JPS6336490B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention removes the unexposed areas of a photosensitive material coated on a support with a photosensitive composition containing a polymer compound having a monomer having an aromatic hydroxyl group in its polymer structure and a photosensitive diazo compound as main components. The present invention relates to a developer composition. BACKGROUND ART Photosensitive materials such as lithographic printing plate materials, ceramic patterned materials, etc., in which a photosensitive composition containing a polymer compound having an aromatic hydroxyl group and a photosensitive diazo compound as main components are coated on a support are widely known. After exposure, these photosensitive materials are developed to dissolve unexposed areas to form patterns, characters, and figures. However, when developing with a conventional developer, even if development is easy immediately after the photosensitive material is manufactured, development becomes difficult over time, and eventually becomes impossible.
In order to prevent this, attempts have been made to add stabilizers and the like to photosensitive compositions, but no satisfactory results have yet been obtained. On the other hand, improvements have been made to developing solutions, such as those consisting of organic solvents that mix freely with water, such as butyl cellosolve, alkaline agents, anionic surfactants, and water (Japanese Patent Publication No. 51-6565); It has been proposed to use bezyl alcohol (solubility in water about 4%) instead (Japanese Patent Application Laid-open No. 77401/1983). However, since these developers use organic solvents that are easily miscible with water, they not only have a weak developing ability, but also require a large amount of organic solvent, which poses undesirable problems in terms of pollution and occupational health. The object of the present invention is to solve these problems and provide a developer composition that has improved developing ability and is good in terms of pollution and occupational health by using a small amount of organic solvent. As a result of intensive research to solve this problem, the present inventors found that the organic solvent in the developer can dissolve or swell the unexposed areas of the photosensitive layer, and its solubility in water at room temperature (20°C) is 3. The inventors have found that the problem can be solved by using an organic solvent with a content of less than % by weight, and have completed the present invention based on this knowledge. The gist of the present invention is to provide a photosensitive material having, on a support, a photosensitive layer mainly composed of a polymer compound having 1 to 80 mol% of a monomer having an aromatic hydroxyl group in the polymer structure and a photosensitive diazo compound. A developer composition for developing an organic solvent, an alkaline agent, which has a solubility in water of 3% by weight or less at room temperature (20°C) that can dissolve or swell the unexposed areas of the photosensitive layer;
A developer composition containing an anionic surfactant and water. Examples of the polymer compound of the photosensitive composition include (1) a monomer having an aromatic hydroxyl group, such as N
-(4-hydroxyphenyl)acrylamide,
Copolymers of N-(4-hydroxyphenyl) methacrylamide, N-(4-hydroxynaphthyl) methacrylamide, etc. and other monomers (see Japanese Patent Publication No. 52-34930) (2) o-, Copolymers of m- or p-hydroxystyrene and other monomers (3) Examples include copolymers of o-, m-, or p-hydroxyphenyl methacrylate and other monomers. Examples of the other monomers include (1) α, β unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and maleic anhydride, (2) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-chloroethyl acrylate, 2-
Alkyl acrylates such as hydroxyethyl acrylate, glycidyl acrylate, N-dimethylaminoethyl acrylate, (3) methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl Alkyl methacrylates such as methacrylate, glycyl methacrylate, and N-dimethylaminoethyl methacrylate. (4) Acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N-ethylacrylamide, N
-hexyl methacrylamide, N-cyclohexyl acrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide,
Acrylamides such as N-nitrophenyl acrylamide and N-ethyl-N-phenylacrylamide, methacrylamides, (5) Ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, (6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, and vinyl benzoate; (7) Styrenes such as styrene, α-methylstyrene, methylstyrene, and chloromethylstyrene; (8) ) Methyl vinyl ketone, ethyl vinyl ketone,
Vinyl ketones such as propyl vinyl ketone and phenyl vinyl ketone, (9) Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene, (10) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, Examples include methacryl nitrile, but any other monomer that can be copolymerized with a monomer containing an aromatic hydroxyl group may be used. It also includes resins obtained by partially esterifying or etherifying aromatic hydroxyl groups, such as homopolymers and copolymers of monomers having aromatic hydroxyl groups, and phenol novolacs. However, the structural unit (monomer) having an aromatic hydroxyl group contained in the polymer is 1 to 80 mol%, preferably 5 to 60 mol%. If the structural unit content is less than 1 mol%, there is a problem with storage stability, and if it exceeds 80 mol%, the exposed area will dissolve to provide a positive-positive type photosensitive copying layer, and the photosensitive copying layer of the present invention may It becomes unsuitable as a composition. The photosensitive diazo compounds used in the present invention include diazo resins represented by condensates of aromatic diazonium salts and, for example, active carbonyl-containing compounds, especially formaldehyde, among which diazo resins soluble in organic solvents are preferred. . Diazo resins include, for example, organic solvent-soluble reaction products of p-diazodiphenylamine and formaldehyde or acetaldehyde condensates and hexafluorophosphates, tetrafluoroborates, perchlorates, and periodates. diazo resin inorganic salts, which are diazo resins, and also the condensates thereof with sulfonic acids such as para-toluenesulfonic acid or its salts, phosphinic acids such as benzenephosphinic acid or its salts, as described in U.S. Pat. No. 3,300,309; Hydroxyl group-containing compounds such as 2,4-dihydroxybenzophenone, 2-hydroxy-4
-Methoxy-benzophenone-5-sulfonic acid or a salt thereof, which is a reaction product such as an organic solvent-soluble diazo resin organic acid salt. The content of the diazo resin in the photosensitive composition of the present invention is 1 to 30% by weight, preferably 3 to 15% by weight. Various additives can also be added to the photosensitive composition to improve its performance. Examples include: (1) Alkyl ethers to improve coating properties, (2) Plasticizers to impart flexibility and abrasion resistance to coating films, (3) Coloring substances to visualize images, (4) ) Photochromic substances for visualizing images by exposure to light The amount of these substances added is generally based on the total solid content.
