JPH0157777B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to photosensitive compositions containing compounds that generate free radicals when exposed to light. More specifically, the present invention relates to a photosensitive composition containing a disulfone compound as a free radical generating agent. Compounds that decompose to produce free radicals upon exposure to light (free radical generators) are well known in the graphic arts field. They are widely used as photoinitiators in photopolymerizable compositions, photoactivators in free radical photographic compositions, and photoinitiators for reactions catalyzed by photogenerated acids. Such free radical generators are used to make a variety of photosensitive materials useful in printing, duplication, copying and other imaging systems. Organic halogen compounds are generally known as the above-mentioned free radical generating agents. Organic halogen compounds photolyze to give halogen radicals such as chlorine radicals and bromine radicals. These halogen radicals are good hydrogen abstractors and produce acids in the presence of hydrogen donors. Furthermore, halogen free radicals are good polymerization initiators, and a polymerization reaction occurs when a compound having a polymerizable double bond is present. Applications of these to free radical photography and photopolymerization processes are discussed in J. Kosar,
"Light Sensitive Systems" J. Willy & Sons (New York. 1965) PP -
180-181 and PP361-370. Conventionally, carbon tetrabromide, iodoform, tribromoacetophenone, and the like have been widely used as representative compounds that generate halogen free radicals by the action of this type of light. However, since these free radical generating agents sublimate or have a bad odor, when used in a photosensitive material with a photosensitive layer provided on a support, the photosensitive layer may be damaged during the production, use, or storage of the photosensitive material. It volatilized from the water, reducing its effectiveness and becoming a sanitary problem. Furthermore, these free radical generating agents have problems in compatibility with other elements contained in the photosensitive layer. Furthermore, since they have low photodecomposition sensitivity to light sources (such as metal halide lamps) commonly used in the production of printing plates, it is necessary to add them in large quantities in order to exhibit sufficient effects. Therefore, it is an object of the present invention to provide a photosensitive composition that exhibits high sensitivity to commonly used ultraviolet light sources. Another object of the present invention is to provide photosensitive compositions containing novel free radical generators. Yet another object of the present invention is to provide a highly sensitive photosensitive composition capable of providing a photosensitive layer with excellent physical properties and developability. In order to achieve the above object, the present inventors have conducted various studies and have arrived at the present invention.
Its gist includes a disulfone compound represented by the following general formula (). R ₁ −SO ₂ −SO ₂ −R ₂ () (wherein R ₁ and R ₂ each independently represent an aryl group or a substituted aryl group.) It is a photosensitive composition. R ₁ and R ₂ in the compound represented by the general formula () each independently represent an aryl group or a substituted aryl group, and the aryl group is preferably a monocyclic or bicyclic group, such as a phenyl group, an α- Includes naphthyl group, β-naphthyl group, etc. The substituted aryl group for R ₁ and R ₂ is an alkyl group having 1 to 2 carbon atoms such as a methyl group or an ethyl group, or an alkyl group having 1 to 2 carbon atoms such as a methoxy group or an ethoxy group. ~2
This includes those substituted with alkoxy groups such as halogen atoms such as chlorine atoms and bromine atoms, nitro groups, phenyl groups, carboxy groups, cyano groups, and specifically, 4-chlorophenyl groups, 2-chlorophenyl groups, 4-bromophenyl group, 4-nitrophenyl group, 3-nitrophenyl group, 4-phenylphenyl group, 4-methylphenyl group, 2-methylphenyl group, 4-ethylphenyl group, 4-methoxyphenyl group, 2-methoxyphenyl group, 4
-Ethoxyphenyl group, 2-carboxyphenyl group, 4-cyanophenyl group, 4-methyl-1-naphthyl group, 4-chloro-1-naphthyl group, 5-nitro-1-naphthyl group, 6-chloro-2 -naphthyl group, 4-bromo-2-naphthyl group, 5-nitro-2-naphthyl group, etc. The compound represented by the general formula () used in the present invention is described in GCDenzer, Jr. et al., Journal of
Organic Chemistry, 31--, 3418-3419 (1966)
Method of Description, by T.P. Hilditch, Journal of
Chemical Society, 93--, 1524-1527 (1908) or O. Hinsberg, Berichte.
der Deutschen Chemischen Gesell-schaft,
49--, 2593-2594 (1916). That is, a method of synthesizing from sulfinic acid represented by the general formula () using cobalt sulfate () in an aqueous sulfuric acid solution, a method of synthesizing from sulfonic acid chloride represented by the general formula () using ethyl xanthate, or Examples include a method of synthesizing a sulfinic acid represented by the general formula () and a sulfonic acid chloride represented by the general formula () under basic conditions. R-SO ₂ H () R'-SO ₂ Cl () (Here, R and R' have the same meanings as R ₁ and R ₂ defined in the general formula ().) Specific examples of compounds represented by the general formula () used are illustrated below. Some production examples of compounds represented by the general formula () are shown below. Production example 1 Diphenyl disulfone (free radical generator No. 1)
Production of sodium benzenesulfinate dihydrate 22.0g
and 17.7 g of benzenesulfonic acid chloride were added to 25 ml of water and stirred at room temperature for 24 hours. Add the reactant to water500
ml, collect the precipitate, and recrystallize it from a mixed solvent of benzene and ethanol to obtain diphenyldisulfone.
