JPS5822736B2 - Genzou exo saves - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a developer composition for photosensitive sheets, and particularly to a developer composition for lithographic printing materials.

More specifically, the present invention relates to a developer composition for developing an exposed photosensitive sheet (lithographic printing material) to remove non-image areas and form a relief image.

Lithographic printing is a method of printing using water and oil-based ink using a plate material on which a lipophilic image is formed on a support having a hydrophilic surface.

That is, the non-image area is hydrophilic, so it accepts water but not oil-based ink, while the image area is lipophilic, so it accepts oil-based ink but not water.

Therefore, if you transfer this to a blanket and then to paper, you can change the printed matter.

As described above, in order to make a lithographic printing plate, the photosensitive material is introduced onto a suitable hydrophilic support by coating at a coating weight of 05 to 59/2.
m'), if you expose the printing plate to light through a photographic negative film, only the areas hit by the light will harden and become insoluble in the developer, so if you develop the printing plate, the unexposed areas will be removed. A positive image is formed.

The developer used at this time plays an important role in producing a lithographic printing plate, and is preferably one that completely removes non-image areas and protects image areas.

The present inventors coated a photosensitive composition comprising an acrylic acid-based or methacrylic acid-based polymer having an acid value of 10 to 300 and a hydroxyl group and a cyano group in the side chain, and a diazo compound. Ammonium borate,
By using an aqueous ammonium salt solution of at least one weak acid selected from the group consisting of ammonium pentaborate, ammonium carbonate, ammonium silicate, tertiary ammonium phosphate, and tertiary ammonium phosphate, the image area can be made oil-sensitive. The present invention was completed based on the discovery that an image with long printing durability can be formed without deteriorating the printing quality and is low in pollution.

JP-A No. 50-3292 filed by the present applicant describes an organic polymer having an acid value of 10 to 300 containing a cis-4-cyclohexene-1,2-dicarboxylate group in its side chain. It is described that an aqueous solution of sulfur silicate is used as a developer for a photosensitive composition consisting of a polymer containing a diazo resin and an aromatic azide compound as a photosensitive compound, and the present applicant's application JP-A-50-118802 discloses that silica is used as a developer for a photosensitive composition comprising a hydroxyalkyl (meth)acrylate-(meth)acrylonitrile copolymer having an acid value of 10 to 100 and a diazo compound. Although it is described that an aqueous solution of sulfur-IJ is used, it has the disadvantage that if the development time is excessive or the development temperature is high, the printing durability during printing will deteriorate.

In contrast, according to the present invention, a photosensitive composition containing an acrylic or methacrylic acid-based polymer and a diazo compound having an acid value of 10 to 300 and having a hydroxyl group and a cyanide group in the side chain is used. When a developer consisting of an aqueous solution of ammonium salt of at least one weak acid selected from the above-mentioned specific compound group is used as a developer for removing the unexposed portion of the provided photosensitive sheet,
The above-mentioned drawbacks are eliminated.

In the present invention, a photosensitive composition from which particularly favorable results can be obtained is the general formula CI) described in JP-A-50-118802 (wherein R1 is a hydrogen atom or a methyl group, R2
represents a hydrogen atom, a methyl group, an ethyl group, or a chloromethyl group, and n is an integer of 1 to 10.

) and the following general formula (II) (wherein, R3 is a hydrogen atom or a methyl group).

) and has an acid value of 10 to 10
This is a photosensitive composition consisting of a polymer with a diazo compound of 0.0 and a diazo compound.

In order to give the above polymer an acid value of 10 to 300, acid groups such as carboxyl groups are introduced into the side chains. Known methods such as combining methods can be used.

On the other hand, as specific diazo compounds, those having compatibility with the above-mentioned polymers are preferred.

Particularly preferred diazo compounds include salts of condensates of P-diazodiphenylamine 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-ditetrabenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-chloro-5-nitrobenzenesulfonic acid, 2-fluorocaprylnaphthalenesulfonic acid, Having two or more diazo groups in one molecule, such as salts of sulfonic acids such as 1-naphthol-5-sulfonic acid, 2-methoxy-4-hydroxy-5-benzoyl-benzenesulfonic acid, and para-toluenesulfonic acid. It is a compound.