It is 0.5-30% by weight. Examples of organic solvents that can dissolve or swell the unexposed areas of the photosensitive layer and have a solubility in water of 3% by weight or less at room temperature include ethylene glycol dibutyl ether, ethylene glycol benzyl ether, and ethylene glycol monophenyl ether. ,
Examples include methylphenylcarbitol, n-amyl alcohol, methylamyl alcohol, isophorone, methylcyclohexane, acetophenone, and the like. However, it is not limited to this. Among these, ethylene glycol phenyl ether is particularly effective. The content of these organic solvents in the developer composition is 1 to 15% by weight, preferably 2 to 8% by weight.
It is. The alkaline agents used in the present invention include (1) sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium or ammonium salt of dibasic or tertiary phosphoric acid, sodium metasilicate; , sodium carbonate, inorganic alkaline agents such as ammonia, (2) mono-, di-, or trimethylamine, mono-, di-, or triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di-, or triethanolamine, mono-, di-, or triethylamine; Alternatively, organic amine compounds such as triisopropanolamine, ethyleneimine, and ethylenediimine may be mentioned. The content in the developer composition is 0.05 to 4% by weight, preferably 0.5 to 2% by weight. 0.05
If it is less than 4% by weight, the development will be poor.
Exceeding this will have an adverse effect on the printing performance of the lithographic printing plate. The anionic surfactants used in the present invention include (1) higher alcohol sulfate esters (for example, sodium salt of lauryl alcohol sulfate, sodium salt of octyl alcohol sulfate, ammonium salt of lauryl alcohol sulfate, (2) Aliphatic alcohol phosphate ester salts (e.g., sodium salt of cetyl alcohol phosphate, etc.) (3) Alkylaryl sulfonates (e.g.,
(4) Alkylamide sulfonate salts

[Formula] (5) Sulfonic acid salts of dibasic fatty acid esters (e.g., dioctyl sodium sulfosuccinate, dihexyl sodium sulfosuccinate, etc.) (6) Formaldehyde condensates of alkylnaphthalene sulfonates (e.g., formaldehyde of sodium dibutylnaphthalene sulfonate) condensates, etc.). Among these, sodium butylnaphthalene sulfonate and a formaldehyde condensate of sodium butylnaphthalene sulfonate are particularly effective. The content of these in the developer composition is 0.5 to 10% by weight, preferably 1 to 5% by weight. If it is less than 0.5% by weight, no effect will be observed, and if it exceeds 10% by weight, the developability will be excessive and will have an adverse effect on the printability of a lithographic printing plate. Example 1 27 g of N-(4-hydroxyphenyl) methacrylamide, 2-hydroxyethyl methacrylate
39g, methyl methacrylate 48g, methacrylic acid
6.0g and 0.4g of azobisisobutyronitrile,
It was dissolved in 300 ml of dioxane and heated at 65°C for 30 hours in a sealed tube purged with nitrogen. After the reaction was completed, the reaction solution was poured into water 5 with stirring,
The resulting white precipitate was dried to obtain copolymer-1,
97.0g was obtained. Mix 200 ml of 5% diazo resin (zinc chloride/sulfuric acid double salt) aqueous solution and 50 ml of 10% ammonium hexafluorophosphate aqueous solution at room temperature, immediately suction the formed precipitate, and dry it under reduced pressure at 30 to 40°C. , 10 g of diazo resin-1 (hexafluorophosphate) was obtained. An aluminum plate is immersed in a 20% sodium phosphate aqueous solution to degrease it, and then sealed with a sodium metasilicate aqueous solution to produce an aluminum plate for use in lithographic printing plates.
