photosensitive composition containing 0/20. [Chemical 1] In the general formula [I], R ¹ and R ² may be the same or different from each other, and are a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, -COR ⁵ or -CO-.
NR ⁶ R ⁷ is shown, or R ¹ and R ² may form a heterocyclic ring composed of a non-metal atom together with the nitrogen atom to which it is bonded. R ⁵ represents an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, and R ⁶ and R ⁷ may be the same or different from each other, a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group. Represents a group. R ³ , R ⁴
Represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. X and Y may be the same as or different from each other and each represents a chlorine atom or a bromine atom. m and n are 0, 1 or 2
Represents 2. The photosensitive composition according to claim 1, wherein the difference in λmax between the S-triazine compounds (b) and (c) is 10 nm or more.