JPH0354338B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a developer composition, and more particularly to a developer composition for a lithographic printing plate having a diazo photosensitive layer containing as one component an organic polymer having an acid value of 10 to 200. The present invention relates to a developer composition for removing exposed areas.

Japanese Patent Publication No. 56-39464 describes the use of an anionic surfactant, benzyl alcohol, and an alkaline agent as a developer for removing the unexposed portions of a photosensitive layer consisting of a weakly alkaline water-soluble organic polymer and a photosensitive diazo resin. and water are disclosed. However, this developer composition did not necessarily have a sufficient ability to completely remove the photosensitive layer near the surface of the support in unexposed areas. Therefore, when this composition was used as a developer for photosensitive planographic printing plates, it had the disadvantage of causing stains.
It is known that such defects can be improved by adding a sulfite salt to the above composition as described in Japanese Patent Publication No. 56-42860. However, by adding inorganic sulfite, the problem of staining in non-image areas during printing was solved, but on the other hand, even when attempts were made to concentrate the developer and supply it to users, it was only possible to concentrate it to a certain extent. .

An object of the present invention is to improve the above-mentioned drawbacks and to provide a developer composition that can be concentrated four times or more. Another object is to provide a developer composition in which the unexposed, non-image areas are not smeared during printing.

The present inventors conducted extensive research to achieve the above object, and found that the above object could be achieved by using organic sulfopyrazolone (salt) or hydroxynaphthalene sulfonic acid (salt) instead of inorganic sulfite. found that it can be achieved. That is, a photosensitive material in which a photocurable photosensitive layer comprising an organic polymer compound having an acid value of 10 to 200, substantially water-insoluble and capable of forming a film, and a substantially water-insoluble diazo resin is provided on a support. The developing solution composition for removing the unexposed portion of the photosensitive layer includes an anionic surfactant, an organic solvent with a solubility in water of 10% by weight or less at 25°C, an alkaline agent, water, sulfopyrazolone, its salt, hydroxyl, etc. A developer composition containing at least one selected from the group consisting of naphthalene sulfonic acid and its salts has been found.

Examples of the anionic surfactant used in the present invention include sodium salt of lauryl alcohol sulfate, sodium salt of octyl alcohol sulfate, ammonium salt of lauryl alcohol sulfate, and sodium alkyl sulfate having 8 or more carbon atoms. 22 higher alcohol sulfate ester salts, such as the sodium salt of cetyl alcohol phosphate ester, fatty alcohol phosphate ester salts, such as the sodium salt of dodecylbenzenesulfonic acid, the sodium salt of isopropylnaphthalenesulfonic acid, the sodium salt of metanitrobenzenesulfonic acid Alkylaryl sulfonates such as salts, e.g.
Sulfonates of alkylamides such as C ₁₇ H ₃₃ CON(CH ₃ )CH ₂ CH ₂ SO ₃ Na, etc. Sulfones of dibasic fatty acid esters such as sodium sulfosuccinate dioctyl ester, sodium sulfosuccinate dihexyl ester, etc. Contains acid salts, etc.

Other useful anionic surfactants include or (R:H or CH ₃ , n: 1-10).

It is appropriate that the anionic surfactant be contained in an amount of 0.1 to 5% by weight based on the total weight of the developer at the time of use. If it is less than 0.1% by weight, the effectiveness of its use will be reduced, and if it is more than 5% by weight, for example, the dye contained in the photocurable photosensitive layer may elute excessively (color loss), or This may cause side effects such as deterioration of mechanical and chemical strength such as abrasion resistance of the cured image. Therefore, the preferred amount used is in the range of 0.5 to 1.5% by weight.

The organic solvent used in the developer composition of the present invention is suitably selected from those having a solubility in water of about 10% by weight or less, preferably about 2% by weight or less. Examples of such organic solvents include 1-phenylethanol, 2-phenylethanol, and 3-phenylethanol.
-Phenylpropanol-1, 4-phenylbutanol-1, 4-phenylbutanol-2, 2-
Phenylbutanol-1,2-phenoxyethanol, 2-benzyloxyethanol, o-methoxybenzyl alcohol, m-methoxybenzyl alcohol, p-methoxybenzyl alcohol,
Benzyl alcohol, cyclohexanol, 2-
Examples include methylcyclohexanol, 4-methylcyclohexanol, and 3-methylcyclohexanol.

The content of the organic solvent is preferably 1 to 5% by weight based on the total weight of the developer at the time of use. The amount used is closely related to the amount of surfactant used, and it is preferable to increase the amount of anionic surfactant as the amount of organic solvent increases. This is because if the amount of anionic surfactant is small and the amount of organic solvent is large, the organic solvent will not dissolve, and therefore good developability cannot be expected to be ensured.

Examples of the alkaline agents used in the developer composition of the present invention include sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate,
Tertiary ammonium phosphate, dibasic ammonium phosphate,
Inorganic alkaline agents such as sodium metasilicate, sodium bicarbonate, sodium borate, ammonium borate, ammonia, etc., and monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, n-butylamine, There are organic amine compounds such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine, pyridine, etc., which can be used alone or in combination.
Particularly preferred are organic amine compounds. The content of the alkaline agent is suitably 0.05 to 3% by weight based on the total weight of the developer at the time of use, preferably
It is 0.1 to 1% by weight. If it is less than 0.05% by weight, removal of the uncured photosensitive layer will be incomplete. on the other hand,
When the amount exceeds 3% by weight, the mechanical and chemical strength of the photocured portion of the photosensitive layer deteriorates, and for example, in the case of a lithographic printing plate, this appears as a decrease in printing durability.

Sulfopyrazolone or its salt or hydroxynaphthalenesulfonic acid or its salt used in the present invention includes 1-(4'-sulfophenyl)-3-methyl-pyrazolone-(5), 1-(4'-sulfo-2' ,5′−
dichlorophenyl)-3-methyl-pyrazolone-
(5), 2,3-dihydroxynaphthalene-6-sulfonic acid, 1,8-dihydroxynaphthalene-4-
Sulfonic acid, 1,5-dihydroxynaphthalene-
3,7-disulfonic acid, 1,8-dihydroxynaphthalene-3,6-disulfonic acid, 1-amino-
These include 8-hydroxynaphthalene-3,6-disulfonic acid and their sodium and potassium sulfonates.

The content of these sulfopyrazolone (salt) and hydroxynaphthalene sulfonic acid (salt) in the developer when used is preferably 0.05 to 1% by weight.
If the content is lower than 0.05% by weight, the ability to prevent stains in non-image areas will not be sufficient. If the amount exceeds 1% by weight, the mechanical strength of the photocured portion of the photosensitive layer will deteriorate. Therefore preferably
It is 0.1-0.5% by weight.

Although the remaining component of the developer composition of the present invention is water, it may further contain various additives known in the art, if necessary. For example, when a concentrated solution is used after being diluted with hard water by containing a water softener, poor development due to hard water can be prevented.

Examples of water softeners used as necessary in the present invention include Na ₂ P ₂ O ₇ , Na ₅ P ₃ O ₃ ,
Polyphosphates such as Na ₃ P ₃ O ₉ , Na ₂ O ₄ P (NaO ₃ P) PO ₃ Na ₂ , Calgon (sodium polymetaphosphate), such as ethylenediaminetetraacetic acid, its potassium salt, its sodium salt; diethylenetriaminepentaacetic acid , its potassium salt, sodium salt; triethylenetetraminehexaacetic acid, its potassium salt, its sodium salt; hydroxyethylethylenediaminetriacetic acid, its potassium salt, its sodium salt; nitrilotriacetic acid, its potassium salt, its sodium salt; 1,2 Examples include aminopolycarboxylic acids such as -diaminocyclohexanetetraacetic acid, its potassium salt, and its sodium salt; 1,3-diamino-2-propanoltetraacetic acid, its potassium salt, and its sodium salt. The optimal amount of such water softeners varies depending on the hardness of the hard water used and the amount used, but the general amount used is 0.01 to 5% by weight in the developer when used. Preferably 0.01
It is contained in a range of 0.5% by weight.

The photosensitive material that can be developed with the developer of the present invention has an acid value of
It has a photosensitive layer made of an organic high molecular weight polymer having a molecular weight of 10 to 200 and a photosensitive diazo compound.

Specific examples of organic polymers having an acid value of 10 to 200 include copolymers containing acrylic acid, methacrylic acid, crotonic acid, or maleic acid as essential polymerization components, such as those described in U.S. Pat. No. 4,123,276. 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, acrylonitrile or methacrylonitrile, tertiary or quaternary copolymers with acrylic acid or methacrylic acid and optionally further copolymerizable monomers, Acrylic acid or methacrylic acid, acrylic acid or methacrylic acid which has a hydroxyl group at the end and is esterified with a group containing a dicarboxylic acid ester residue, as described in JP-A-53-120903, and optionally Copolymer with other copolymerizable monomers, JP-A-54-98614
A monomer having an aromatic hydroxyl group at the end (for example, N-(4-hydroxyphenyl) methacrylamide, etc.), acrylic acid or methacrylic acid, and other co-acrylic acid as necessary. Copolymers with at least one polymerizable monomer, including copolymers of alkyl acrylates or methacrylates, acrylonitrile or methacrylonitrile, and unsaturated carboxylic acids as described in JP-A-56-4144. It will be done. Also useful are acidic polyvinyl alcohol derivatives and acidic cellulose derivatives.

On the other hand, as the photosensitive diazo compound, a diazo resin represented by a condensate of p-diazodiphenylamine and formaldehyde is useful, and it is a diazo resin that is substantially water-insoluble and organic solvent-soluble. Such preferred diazo resins are disclosed in U.S. Pat.
It is described in detail in No. 3300309 and Japanese Patent Application Laid-Open No. 54-98613. In the present invention, "substantially water-insoluble" refers to a material having a solubility in water of 1% by weight or less at room temperature. The photosensitive diazo compound is contained in the photocurable photosensitive layer in an amount of 5 to 50% by weight, preferably 8 to 20% by weight.

The photocurable photosensitive layer as described above is provided on various supports depending on the purpose. For example, in the case of photosensitive lithographic printing plates, metal supports such as aluminum plates are preferred. The surface of the aluminum plate is based on U.S. Patent No.
2714066, a chemical conversion treatment with aqueous solutions of alkali metal silicates, U.S. Pat.
After anodizing as described in No. 3181461, it is preferable to treat with an aqueous solution of an alkali metal silicate, and the above-mentioned photosensitive layer is deposited at 0.1 to 7 g/m ² on the thus surface-treated aluminum plate. ,
It is preferably applied at a coverage of 0.2 to 5 g/ ^m2 ,
It is considered a photosensitive lithographic printing plate. The photosensitive lithographic printing plate is imagewise exposed through a transparent original using a light source rich in ultraviolet light, such as a metal halide lamp, and then treated with the developer of the present invention to remove the photosensitive layer in the unexposed areas, resulting in lithographic printing. You can get the version.

The developing solution of the present invention is generally supplied to the user as a 4 times or more concentrated solution, and the user dilutes it with water to prepare the developing solution for use.

The developer of the present invention is useful not only as a developer for photosensitive planographic printing plates as described above, but also for photosensitive materials for photomasks and photoresists.

Hereinafter, the present invention will be explained in more detail based on examples. Note that percentages are by weight unless otherwise specified.
shall be shown.

Example 1 300 g of ethylene glycol monomethyl ether was heated to 100°C under a nitrogen stream, and a mixed solution of 70 g of 2-hydroxyethyl methacrylate, 80 g of acrylonitrile, 130 g of benzyl methacrylate, 20 g of methacrylic acid, and 1.2 g of benzoyl peroxide was added thereto. The mixture was added dropwise over 2 hours. 15 minutes after the completion of the dropwise addition, 300 g of ethylene glycol monomethyl ether and 0.3 g of benzoyl peroxide were added, and the mixture was allowed to react for 4 hours. After the reaction was completed, the copolymer was diluted with methanol and poured into water to precipitate the copolymer, followed by vacuum drying at 70°C. The acid value of this 2-hydroxyethyl methacrylate copolymer (2) was 40.2.

A 2S aluminum plate with a thickness of 0.15 mm was degreased by immersing it in a 10% aqueous solution of tribasic sodium phosphate kept at 80°C for 3 minutes, and after graining with a nylon brush using Pumice slurry as an abrasive, it was heated to 60°C. It was desmatted with a 3% aqueous sodium aluminate solution. The aluminum plate was anodized in 20% sulfuric acid at a current density of A/dm ² for 2 minutes and then treated with a 2.5% aqueous solution of sodium silicate at 70° C. for 1 minute.