5.0 g was obtained (melting point 198-200°C). Production example 2 Production of dip-p-chlorophenyl disulfone (free radical generator No. 4) Dissolve 189 g of sodium sulfite in 600 ml of water and dissolve
The mixture was heated to ~70°C, and 63 g of p-chlorobenzenesulfonic acid chloride was added thereto, followed by reaction at 50 to 60°C for 5 hours. After removing the insoluble matter, the reaction solution was returned to room temperature, and concentrated hydrochloric acid was added to make the reaction system acidic. Collect the precipitate and add p-chlorobenzenesulfinic acid.
Obtained 52g. 8.8g of p-chlorobenzenesulfuric acid and 15g of water
ml and to this was added a solution of 2 g of sodium hydroxide dissolved in 5 ml of water. While stirring this solution at room temperature, a solution of 10.6 g of p-chlorobenzenesulfonic acid chloride dissolved in 20 ml of acetonitrile was added, and the reaction was further stirred at room temperature for 24 hours. Pour the reaction solution into 300 ml of water, collect the precipitate, recrystallize it from a mixed solvent of benzene and ethanol, and add
Obtained 3.0 g of chlorophenyl disulfone (melting point 193
~195℃). Production Example 3 Production of 2,4-dimethylphenyl p-chlorophenyl disulfone (free radical generator No. 9) Add 20 ml of water to 9.7 g of p-chlorobenzenesulfinic acid produced in Production Example 2, and add sodium carbonate to this. A solution of 3.2 g dissolved in 10 ml of water was added. A solution of 10.2 g of 2,4-dimethylbenzenesulfonic acid chloride dissolved in 10 ml of acetone was added dropwise to the above reaction solution at room temperature, and the mixture was further heated for 24 hours at room temperature.
The reaction was stirred for hours. Pour the reaction solution into 250 ml of water, collect the precipitate, recrystallize from ethanol,
2.5 g of 4-dimethylphenyl p-chlorophenyl disulfone was obtained (melting point 158-161°C). Production example 4 Production of α-naphthyl p-methylphenyl disulfone (free radical generator No. 14) Sodium p-toluenesulfinate dihydrate
11.8 g was dissolved in 20 ml of water, 11.3 g of α-naphthalenesulfonic acid chloride was added thereto, and the reaction was stirred at room temperature for 24 hours. 250 ml of water was added to this, the precipitate was collected, and recrystallized from a mixed solvent of benzene and ethanol to obtain 6.5 g of α-naphthyl p-methylphenyl disulfone (melting point: 185-186°C). Production Example 5 Production of 1-(4-ethoxy)naphthyl p-chlorophenyl disulfone (free radical generator No. 16) 49.2 g of sodium 4-hydroxy-1-naphthalene sulfonate and 16.0 g of sodium hydroxide were dissolved in water.
The solution was dissolved in 150 ml, and 30.8 g of diethyl sulfate was added dropwise with stirring at room temperature, followed by further reaction at 40 to 50°C for 2 hours. After returning to room temperature, add 40g of sodium chloride.
4-ethoxy-
40 g of sodium 1-naphthalenesulfonate was obtained. 25 g of phosphorus pentachloride was added to 50 g of phosphorus oxychloride, and while stirring, 27.4 g of sodium 4-ethoxy-1-naphthalenesulfonate was added, and the mixture was reacted at 100 to 110° C. for 6 hours. After returning to room temperature, the mixture was poured into ice water and the resulting precipitate was collected to obtain 20 g of 4-ethoxy-1-naphthalenesulfonic acid chloride. 6.2 g of p-chlorobenzenesulfinic acid produced in Production Example 2 was added to 30 ml of water, a solution of 1.5 g of sodium carbonate dissolved in 10 ml of water was added with stirring, and 8.1 g of 4-ethoxy-1-naphthalenesulfonic acid chloride was added to 1 g of 4-ethoxy-1-naphthalenesulfonic acid chloride. , 4-dioxane (30 ml) was added dropwise, and the mixture was stirred and reacted at room temperature for 24 hours. After adding 200ml of water, collect the precipitate.
Recrystallized from a mixed solvent of benzene and ethanol.