1 was created. The following photosensitive solution was applied to aluminum plate-1 using a rotary coater to obtain photosensitive lithographic printing plate A. Photosensitive liquid copolymer-1 5.0g Diazo resin-1 0.5g Dyurimer AC10L (manufactured by Nippon Pure Chemical Industries, Ltd. (stabilizer, polyacrylic acid) 0.05g Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) )Dye 0.1g Methyl cellosolve 100ml The obtained photosensitive lithographic printing plate A was heated with a metal halide lamp Idolfin 2000 (manufactured by Iwasaki Electric Co., Ltd.).
Image exposure was carried out for 30 seconds from a distance of 80 cm, and the plate was developed with the following developer-1 to obtain a lithographic printing plate A-1. Developer -1 Ethylene glycol monophenyl ether 40g Sodium metasilicate 10g Alkanol Developer -2 Butyl cellosolve 400ml Diethanolamine 60ml Caustic soda 10g Anionic activator 2g Water 1000ml The storage stability of the photosensitive lithographic printing plate thus obtained and the printing durability of the lithographic printing plate were examined.
The results shown in Table 1 were obtained.

[Table] However, in the table, the storage stability is 40% for photosensitive lithographic printing plates.
℃, stored in an atmosphere with 80% humidity, developer-1,
-2 and compared with the control (exposed and developed immediately after the photosensitive lithographic printing plate was manufactured), so-called background smudge development, in which printing ink adheres to the non-image area during printing, occurs as soon as printing starts. Printing resistance is the number of days printed on a sheet-fed offset printing machine Hamadastar CD×
900 (manufactured by Hamada Seisakusho Co., Ltd.) and printed on high-quality paper for testing. As is clear from Table 1, the results show that the storage stability and printing durability are significantly superior when the developer-1 of the present invention is used. Example 2 Copolymer-2 was synthesized in the same manner as in Example 1. The composition of copolymer-2 is N-(4-hydroxyphenyl) methacrylamide: acrylonitrile: methyl methacrylate: methacrylic acid = 10:
The molar ratio was 48:32:10. At room temperature, mix 200 ml of 5% diazo resin (zinc chloride/sulfuric acid double salt) aqueous solution and 50 ml of 10% ammonium tetrafluoroborate aqueous solution, filter the resulting precipitate, and dry under reduced pressure at 30 to 40°C. Diazo resin-2 (pertetrafluoroborate salt) 10
I got g. Aluminum plate used in Example 1
1 was coated with the photosensitive solution shown below using a spin coater. Photosensitive liquid copolymer-2 5.0g Diazo resin-2 0.5g Cellulose ethyl ether 0.2g Tricresyl phosphate 0.5g Victoria Blue Base F4R (manufactured by Vadeitsch Aniline Soda) 0.1g Methyl cellosolve 95ml Dimethyl formamide 5ml Obtained A photosensitive lithographic printing plate immediately after manufacturing,
When stored for 10 days or more under the same storage conditions as in Example 1, exposed in the same manner as in Example 1, and developed with the developer shown below, offset printing was performed on the resulting lithographic printing plate. A large number of prints with clear images and no blemishes were obtained in the same manner as in Example 1. Developer ethylene glycol monophenyl ether 20g Sodium metasilicate 20g Pionin A-44B (surfactant manufactured by Takemoto Yushi Co., Ltd.)
30g Water 1000ml Example 3 Copolymer-3 was synthesized in the same manner as in Example 1. The composition of copolymer-3 was parahydroxystyrene:acrylonitrile:methyl methacrylate:methacrylic acid=15:48:30:7 (molar ratio). In the photosensitive liquid used in Example 1, copolymer-
A photosensitive solution using Copolymer-3 instead of Copolymer-1 was applied to the aluminum plate-1 used in Example 1 using a spin coater to obtain a photosensitive lithographic printing plate. The obtained photosensitive lithographic printing plate was stored under the same storage conditions as in Example 1.
The plate was stored for 10 days, exposed to light in the same manner as in Example 1, and developed with the developer shown below, and the resulting plate was printed using an offset printing machine. In the same manner as in Example 1, a printed matter with a clear image and no background smudge was obtained. Developer ethylene glycol monophenyl ether 80g Soda carbonate 5g Pionin A-45 (surfactant manufactured by Takemoto Yushi Co., Ltd.)
20g N-Methylpyrrolidone 20g Water 1000ml As described above, the developer composition of the present invention provides excellent development effects even after the photosensitive material has been manufactured. For example, when it is used as a lithographic printing plate, Excellent printing with no background smudges can be achieved three times as much as with conventional methods, and the developer composition requires only a small amount of organic solvent, resulting in superior results in terms of pollution and occupational health. It is effective.

Claims (1)

[Claims] 1 A developer for developing a photosensitive material having a photosensitive layer on a support, the main components of which are a polymer compound having 1 to 80 mol% of a monomer having an aromatic hydroxyl group in the polymer structure and a photosensitive diazo compound. A composition containing an organic solvent, an alkaline agent, an anionic surfactant, and water having a solubility in water of 3% by weight or less at room temperature (20°C) that can dissolve or swell the unexposed areas of the photosensitive layer. A developer composition characterized by: