JPH04180067A - Method for making planographic printing plate - Google Patents

Abstract

PURPOSE:To prevent occurrences of precipitates, sludge, and the like during long-time development processing by using an o-quinonediazido compound as a photosensitive substance and developing it with an aqueous solution of an inorganic acid alkali metal salt or ammonium salt or the like. CONSTITUTION:An aluminum plate support is treated to enhance hydrophilicness and coated with the photosensitive solution containing the o-quinone diazido compound and an organic polymer, next, after drying, it is imagewise exposed to carbon arc light, and developed with the aqueous solution containing at least one of the alkali metal oxide, ammonium hydroxide, alkali metal salt of inorganic acid except silicic acid, ammonium salt, and water-soluble organic amine, thus permitting occurrences of depositions and sludge and the like to be prevented during the long-time development processing and the fatigued solution to be easily neutralized, and developability and staining resistance of the printing plate and the like to be improved.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for developing a photosensitive lithographic printing plate containing an 0-quinonediazide compound as a component of the photosensitive layer.

(Prior Art) Recently, positive-type PETs having a photosensitive layer containing an 0-quinonediazide compound as a photosensitive substance on an aluminum support have been developed.
As a developing solution for the S plate, a sodium silicate aqueous solution or a potassium silicate aqueous solution is relatively advantageously used. This is because the developability and stability can be easily adjusted by adjusting the content ratio and concentration of silicon oxide and sodium silicate (or potassium), which are components of sodium silicate (or potassium). However, when this type of developer is repeatedly processed in an automatic processor, water-insoluble sludge and sludge caused by silicon oxide are formed at the bottom of the developer tank, and furthermore, there are problems such as the spray pipe and nozzle becoming clogged. Ta. Furthermore, due to drying and liquid splashing when the automatic developing machine is stopped, water-insoluble silica is deposited around the developing bath, causing various problems. Furthermore, when this type of developer is neutralized when it is disposed of, silicon oxide precipitates in the form of a gel, causing environmental pollution, which is a problem.

Therefore, several attempts have been made to develop developing solutions that do not contain silicon oxide. However, with a developer without silicon oxide, the hydrophilicity of the non-image area of the printing plate is insufficient, resulting in staining during printing, or the lack of silicon oxide causes the support to be etched by the alkaline component in the developer. There was a problem that the aluminum component of the support was eluted in large quantities and the developability was significantly impaired.

(Problems to be Solved by the Invention) Therefore, an object of the present invention is to prevent the precipitation of silicic acid even when long-term processing is carried out in an automatic processor, and to prevent troubles such as clogging of spray nozzles due to accumulation of sludge and sludge. The object of the present invention is to provide a development processing method that is Another object of the present invention is to provide a developing processing method that reduces the load during waste liquid neutralization processing and reduces environmental pollution. Furthermore, another object of the present invention is to provide a developing method suitable for producing a photosensitive lithographic printing plate having excellent developability and stain resistance during printing.

(Means for Solving the Problems) An object of the present invention is to form a positive-working photosensitive lithographic printing plate having a photosensitive layer containing an 0-quinonediazide compound and an organic polymer on a hydrophilic support. After exposure, it contains at least one compound selected from the group consisting of alkali metal hydroxides, ammonium hydroxide, alkali metal salts of inorganic acids other than silicic acid, ammonium salts of inorganic acids other than silicic acid, and water-soluble organic amine compounds. Solved by treatment with aqueous solution.

The present invention will be explained in detail below.

Examples of the hydroxide contained in the developer of the present invention include potassium hydroxide, sodium hydroxide, lithium hydroxide, and ammonium hydroxide, and examples of salts of inorganic acids other than silicic acid include tertiary sodium phosphate, Tertiary potassium phosphate, Tertiary ammonium phosphate, Dibasic sodium phosphate, Dibasic potassium phosphate, Dibasic ammonium phosphate, Sodium bicarbonate, Potassium bicarbonate, Ammonium bicarbonate, Sodium carbonate, Potassium carbonate, Ammonium carbonate , sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, ammonium borate, and the like. Particularly preferred are bicarbonates, carbonates, and hydrogen carbonates. These may be used alone or in combination.