2.5 g of (4-ethoxy)naphthyl p-chlorophenyl disulfone was obtained (melting point 104-106°C). The compound represented by the above general formula () is approximately
When irradiated with actinic radiation within the range of 250 nm to about 500 nm, it generates free radicals very efficiently. Therefore, photosensitive compositions containing as an essential component a component that generates free radicals when irradiated with actinic rays (hereinafter referred to as free radical generator), such as lithography, letterpress, intaglio printing, etc. Photosensitive compositions used to produce light-sensitive materials, photoresist materials and other photographic elements that are subjected to plate making and which, upon exposure alone, immediately provide a visible contrast between the unexposed areas. When a compound represented by the above general formula is used as the free radical generator of the composition, a highly sensitive photosensitive composition can be obtained. The compound represented by the general formula () according to the present invention can be added to a photosensitive resist-forming composition for producing lithographic printing plates, IC circuits, photomasks, etc., immediately between the non-exposed area and the non-exposed area without causing any phenomenon upon exposure. This is particularly useful when providing the ability to provide visible contrast (hereinafter referred to as printout ability). Since a photosensitive resist composition having such printout ability can obtain a visible image only by exposure under a yellow safety light during an exposure operation, it can be used, for example, in the process of exposing many printing plates at the same time. When printing is interrupted, it becomes possible for the plate maker to know whether the plate given to him has been exposed or not. Similarly, for example, when a large plate is exposed to light many times, such as in the so-called reprint printing method when making planographic printing plates,
The operator can immediately see which parts have been exposed. The composition used to provide such printout ability (hereinafter referred to as printout composition) contains a free radical generating agent and a color changing agent that changes color due to the free radicals generated from the free radical generating agent. According to the present invention, a compound represented by the above general formula () is used as the free radical generating agent. In the present invention, as a color change agent, there are two types: one that changes from an originally colorless state to a colored state due to the action of a photoseparation product of a free radical generator (a compound represented by the above general formula ()), and one that changes from an originally colorless state to a colored state. There are two types: those that have color and those that change color or bleach. Typical examples of color changing agents belonging to the former type include arylamines. Arylamines suitable for this purpose include simple arylamines such as primary and secondary aromatic amines, as well as so-called leuco dyes, examples of which are as follows. Diphenylamine, dibenzylaniline, triphenylamine, diethylaniline, diphenyl-p-phenylenediamine, p-toluidine,
4,4'-biphenyldiamine, o-chloroaniline, o-bromoaniline, 4-chloro-o-phenylenediamine, o-bromo-N,N-dimethylaniline, 1,2,3-triphenylguanidine, Naphthylamine, diaminodiphenylmethane, aniline, 2,5-dichloroaniline, N-
methyldiphenylamine, o-toluidine, p,
p′-tetramethyldiaminodiphenylmethane,
N,N-dimethyl-p-phenylenediamine,
1,2-dianilinoethylene, p,p′,p″-hexamethyltriaminotriphenylmethane, p,
p′-tetramethyldiaminotriphenylmethane,
p,p′-tetramethyldiaminodiphenylmethylimine, p,p′,p″-triamino-o-methyltriphenylmethane, p,p′,p″-triaminotriphenylcarbinol, p,p′- tetramethylaminodiphenyl-4-anilinonaphthylmethane,
p, p′, p″-triaminotriphenylmethane,
p,p′,p″-hexapropyltriaminotriphenylmethane. Also, as a color-changing agent that originally has a unique color, this color changes or is decolored by the photodecomposition product of the free radical generating agent. Various dyes such as , diphenylmethane, triphenylmethane, thiazine, oxazine, xanthene, anthraquinone, iminonaphthoquinone, and azomethine are effectively used. Examples of these are as follows. Brilliant green, eosin, ethyl violet, erythrosin B, methyl green, crystal violet, basic fuchsin, phenolphthalein, 1,3-diphenyl triazine, alizarin red S, thymol phthalein,
Methyl Violet 2B, Quinaldine Red, Rose Bengal, Methanil Yellow, Thymol Sulfophthalein, Xylenol Blue, Methyl Orange, Orange, Diphenylthiocarbazone,
2,7-dichlorofluorescein, paramethyl red, congo red, benzopurpurin 4B,
α-Naphthyl Red, Nile Blue 2B, Nile Blue A, Phenacetarin, Methyl Violet, Malachite Green, Parafuchsin, Oil Blue #603 [manufactured by Orient Chemical Industry Co., Ltd.], Oil Pink #312 [manufactured by Orient Chemical Industry Co., Ltd.] , Oil Red 5B [manufactured by Orient Chemical Industry Co., Ltd.], Oil Scarlet #308 [manufactured by Orient Chemical Industry Co., Ltd.], Oil Red OG [manufactured by Orient Chemical Industry Co., Ltd.], Oil Red RR [manufactured by Orient Chemical Industry Co., Ltd.] ], Oil Green #502 [manufactured by Orient Chemical Industry Co., Ltd.], Spiroled BEH Special [manufactured by Hodogaya Chemical Industry Co., Ltd.]