Other desirable diazo compounds include the above-mentioned salts.
．． 5-Dimethoxy-4-P-tolylmercaptone Condensate of benzenediazonium and formaldehyde, 2,5-
Included are condensates of dimethoxy-4-morpholinobenzenediazonium and formaldehyde or acetaldehyde, and compounds represented by the following general formula as described in JP-A-48-33907.

In the formula, R1, R2, R3 and R4 each have 1 to 4 carbon atoms.
An alkyl group, such as a methyl group, an ethyl group, a propyl group, a butyl group, etc.; ] represents a hydroxyalkylamino group such as an amino group, and Y represents an anion of the acid as described above.

Specifically, for example, 2,6-bis(4-diazodi2
．． 2-Methoxy-4-hydroxy-5-benzoylbenzenesulfonate of 5-dimethoxyphenylamino)-4-N,N-(cyβ-hydroxyethyl)amino-1,3,5-triazine, 2,6- Bis(4-diazodi2
,5-dimethoxyphenylamino)-4-N-(β-hydroxyethyl)amino-1,3,5-triazine 2
-methoxy-4-hydroxy-5-benzoylbenzenesulfonate, 2,6-bis(4-diazodi2,5-jethoxyphenylamine)-4-N-(β-hydroxyethylamino-1,3, Examples include 2-methoxy-4-hydroxy-5-benzoylbenzenesulfonate of 5-1-riazine.

Additionally, other useful diazo compounds are described in U.S. Pat.
, 649,373.

The blending amount of the diazo compound is 2 to 4 with respect to the polymer.
00 weight ratio, preferably 8 to 100 weight ratio.

The ammonium salt of a weak acid used in the present invention has a pI of 7.5 to 10.0 in an aqueous solution of 1 weight.
Selected from those that indicate

Representative examples include ammonium borate, ammonium pentaborate, ammonium carbonate, ammonium silicate, and phosphoric acid.

Examples include secondary ammonium and tertiary ammonium phosphate.

The concentration of the ammonium salt of a weak acid in the developer composition is from 0.1 to 5 parts by weight, preferably from 0.5 to 2 parts by weight.

In order to increase the development rate of developer compositions made from aqueous solutions of ammonium salts of weak acids according to the invention, surfactants and water-miscible organic solvents can also be added.

As the surfactant, nonionic surfactants and anionic surfactants are effective.

Specifically, such surfactants include: For example, higher alcohol (08-C22) sulfate ester salts,
Fatty alcohol phosphate ester salts, dibasic fatty acid ester sulfonates, fatty acid amide sulfonates, alkylaryl sulfonates, polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl esters, polyoxyalkylene alkyl Aryl ethers, polyoxyethylene alkyl amines,
These include polyoxyethylene alkylamides, polyoxyethylene sorbitan alkyl esters, Pluronics type and Tetronics type surfactants.

The amount of these surfactants in the developer composition ranges from 0.1 to
10 parts by weight, preferably 0.5 to 3 parts by weight.

Organic solvents that are miscible with water include benzyl alcohol, cyclohexanone, cyclohexanol, dimethylformamide, dimethyl sulfoxide, isopropanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, Ascent alcohol, etc.

The amount of these organic solvents is 0.5 to 1 in the developer composition.
0 weight ratio, preferably 1 to 4 weight ratio.

Among the above-mentioned surfactants and organic solvents, a combination of isoprobylnafucrene sodium sulfonate and benzyl alcohol is particularly preferred.

In the developer comprising an aqueous solution of ammonium salt of a weak acid according to the present invention, the pH of the liquid body is close to the neutralization point (for example, the pH of a 1 weight aqueous solution of ammonium borate is 8.3).

), there is no need to neutralize the waste liquid when it is disposed of, and the pollution is extremely low.

Moreover, the printing durability of the lithographic printing plate treated with the developer of the present invention is inferior to that of the plate treated with a developer made of other alkaline agents, for example, an aqueous solution of sodium silicate. Even if the development time becomes excessive or the development temperature becomes high, the deterioration in printing durability is extremely small.

The developer composition of the present invention further comprises a photoresist material,
It can also be used for developing photomasks, etc.

Next, the present invention will be explained in more detail by giving examples.

Note that the percentages in the following examples are by weight unless otherwise specified.

Example 1 300 g of dioxane was heated to 100°C under a nitrogen stream, and 150 g of 2-hydroxyethyl meccrylate and 79.57 g of methyl methacrylate were added. , acrylonitrile 60
g, methacrylic acid 10.5 g and benzoyl peroxide 1
．． 2 g of the mixture was added dropwise over a period of 2 hours.

15 minutes after the completion of the dropwise addition, 300 g of dioxane 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 it, followed by vacuum drying at 70°C.

The acid value of this 2-hydroxyethyl methacrylate copolymer was 20, and the viscosity of the 2-methoxyethanol 33 solution at 25°C was 4,980 centipoise.

A 38 aluminum plate with a thickness of 0.15 mm was immersed for 3 minutes in a 10% aqueous solution of tertiary sodium phosphate kept at 80°C, degreased and washed with water, then desmutted with a 70% nitric acid aqueous solution and washed with water. Sodium silicate at 70℃ 1.
It was immersed in a 25% aqueous solution for 1 minute to produce a smooth aluminum plate without grains.

A photosensitive composition solution having the following composition was applied to this aluminum plate using a boiler.

Drying was performed at 100°C for 2 minutes.

2-hydroxyethyl methacrylate Sea 1-2-methoxy copolymer Ethanol 33 solution 25.5g.

2-Methoxy-4-hydroxy-5-benzoylbenzene sulfonate of condensate of P-diazodiphenylamine and paraformaldehyde L25,9 Oil Blue 8603 (manufactured by Orient Chemical Co., Ltd.) 0. :12-methoxyethanol 90g methanol
90g ethylene dichloride
90g.

The dry coating weight was 0.82% J/m''.

This photosensitive lithographic printing plate was exposed to a 30 ampere carbon arc lamp from a distance of 70 cIrL for 20 seconds, resulting in a three-level solid gray scale.

This was an exposure amount that was half the appropriate exposure time.

). Then, below. The sample was immersed in a developer having the following composition at 25° C. for 1 minute, and then washed with water while being lightly rubbed with absorbent cotton for 30 seconds.

Benzyl alcohol 205 + sodium isoprobylnafucrene sulfonate 10g alkaline agent xg water
When 1000 g of the printing plate thus obtained was printed on high-quality paper using a Harris Ausilia 125 printing machine, the results shown in Table 1 were obtained.

Comparative Examples 1 to 3 The same method as in Example 1 was carried out except that the type and amount of the alkaline agent were changed to those shown in Table 1.
The table results have been changed.

As is clear from the results in Table 1, those using ammonium borate have printing durability that is 2 to 6 times longer than those using other alkaline agents.

Furthermore, the pH of the developing solution was 8.3, which was close to neutral, so it was low pollution.

Example 2 The photosensitive lithographic printing plate used in Example 1 was exposed to light for 40 seconds from a distance of 70 cTL using a 30 ampere carbon arc lamp, resulting in a 5-level gray scale.

This was an appropriate exposure time. ), and then developed with a developer having the following composition at 25° C. for 30 seconds using an Autoprocessor 80O8 automatic processor (manufactured by Fuji Photo Film Co., Ltd.).

Benzyl alcohol 300g Sodium isopropylnaphthalene sulfonate 150g Ammonium borate 100g Water
When 10,000 g of the lithographic printing plate thus obtained was printed on high-quality paper using a Norris Aucilia 125 printing machine, more than 30,000 sheets could be printed.

Also, when we investigated the processing ability of this developer, we found that it was 30 r
It was possible to process n:/1 or more, the development speed was almost the same as that of the new solution, and no staining of non-image areas occurred during printing.

This 30 rrl/1! The developer treated with this process was thick and colored due to the dye eluted from the photosensitive composition and the binder 2-hydroxyethyl methacrylate copolymer, but when a small amount of aluminum sulfate was added to this developer, When the pH was lowered to 7 or lower, the dye and binder precipitated, resulting in a clear liquid.

This clear liquid no longer had the ability to develop, but BO
Almost all organic matter was removed from the D measurement.

In this way, the treatment of developer waste containing ammonium borate was also simple.

Claims (1)

[Claims] 1. Unexposed photosensitive sheet coated with a photosensitive composition containing an acrylic or methacrylic acid polymer and a diazo compound having an acid value of 10 to 300 and having a hydroxy group and a cyan group in the side chain As a developer for removing the portion, at least one weak acid selected from the group consisting of ammonium borate, ammonium pentaborate, ammonium carbonate, ammonium silicate, tertiary ammonium phosphate, and tertiary ammonium phosphate is used. A developer composition comprising an aqueous ammonium salt solution.