The water-soluble organic amine compounds used in the developer of the present invention include monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, n-butylamine, monoethanolamine, jetanolamine. , triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine, pyridine, and the like. Among these, monoethanolamine, jetanolamine, triethanolamine, etc. are particularly preferred, and may be used in combination with inorganic alkali metal salts.

The concentration of these basic compounds in the aqueous solution is preferably 0.05% by weight to 10% by weight. More preferably, if the pH of these materials is less than 11, they can be easily handled during plate-making work, and neutralization treatment can also be easily performed.

An anionic surfactant may also be added to the developer, if necessary. Furthermore, an organic solvent can also be added. Examples of anionic surfactants include sodium salts of lauryl alcohol sulfate, sodium salts of octyl alcohol sulfate, ammonium salts of lauryl alcohol sulfate, higher alcohol sulfate ester salts having 8 to 22 carbon atoms, such as disodium alkyl sulfate, and -2. , aliphatic alcohol phosphate ester salts such as, for example, the sodium salt of heptyl alcohol phosphate ester, alkyl salts such as the sodium salt of dodecylbenzenesulfonic acid, the sodium salt of isopropylnaphthalenesulfonic acid, the sodium salt of metanitrobenzenesulfonic acid, etc. Aryl sulfonates, such as C
,,H33CON(CH3) CHzCHzSOJa
Sulfonic acid salts of alkylamides such as, for example, sulfonic acid salts of dibasic fatty acid esters such as sodium sulfosuccinic acid dioctyl ester and sodium sulfosuccinic acid dihexyl ester.

It is appropriate that the anionic surfactant is 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 lowered, and if it is more than 5% by weight, for example, the dye contained in the photocurable photosensitive liquid may elute excessively (color loss). This results in disadvantages such as deterioration of mechanical and chemical strength such as abrasion resistance of photocured images.

Suitable organic solvents are those having a solubility in water of about 10% by weight or less, preferably 5% by weight or less. For example, 1-phenylethanol, 2-
Phenylethanol, 3-phenylpropanol 1.
4-Phenylphthanol-1,4-phenylbutanol-2,2-phenylbutanol-1,2-phenoxyethanol, 2-benzyloxyethanol, 0-methoxybenzyl alcohol, m-methoxyndyl alcohol, p -methoxybenzyl alcohol, benzyl alcohol, cyclohexanol, 2-methylcyclohexanol, 4-methylcyclohexanol, and 3-methylcyclohexanol.

The content of organic solvent is 1% based on the total weight of the developer when used.
~5% by weight is preferred. The amount used is closely related to the amount of surfactant used, and as the amount of organic solvent increases,
Preferably, the amount of anionic surfactant is increased.

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.

Furthermore, additives such as an antifoaming agent and a water softener can be added as required. Examples of water softeners include Na2PJt, Na5P303゜Na5P3
0. , Na, O, P(NaO,P)POJa,, polyphosphates such as carvone (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-diaminocyclohexanetetraacetic acid, its potassium salt, its sodium salt; 1,3-diamino-2- propatool tetraacetic acid,
・Aminopolycarboxylic acids such as its potassium salt and its sodium salt can be mentioned.

The optimal amount of such water softeners varies depending on the hardness of the hard water used and the amount used, but if the amount used is 0.01 to 5 weight by weight in the developer solution at the time of use, %, more preferably in the range of 0.01 to 0.5% by weight.

The positive photosensitive layer to which the present invention is applied includes those conventionally known as positive photosensitive compositions containing an 0-quinonediazide compound. Particularly preferred are those containing an O-quinonediazide compound and a phenolic resin.

The ○-quinonediazide compound is a compound having at least one ○-quinonediazide group, which increases its alkali solubility upon irradiation with actinic rays, and compounds having a wide variety of structures can be used. Regarding such O-quinonediazide compounds, see "Light-Sensitive Systems" by J. Koser, John Wiley & Co.
5ons, Inc.), pages 339-352. In particular, O- obtained by reacting with various aromatic polyhydroxy compounds or aromatic amino compounds
Sulfonic acid esters or sulfonamides of quinonediazide are preferred.

Among 0-quinonediazide compounds, Japanese Patent Publication No. 1984-284
Benzoquinone (1
, 2)-diazide sulfonic acid chloride or naphthoquinone-(1,2)-diazide sulfonic acid chloride and pyrogallol-acetone resin are most preferred. Other suitable 0-quinonediazide compounds include:
U.S. Pat. No. 3.046.120 and U.S. Pat. No. 3.188
．． Benzoquinone = (1
, 2)-diazide sulfonic acid chloride or naphthoquinone-(1,2)-diazide sulfonic acid chloride and esters of phenol-formaldehyde resins.

As other useful O-quinonediazide compounds, those reported in numerous patents and known can be used. For example, JP-A-47-5303, JP-A-48-63
No. 802, No. 63803, No. 48-63, No. 96-96.
No. 575, No. 49-38701, No. 133-1973
No. 54, Special Publication No. 11222/1973, 961/1973
No. 0, Publication No. 49-17481, U.S. Patent No. 2.7
No. 97.213, No. 3.454.400, No. 3.
No. 544.323, No. 3.573.917, No. 3
, 674.495, 3.785.825, British Patent No. 1, 227.602, 1.251.345
No. 1.267, 005, No. 1.329.88
No. 8, No. 1.330.932, German Patent No. 854
．． Examples include those described in various specifications such as No. 890.

Further, although such a ○-quinonediazide compound can be used alone in a positive photosensitive composition, it is preferably used in combination with a binder. Suitable binders include aqueous alkaline soluble novolak resins. Typical examples of such novolac resins include phenol-formaldehyde resin, cresol-formaldehyde resin, phenol-cresol-formaldehyde resin, and phenol-modified xylene resin.

Particularly preferred is phenol-formaldehyde novolac.

Other suitable binders include copolymers whose structural units are monomers shown in (1) to α■ below and which usually have a molecular weight of 1 to 200,000.

(1) Acrylamides, methacrylamides, acrylic esters, methacrylic esters and hydroxystyrene L having an aromatic hydroxyl group, such as N-(
4-hydroxyphenyl)acrylamide or N-(4
-hydroxyphenyl) methacrylamide, o-, m-
, p~hydroxystyrene, o-, m-, p-hydroxyphenyl-acrylate or methacrylate, o-,
m-, p-hydroxystyrene, (2) acrylic esters and methacrylic esters having aliphatic hydroxyl groups, such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, (3) acrylic acid, methacrylic acid, anhydride Unsaturated carboxylic acids such as maleic acid and itaconic acid, (4) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, acrylic acid-
(Substituted) alkyl acrylates such as 2-chloroethyl, glycidyl acrylate, N-dimethylaminoethyl acrylate, (5) methyl methacrylate, ethyl methacrylate,
Propyl methacrylate, butyl methacrylate, amyl methacrylate, cyclohexyl methacrylate, 4
(Substituted) alkyl methacrylates such as -hydroxybutyl methacrylate, glycidyl methacrylate, N-dimethylaminoethyl methacrylate, (6) acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-ethylacrylamide, N-hexyl Methacrylamide, N-cyclohexyl acrylamide, N-
Acrylamides or methacrylamides such as hydroxyethyl acrylamide, N-phenylacrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenylacrylamide, (7) ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, Vinyl ethers such as butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether, etc. (8) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate, etc. (9) Styrene, α-methylstyrene, methylstyrene, chloro Styrenes such as methylstyrene, vinyl ketones such as αO methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, phenyl vinyl ketone, olefins such as ethylene, propylene, isobutylene, butadiene, isoprene, 021N-vinylpyrrolidone, N- Vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylaterile, etc., 031N-(o-aminosulfonylphenyl)methacrylamide, N-(m-aminesulfonylphenyl)methacrylamide, N-(p-amino)sulfonylphenylmethacrylamide, Methacrylamides such as N-(1-(3-aminosulfonyl)naphthyl)methacrylamide, N-(2-aminosulfonylethyl)methacrylamide, acrylamides having the same substituents as above, and 0-amino Sulfonylphenyl methacrylate, m-aminosulfonylphenyl methacrylate, p
-aminosulfonylphenyl methacrylate, 1-(3
-aminosulfonylnaphthyl) methacrylate, and unsaturated sulfonamides such as acrylic esters having the same substituents as above.

Furthermore, a monomer that can be copolymerized with the above-mentioned polymer may be copolymerized. It also includes, but is not limited to, copolymers obtained by copolymerizing the above monomers and modified with glycidyl methacrylate, glycidyl acrylate, and the like.

More specifically, a copolymer having a hydroxyl group or a sulfonamide group containing the mercury listed in (1) and (2) above is preferable, and a copolymer having an aromatic hydroxyl group or a sulfonamide group is preferable. is even more preferable.

The above copolymer preferably contains an unsaturated carboxylic acid listed in (3), and the preferred carboxylic acid value of the copolymer is 0 to 3 meq/g, more preferably 0.5.
~2.5 meq/g.

The preferred molecular weight of the copolymer is 10,000 to 100,000.

Further, a polyvinyl butyral resin, a polyurethane resin, a polyamide resin, or an epoxy resin may be added to the above copolymer as necessary. The amount of 00-quinonediazide compound in the total composition is preferably 10-50% by weight, more preferably 20-40% by weight. The amount of binder resin in the entire composition is preferably 45 to 80.
The amount is preferably 50 to 70% by weight.

The positive photosensitive composition further contains fillers, pigments, dyes, pigments, photodegradable acid generators, such as 1°2-naphthoquinonediazide-(2)-4-sulfonic acid chloride, for improving coating properties. fluorosurfactants, and other conventional additives and auxiliaries. These additives vary depending on their type, but in general, the appropriate amount of additives to be added is 0.01 to 20% by weight, preferably 0.05 to 10% by weight, based on the total composition.

In order to prepare a lithographic printing plate printing material by installing such a positive photosensitive layer on a support, a photosensitive solution is prepared by dissolving predetermined amounts of the above-mentioned diazo compound, binder, and additives in an appropriate solvent. , applied onto a support and dried.

The coating amount of the photosensitive layer may be 0.1 to 7 g/m', preferably 0.2 to 5 g/m'.

Supports on which the positive photosensitive layer is placed include paper, paper laminated with plastic (such as polyethylene, polypropylene, polystyrene, etc.), metal plates such as aluminum (including aluminum alloys), zinc, copper, etc. Films of plastics such as cellulose acetate, cellulose triacetate, cellulose propionate, cellulose butyrate o-x, cellulose WIW&Wl, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, hollyvinyl acetal, etc., metals such as those mentioned above. Examples include paper or plastic film on which is laminated or vapor-deposited. In particular, in the case of photosensitive lithographic printing plates, metal supports such as aluminum plates are preferred. The surface of the aluminum plate is subjected to a hydrophilic treatment after being anodized.

As the hydrophilic treatment used in the present invention, US Pat.
．． No. 714.066, No. 3.181.461, No. 3.
There are alkali metal silicate (e.g. aqueous sodium silicate) methods as disclosed in No. 280.734 and No. 3.902.734. In this method, the support is immersed in an aqueous sodium silicate solution or electrolytically treated. Alternatively, potassium fluorozirconate disclosed in Japanese Patent Publication No. 36-22063 and U.S. Patent No. 3.276,868, No. 4.153.461,
A method such as treatment with polyvinylphosphonic acid as disclosed in No. 4,689,272 is used. Furthermore, a hydrophilic cellulose undercoat layer containing a water-soluble metal salt as described in US Pat. No. 3,860,426 may be provided. Among them, the most preferred treatment is alkali metal silicate treatment.