], m-cresol purple, cresol red, rhodamine B, rhodamine 6G, first aid biolette P, sulfolotamine B,
Auramine, 4-p-diethylaminophenyl imino naphthoquinone, 2-carboxyanilino-4
-p-diethylaminophenylimino naphthoquinone, 2-carbostearylamino-4-p-dihydroxyethyl-amino-phenylimino naphthoquinone, p-methoxybenzoyl-p'-diethylamino-o'-methylphenyliminoacetanilide, cyano -p-diethylaminophenyl iminoacetanilide, 1-phenyl-3-methyl-
4-p-diethylaminophenylimino-5-pyrazolone, 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone. The ratio of the color change agent as described above to the compound represented by the general formula () is about 0.01 part by weight to about 100 parts by weight, more preferably about 100 parts by weight of the compound represented by the general formula () per 1 part by weight of the color change agent. It is used in a range of 0.1 to 10 parts by weight, most preferably 0.5 to 5 parts by weight. On the other hand, the photosensitive resist-forming composition, which is the object to which printout ability is imparted by the printout composition according to the present invention, can be used to prepare various printing plates such as lithographic printing plates, IC circuits, photomasks, etc. It includes a variety of things that are used to do this. The typical ones will be explained below. (1) Composition made of diazo resin The diazo resin represented by the condensate of p-diazodiphenylamine and paraformaldehyde may be water-soluble or water-insoluble, but preferably water-insoluble and water-insoluble. Those soluble in common organic solvents are used. Particularly preferred diazo compounds include salts of condensates of p-diazophenylamine and formaldehyde or acetaldehyde, such as phenol salts, fluorocaprates, and triisopropylnaphthalenesulfonic acid, 4,4-biphenyldisulfonic acid, 5 -Nitroortho-toluenesulfonic acid, 5-sulfosalicylic acid, 2,5-dimethylbenzenesulfonic acid, 2-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-
Bromobenzenesulfonic acid, 2-chloro-5-
Nitrobenzenesulfonic acid, 2-fluorocaprylnaphthalenesulfonic acid, 1-naphthol-
A compound having two or more diazo groups in one molecule, such as salts of sulfonic acids such as 5-sulfonic acid, 2-methoxy-4-hydroxy-5-benzoyl-benzenesulfonic acid, and para-toluenesulfonic acid. . Other desirable diazo resins include a condensate of 2,5-dimethoxy-4-p-tolylmercapton benzenediazonium and formaldehyde containing the above salts, 2,5-dimethoxy-4-p-tolylmercapton, and formaldehyde
Contains a condensate of -dimethoxy-4-morpholinobenzenediazonium and formaldehyde or acetaldehyde. Also preferred are the diazo resins described in British Patent No. 1312925. The diazo resin can be used alone as a photoresist for making a resist, but is preferably used in conjunction with a binder. Various polymer compounds can be used as such binders, including hydroxy, amino,
Those containing groups such as carboxylic acid, amide, sulfonamide, active methylene, thioalcohol, and epoxy are preferred. Such preferred binders include sierachiac as described in GB 1350521, hydroxyethyl acrylate units or hydroxyl acrylate units as described in GB 1460978 and US 4123276. Polymers containing ethyl methacrylate units as the main repeat unit, polyamide resins as described in US Pat. No. 3,751,257, phenolic resins as described in British Patent No. 1,074,392 and e.g. polyvinyl formal resins, Polyvinyl acetal resins such as butyral resins, linear polyurethane resins as described in U.S. Pat. No. 3,660,097, phthalated resins of polyvinyl alcohol, epoxy resins condensed from bisphenol A and epichlorohydrin, polyaminostyrenes and polyalkyls. polymers containing amino groups, such as amino (meth)acrylates,
Celluloses such as cellulose acetate, cellulose alkyl ether, and cellulose acetate phthalate are included. The content of the binder in the photosensitive resist-forming composition is suitably 40 to 95% by weight. As the amount of binder increases (ie, as the amount of diazo resin decreases), the photosensitivity naturally increases, but the stability over time decreases. The optimum amount of binder is about 70-90% by weight. The composition comprising the diazo resin may further contain phosphoric acid as described in U.S. Pat. No. 3,236,646;
Additives such as dyes and pigments that are not color changing agents can be added. (2) Composition consisting of an o-quinonediazide compound A particularly preferred o-quinonediazide compound is o-quinonediazide compound.
- Naphthoquinonediazide compounds, such as U.S. Patent No. 2766118, U.S. Patent No. 2767092, U.S. Patent No. 2767092,
No. 2772972, No. 2859112, No. 2907665,
Same No. 3046110, Same No. 346111, Same No. 3046115
No. 3046118, No. 3046119, No. 3046119, No. 3046118, No. 3046119, No.
No. 3046120, No. 3046121, No. 3046122,
Same No. 3046123, Same No. 3061430, Same No. 3102809
No. 3106465, No. 36354709, No. 36354709, No. 3106465, No. 36354709, No.
It is described in many publications including the specifications of No. 3647443, and these can be suitably used. Among these, o-naphthoquinonediazide sulfonic acid ester or o-naphthoquinonediazidecarboxylic acid ester of an aromatic hydroxy compound, and o-naphthoquinonediazide sulfonic acid amide or o-naphthoquinonediazidecarboxylic acid amide of an aromatic amino compound are particularly preferred. , in particular, a condensate of pyrogallol and acetone described in U.S. Pat.
Polyester having a hydroxyl group at the terminal described in the specification of No. 4028111 is ester-reacted with o-naphthoquinonediazide sulfonic acid or o-naphthoquinonediazidecarboxylic acid, which is described in the specification of British Patent No. 1494043. U.S. Pat.