Apply the following photosensitive liquid to this aluminum plate,
A photosensitive planographic printing plate was obtained by drying at 100°C for 2 minutes.

2-Hydroxyethyl methacrylate copolymer () 87g 2-methoxy-4-hydroxy condensate of p-diazodiphenylamine and paraformaldehyde
5-benzoylbenzenesulfonate 10g Oil Blue #603 (manufactured by Orient Chemical Co., Ltd., triphenylmethane oil-soluble dye) 3g 2-methoxyethanol 600g methanol 600g ethylene dichloride 600g Dry coating weight was 2.5g/ ^m2. Ta. A transparent negative original image was brought into close contact with this photosensitive lithographic printing plate, and the image was exposed for 40 seconds from a distance of 70 cm using a 30 ampere carbon arc lamp.
A lithographic printing plate was obtained by developing with a developer diluted with hard water at a volume ratio of 1:10 (concentrated developer: hard water) using a commercially available automatic developing machine at 25°C for 50 seconds.

Benzyl alcohol 900g Triethanolamine 300g Sodium isopropylnaphthalene sulfonate (38% aqueous solution) 900g Sodium 2,6-dihydroxynaphthalene-6-sulfonate 60g Trisodium nitrilotriacetate 10g Lithographic printing plate with no residual film in non-image areas due to poor development I got it. When this printing plate was printed on high-quality paper using an offset printing machine, more than 80,000 beautiful prints with no stains in the non-image areas were printed.

Example 2 Hexafluorophosphate (PF ₆
Salt substitution rate 89%) 10g, 2-hydroxyethyl methacrylate/acrylonitrile/ethyl methacrylate/methacrylic acid = 50/26/20/4% by weight
(Monomer preparation ratio) 90 g of copolymer, 1 g of sodium isopropylnaphthalene sulfonate, 2 g of phosphorous acid, 3 g of Victoria Pyu Blue BOH (manufactured by Hojigaya Chemical Co., Ltd.), 7 g of tricresidyl phosphate
g, ethylene glycol monomethyl ether 600
g, methanol 600g and ethylene chloride 600g
A photosensitive solution consisting of the following was applied onto the aluminum plate used in Example 1. Coating weight after drying is 1.5g/
It was ^m2 . After image exposure of this photosensitive printing plate, the concentrated solution of Example 1 was mixed with AH70ppm well water at a volume ratio of 1:15.
A planographic printing plate was obtained by developing for 50 seconds at 25° C. using a commercially available automatic machine using a developer diluted to 100%. When this printing plate was used for printing in a conventional manner, a beautiful printed matter with no stains in the non-image area was obtained.

Example 3 After image exposure of the photosensitive lithographic printing plate of Example 2, the non-image area was developed in the same manner as in Example 2 using a developer prepared by diluting the following concentrate with AH70ppm well water at a volume ratio of 1:10. A lithographic printing plate with no stains was obtained.

Benzyl alcohol 900g Triethanolamine 300g Monoethanolamine 20g 300g Sodium salt of 1-(4'-sulfophenyl)-3-methyl-pyrazolone-(5) 60g Pure water 600g Example 4 The sulfopyrazolone in the concentrated developer composition of Example 3 was converted to 1-(4'-sulfophenyl)-3-methyl-pyrazolone-(5). The same results as in Example 3 were obtained by replacing -2',5'-dichlorophenyl)-3-methyl-pyrazolone-(5).

Claims (1)

[Claims] 1. A photosensitive layer comprising a support and a photocurable photosensitive layer comprising an organic polymer compound having an acid value of 10 to 200, substantially water-insoluble and capable of forming a film, and a substantially water-insoluble diazo resin. A developer composition for removing a photosensitive layer in an unexposed area of a material, which comprises an anionic surfactant, an organic solvent with a solubility in water of 10% by weight or less at 25°C, an alkaline agent, water, and a sulfopyrazolone. 1. A developer composition comprising at least one selected from the group consisting of hydroxynaphthalene sulfonic acid, hydroxynaphthalene sulfonic acid, and its salt.