A copolymer of p-aminostyrene and other copolymerizable monomers, as described in No. 3759711, which is subjected to an amide reaction with o-naphthoquinonediazide sulfonic acid or o-naphthoquinonediazidecarboxylic acid is extremely Excellent. Although these o-naphthoquinone diazide compounds can be used alone, it is preferable to use them in combination with an alkali-soluble resin. Suitable alkali-soluble resins include novolac type phenolic resins, and specifically include phenol formaldehyde resins, o-cresol formaldehyde resins, m-cresol formaldehyde resins, and the like. Furthermore, the 1970s
As described in Publication No. 125806, in addition to the above-mentioned phenol resin, a phenol substituted with an alkyl group having 3 to 8 carbon atoms such as t-butylphenol formaldehyde resin or a condensate of cresol and formaldehyde is used. It is even more preferable to use them together. The alkali-soluble resin is contained in an amount of about 50 to about 85% by weight, more preferably 60 to 80% by weight, based on the total weight of the photosensitive resist-forming composition. The photosensitive composition comprising the o-quinonediazide compound may further contain pigments, dyes, plasticizers, etc. that are not color change agents, if necessary. (3) Composition comprising a photosensitive azide compound A suitable photosensitive azide compound is an aromatic azide compound in which an azide group is bonded to an aromatic ring directly or via a carbonyl group or a sulfonyl group. In these, the azide group is decomposed by light to produce nitrene, which undergoes various reactions and becomes insolubilized. Preferred aromatic azide compounds include compounds containing one or more groups such as azidophenyl, azidostyryl, azidobenthal, azidobenzoyl and azidocinnamoyl, for example 4,
4′-Diazidochalcone, 4-azido-4′-(4
-azidobenzoylethoxy)chalcone, N,
N-bis-p-azidobenzal-p-phenylenediamine, 1,2,6-tri(4'-azidobenzoxy)hexane, 2-azido-3-chloro-benzoquinone, 2,4-diazido-4'-ethoxyazobenzene , 2,6-di(4′-azidobenzal)-4-methylcyclohexanone, 4,
4'-Diazidobenzophenone, 2,5-diazido-3,6-dichlorobenzoquinone, 2,5-
Bis(4-azidostyryl)-1,3,4-oxadiazole, 2-(4-azidocinnamoyl)thiophene, 2,5-di(4'-azidobenzal)cyclohexanone, 4,4'-diazidodiphenyl Methane, 1-(4-azidophenyl)
-5-Frill-2-Penta-2,4-Diene-
1-one, 1-(4-azidophenyl)-5-
(4-methoxyphenyl)-penta-1,4-
Dien-3-one, 1-(4-azidophenyl)-3-(1-naphthyl)propen-1-one, 1-(4-azidophenyl)-3-(4-
dimethylaminophenyl)-propan-1-one, 1-(4-azidophenyl)-5-phenyl-1,4-pentadien-3-one, 1-
(4-azidophenyl)-3-(4-nitrophenyl)-2-propen-1-one, 1-(4
-azidophenyl)-3-(2-furyl)-2
-propen-1-one, 1,2,6-tri(4'-azidobenzoxy)hexane, 2,6-
Bis-(4-azidobenzylidine-pt-butyl)cyclohexanone, 4,4'-diazidodibenzalacetone, 4,4'-diazidostilbene-2,2'-disulfonic acid, 4'-azide Benzalacetophenone-2-sulfonic acid, 4,4'-
Diazidostilbene-α-carboxylic acid, di-
(4-azido-2'-hydroxybenzal)acetone-2-sulfonic acid, 4-azidobenzalacetophenone-2-sulfonic acid, 2-azido-
1,4-dibenzenesulfonylaminonaphthalene, 4,4'-diazide-stilbene-2,2'-
Examples include disulfonic acid anilide. In addition to these low molecular weight aromatic azide compounds, there are also
No. 45-9613, No. 45-24915, No. 45-25713,
JP-A No. 50-5102, No. 50-84302, No. 50-
The azide group-containing polymers described in Patent Publications No. 84303 and No. 53-12984 are also suitable. These photosensitive azide compounds are preferably used together with a polymer compound as a binder. Preferred binders include alkali-soluble resins, such as natural resins such as silica and rosin, novolac type phenolic resins such as phenol formaldehyde resins and m-cresol formaldehyde resins, and polyacrylic acid, polymethacrylic acid, methacrylic acid-styrene resins, etc. Polymers, homopolymers of unsaturated carboxylic acids such as methacrylic acid-methyl acrylate copolymers, styrene-maleic anhydride copolymers, or copolymers of these with other copolymerizable monomers, polyvinyl acetate Examples include resins in which partially or completely saponified products are partially acetalized with aldehydes such as acetaldehyde, benzaldehyde, hydroxybenzaldehyde, and carboxybenzaldehyde, and polyhydroxystyrene. Furthermore, organic solvent soluble resins including cellulose alkyl ethers such as cellulose methyl ether and cellulose ethyl ether can also be used as binders. The binder is preferably contained in an amount ranging from about 10% by weight to about 90% by weight based on the total weight of the composition comprising the photosensitive azide compound. The composition comprising the photosensitive azide compound may further contain dyes and pigments that are not discolorants, plasticizers such as phthalates, phosphates, aliphatic carboxylates, glycols, and sulfonamides, such as Michler's ketone, 9- Fluorenone, 1-nitropyrene, 1,8-dinitropyrene, 2-chloro-1,2-benzanthraquinone, 2-bromo-1,2-benzanthraquinone, pyrene-1,6-quinone, 2-chloro-1,8 -Additives such as sensitizers such as phthaloylnaphthalene and cyanoacridine can be added. (4) In the main chain or side chain of the polymer

[Formula] A composition consisting of a polymer compound containing a group as a photosensitive group in the main chain or side chain of the polymer.

Those whose main component is a photosensitive polymer such as polyesters, polyamides, and polycarbonates containing [Formula] (for example, U.S. Pat.
Compounds as described in each specification of the No. 1); compounds whose main components are photosensitive polyesters derived from (2-properidene)malonic acid compounds such as cinnamylidenemalonic acid and difunctional glycols. (e.g. U.S. Patent No. 2956878
3,173,787); cinnamate esters of hydroxyl-containing polymers such as polyvinyl alcohol, starch, cellulose and their analogs (e.g. Patent No. 2690966, Patent No. 2752372,
Photosensitive polymers such as those described in various specifications such as No. 2732301 are included. These compositions may also contain sensitizers, stabilizers, plasticizers, pigments and dyes other than color change agents, and the like. (5) Photopolymerizable composition comprising an addition polymerizable unsaturated compound This composition preferably comprises (a) at least 2
It consists of a vinyl monomer having five terminal vinyl groups, (b) a photopolymerization initiator, and (c) a polymer compound as a binder. As the vinyl monomer of component (a),
No. 5093, Special Publication No. 14719, Special Publication No. 14719, Special Publication No. 28727, Special Publication No. 44-28727
Acrylic or methacrylic esters of polyols, such as diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, etc. ) acrylate, etc., or methylenebis(meth)acrylamide, ethylenebis(meth)
Bis(meth)acrylamides such as acrylamide, or unsaturated monomers containing urethane groups, such as di-(2'-methacryloxyethyl)-2,4-tolylene diurethane, di-
Examples include reaction products of diol mono(meth)acrylate and diisocyanate such as (2'-acryloxyethyl)trimethylene diurethane. As the photopolymerization initiator of component (b), the compound represented by the above general formula () can be used, but other types can also be used. For example, "Light Sensitive Systems" by J. Courser.
Examples include carbonyl compounds, organic sulfur compounds, peroxides, redox compounds, azo and diazo compounds, halogen compounds, and photoreducible dyes as described in Chapter 5. More specifically, it is disclosed in British Patent No. 1459563. On the other hand, various known polymers can be used as the binder for component (c). Specific binder details can be found in U.S. Patent No. 4,072,527
It is stated in the specification of the No. Furthermore, British patent no.
The chlorinated polyolefins described in US Pat. No. 1,459,563 are particularly preferred binders. Component (a) and component (c) have a weight ratio of 1:9 to 6:4
Contained in combination within the range. In addition, component (b) is the component
It is contained in a range of 0.5 to 10% by weight based on (a). The photopolymerizable composition further includes a thermal polymerization inhibitor,
It is possible to contain dyes and pigments that are not plasticizers or color change agents. When such a photosensitive resist-forming composition contains the printout composition, based on 100 parts by weight of the photosensitive resist-forming composition,
From about 0.1 parts by weight to about 0.1 parts by weight of the printout composition
It can be contained in an amount of 150 parts by weight, more preferably 1 to 60 parts by weight. Examples of solvents used when applying the photosensitive resist-forming composition imparted with printout ability include ethylene dichloride, cyclohexanone, methyl ethyl ketone, 2-methoxyethyl acetate, monochlorobenzene, toluene, and ethyl acetate. These can be used alone or in combination. A photosensitive resist-forming composition that has been given such printout ability is a photosensitive lithographic printing plate (also called a presensitized plate) that is used especially for creating a lithographic printing plate, and is called a PS plate. It is abbreviated as.)
It is advantageously used as a photosensitive layer. In this case, the support may be, for example, a metal plate made of aluminum (including aluminum alloys), zinc, iron, copper, etc., or a plastic on which such a metal is laminated or vapor-deposited, and most preferably an aluminum plate. be. In the case of a support having a surface of metal, especially aluminum, surface treatments such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, etc., or anodization treatment are performed. It is preferable.
In addition, as described in U.S. Patent No. 2,714,066, an aluminum plate that has been grained and then immersed in a sodium silicate aqueous solution, and as described in U.S. Pat. No. 3,181,461, an aluminum plate can be used as an anode. Those obtained by oxidation treatment and then immersion treatment in an aqueous solution of an alkali metal silicate are also suitably used. The above-mentioned anodizing treatment is carried out using, for example, an aqueous or non-aqueous solution of an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, or boric acid, or an organic acid such as oxalic acid or sulfamic acid, or a salt thereof, either alone or in combination. Among these, it is particularly preferably carried out by passing an electric current through an aluminum plate as an anode in an aqueous solution of phosphoric acid, sulfuric acid, or a mixture thereof. Also effective is silicate electrodeposition as described in US Pat. No. 3,658,662. Furthermore, as described in British Patent No. 1208224, an aluminum plate which is electrolyzed with alternating current in a hydrochloric acid electrolyte and then anodized in a sulfuric acid electrolyte is also preferred. Further, it is preferable to provide an undercoat layer of a cellulose resin containing a water-soluble salt of a metal such as zinc on the aluminum plate anodized in the above process in order to prevent scum during printing. The amount of photosensitive layer provided on such a support is from about 0.1 to about 7 g/m ² , preferably from 0.5 to 4 g/m 2 .
^m2 range. The thus obtained PS plate is subjected to image exposure, and then an image is formed by processing including development using a conventional method. For example, in the case of a PS plate having a photosensitive layer of a photosensitive composition in which the composition (1) made of diazo resin contains a printout composition,
After image exposure, the unexposed portions of the photosensitive layer are removed by development to obtain a lithographic printing plate. In addition, in the case of a PS plate having a photosensitive layer made of a photosensitive composition containing a printout composition in the composition (2) above, after image exposure, the exposed portion is removed by developing with an alkaline aqueous solution. A lithographic printing plate is obtained. No matter what kind of photosensitive layer the PS version has,
The ability to print out according to the present invention does not require any special measures, and a conventionally known developer suitable for each photosensitive composition can be used.
It can be developed. The photosensitive resist-forming composition imparted with the above-mentioned printout ability can be used for producing printing proof plates, films for overhead projectors, and films for second originals. Suitable supports include transparent films such as polyethylene terephthalate film and cellulose triacetate film, and plastic films whose surfaces have been chemically or physically matted. Further, the above composition can also be used for producing a film for photomasks. Suitable supports include polyethylene terephthalate films deposited with aluminum, aluminum alloys, or chromium, and polyethylene terephthalate films provided with colored layers. Furthermore, the composition described above can be used as a photoresist. In this case, various materials such as a copper plate, a copper plated plate, a stainless steel plate, a glass plate, etc. can be used as the support. When the free radical generating agent according to the present invention is exposed to light in a photosensitive resist-forming composition containing various photosensitive resist-forming compounds, it decomposes and efficiently and instantly discolors the coexisting color-changing agent. That is surprising. As a result, a clear boundary is obtained between the exposed and unexposed areas, which can be recognized as a visible image with rich contrast. Further, since a wide range of color changing agents can be used, an appropriate color changing agent can be selected when various additives are added to improve the performance of the photosensitive composition. Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 The surface was grained and anodized to a thickness of 0.24 mm.
Apply the following photosensitive solution to an aluminum plate and heat it at 100℃.
and dried for 2 minutes. Polyester synthesized by condensation of ethyl p-phenylene diacrylate and equimolar amount of 1,4-bis-β-hydroxyethoxycyclohexane (molecular weight approximately 8000) 0.5g 2-benzoylmethylene-3-methyl-β-naphtho Thiazoline 0.03g Free radical generator (listed in Table 1) 0.008g Leucocrystal violet 0.008g Monochlorobenzene 9g Ethylene dichloride 6g The coating weight after drying was 1.2g/m ² . Each of these photosensitive lithographic printing plates was exposed to light through a transparent negative using Plano PS Printer A3 (manufactured by Fuji Photo Film), and the optical density of the photosensitive layer in the exposed and unexposed areas was measured. The image obtained by exposure is the difference (ΔD) between the optical density of the exposed area and that of the unexposed area.
The larger the value, the clearer the image appears. In addition, after exposing under the same conditions as above through a gray scale (21 steps, with an optical density difference of 0.15 between two adjacent steps and an optical density of the first step of 0.1), the surface was exposed using a developer with the following composition. The resist was developed by wiping it, and the resist sensitivity was examined. Sensitivity is indicated by the number of solid steps (the higher the number of steps, the higher the sensitivity). γ-Butyrolactone 1000.0ml Glycerol 100.0ml Methyl abietate 10.0ml Hydrogenated resin (Stabelite resin from Hercules Powder) 1.0g Wetting agent (Zonyl A from Dupont) 10.2ml Phosphoric acid (85%) 25.0ml Distilled water 100.0ml

[Table] As shown in Table 1, when the free radical generating agent of the general formula () is used, it gives a printed image with extremely high contrast compared to the comparative agent (1) which does not use the free radical generating agent. The intended effects of the present invention were fully recognized. Example 2 The following photosensitive solution was applied onto the same aluminum plate as used in Example 1 and dried at 100° C. for 2 minutes. Naphthoquinone-(1,2)-diazide-(2)-5
-Esterification reaction product of sulfonyl chloride and cresol novolac resin 0.75g Cresol novolac resin 2.10g Tetrahydrophthalic anhydride 0.15g Free radical generator No.16 0.04g Crystal Violet 0.01g Oil Blue #603 0.01g (Orient (manufactured by Kagaku Kogyo Co., Ltd.) Ethylene dichloride 18 g 2-methoxyethyl acetate 12 g The coating weight after drying was 2.1 g/m ² . By imagewise exposing this photosensitive lithographic printing plate, it was possible to obtain a clear printed image without developing it. The exposed areas faded, while the unexposed areas remained at their original density, making it possible to recognize the details of the image even under safety lights. Example 3 The following photosensitive solution was applied onto the same aluminum plate as used in Example 1 to obtain a photosensitive lithographic printing plate. Naphthoquinone-(1,2)-diazide-(2)-5
- Esterified product of sulfonyl chloride and poly-p-hydroxystyrene (molecular weight 7000)
0.70g Cresol novolak resin 2.25g p-tert-butylphenol novolak resin
0.05g Tetrahydrophthalic anhydride 0.15g Free radical generator No. 14 0.04g Oil Blue #603 (manufactured by Orient Chemical Industry Co., Ltd.) 0.02g Tetrahydrofuran 18g 2-methoxyethyl acetate 12g By imagewise exposing this plate A clear printout image was obtained without any development. Example 4 The following photosensitive solution was applied to the same aluminum plate as used in Example 1 to obtain a photosensitive lithographic printing plate.
By imagewise exposing this plate, it was possible to obtain a clear printed image without developing it. Naphthoquinone-(1,2)-diazide-(2)-5
-Esterified product of sulfonyl chloride and pyrogallol-acetone resin (US Patent No. 3635709)
0.75g cresol-novolac resin 2.10g p-tert-butylphenol-novolac resin
0.05g Tetrahydrophthalic anhydride 0.15g Thymol Blue 0.02g Free radical generator No. 16 0.03g Ethylene dichloride 18g 2-methoxyethyl acetate 12g Example 6 The following photosensitive solution was applied to an aluminum plate in the same manner as in Example 1. and dried. p-Toluenesulfonate of condensate of p-diazodiphenylamine and paraformaldehyde
0.2 g Polyvinyl formal 0.75 g Free radical generator No. 18 0.04 g N,N-dimethylaniline 0.02 g 2-methoxyethanol 20 g Methanol 5 g The dry coating amount was 1.0 g/m ² . When this photosensitive lithographic printing plate was imaged and exposed, the exposed areas developed a purple color, and the unexposed areas remained their original yellow color, making it possible to obtain printed images that were recognizable in detail even under safety lights. Ta. Example 7 In the same manner as in Example 6, the following photosensitive liquid was applied to an aluminum plate and dried. Polyvinyl alcohol (saponification degree 88% polymerization degree
1000) and p-azidobenzoic acid esterification reaction product 0.5g 1-nitro-4-acetaminonaphthalene
0.02g Free radical generator No. 4 0.008g Leuco crystal violet 0.008g Dioctyl phthalate 0.1g Ethylene dichloride 6g Monochlorobenzene 9g When this photosensitive lithographic printing plate was imagewise exposed,
A printed image with high contrast was obtained. Example 8 In the same manner as in Example 1, the following photosensitive solution was applied to an aluminum plate and dried. Copolymer of methyl methacrylate and methacrylic acid (copolymerization molar ratio = 9:1) 0.62g Trimethylolpropane triacrylate
0.38g 2-benzoylmethylene-3-methyl-β-naphthothiazoline 0.02g Free radical generator No. 1 0.04g Leuco crystal violet 0.008g Methyl ethyl ketone 10g When this photosensitive lithographic printing plate was imagewise exposed,
A printed image with rich contrast was obtained. Thereafter, unexposed areas were removed using a developer consisting of 1.2 g of caustic soda, 300 ml of isopropyl alcohol, and 900 ml of water to obtain a lithographic printing plate. Example 9 After graining with a nylon brush, a silicate-treated aluminum plate was coated with the following photosensitive solution using a rotary coater, and dried at 100°C for 3 minutes to form a photosensitive layer to produce a photosensitive plate. Methyl methacrylate-methacrylic acid (molar ratio 85/15) copolymer (in MEK, intrinsic viscosity 0.166 at 30°C) 62g Trimethylolpropane triacrylate 38g Compound of general formula () 2g Triphenylphosphate 10g Ethyl cellosolve 650ml 350 ml of methylene chloride For exposure, use a vacuum baking device to apply a step wedge (density step 0.15, number of density steps 0 to 0) onto the photosensitive plate.
15 stages) and a metal halide lamp (0.5kW)
was irradiated for 5 minutes, and after exposure, development was performed using a developer having the following formulation. Developer: Trisodium phosphate 25 g Sodium phosphate 5 g Butyl cellosolve 70 g Activator 2 ml Water 1 The highest number of step wedges corresponding to the developed image is shown in Table 2 as the sensitivity of the sample. The higher the number of stages, the higher the sensitivity. Also,
The sensitivity without the addition of the photopolymerization initiator of general formula () is shown in Table 2 as Comparative Example (2).

[Table] As shown in Table 2, when the photopolymerization initiator of general formula () is used, it shows higher sensitivity than Comparative Example (2) which does not use this, and the present invention The effects of the period were fully recognized.

Claims (1)

[Claims] 1. A photosensitive composition containing a disulfone compound represented by the following general formula (). R ₁ −SO ₂ −SO ₂ −R ₂ () (Here, R ₁ and R ₂ each independently represent an aryl group or a substituted aryl group.)