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, and the lithographic printing plate is produced. You can get the version.

If necessary, desensitization treatment may be performed after development, washing with water, desensitization treatment as is, or desensitization treatment after treatment with an acid-containing aqueous solution. Furthermore, in the development process of this type of photosensitive lithographic printing plate, the alkaline aqueous solution is consumed depending on the processing amount and the alkaline concentration decreases, or the alkaline concentration is decreased by air due to long-term operation of the automatic developer. Although the processing capacity decreases, the alkaline activity may be restored with a replenisher.

(Effects of the Invention) According to the method of the present invention, no precipitates or sludge are generated even if development is performed for a long time using an automatic processor, and neutralization of fatigued liquid is easy. Furthermore, the developability is good, and the resulting lithographic printing plate has excellent stain resistance.

The present invention will be explained in more detail with reference to Examples below.

Example 1 A 28 material aluminum plate with a thickness of 0.15 mm was soaked in a 10% aqueous solution of tertiary phosphoric acid kept at 80°C.
After degreasing by dipping for 0 seconds and graining with a nylon brush while pouring the pumice slurry onto an aluminum plate,
It was etched for 10 seconds in an aqueous solution of sodium aluminate at a temperature of 0.degree. C., and then washed with a 3% aqueous solution of sodium hydrogen sulfate. This aluminum plate was heated in 20% sulfuric acid at a current density of 2A/
Anodize for 2 minutes at dm2, then anodize at 70°C for 2 minutes.
．． It was treated with a 5% sodium silicate aqueous solution for 1 minute to produce an aluminum plate support A.

The following photosensitive solution A was applied to this aluminum plate.

Photosensitive liquid A Resin (1N average molecule M: 23υυ) Methyl ethyl ketone 12 parts by weight Methanol 4 parts by weight Ethylene dichloride 4 parts by weight Coated dry weight is 2.1 g
/m'. This photosensitive lithographic printing plate was imagewise exposed for 45 seconds from a distance of 70 cm using a 30 ampere carbon arc lamp, and developed for 30 seconds at 25° C. in an automatic processor using a developer having the composition shown below.

Stock solution (diluted 1:4 with water before use) Water
75 parts by weight potassium hydrogen carbonate
3.5 parts by weight potassium carbonate
When printing was carried out using the printing plate after 7 parts by weight development, good printed matter without stains was obtained. This development process was performed for 10
25 m″/Il of the fatigue liquid was forcibly applied at the place where it was carried out.
No sludge was observed even when % was evaporated. Also, when this fatigue liquid is neutralized by dropping acid,
No particular precipitates were observed, and just adding a small amount of acid turned into a neutral homogeneous solution, which was easy to dispose of.

Comparative Example 1 On the other hand, processing was performed using the same automatic processor using a developer having the following composition.

Triethanolamine 5 parts by weight When printing was carried out using the developed printing plate, good printed matter was obtained, but after this development process was carried out at 10 m'/l, the water of the fatigue solution was forcibly removed. When 25% was evaporated, sludge was observed at the bottom of the bath. In addition, when water evaporation was low (10% or less), no precipitates were observed, but when acid was added dropwise to this fatigue solution to neutralize it, precipitates were observed (precipitation in S102), and the treatment was discarded. It took a lot of difficulty. This is also unfavorable from the standpoint of environmental conservation.

Example 2 An aluminum plate grained with a 0.3 mm thick nylon brush was etched with alkali, further electrolytically etched in an aqueous nitric acid solution, then anodized in an aqueous sulfuric acid solution, and then etched in acetic acid at 70°C. Support B was obtained by treating with an aqueous zinc solution, washing thoroughly, and then drying. Photosensitive liquid B was applied thereon. This photosensitive lithographic printing plate was heated using a PS light (2KW metal halide lamp) manufactured by Fuji Photo Film Co., Ltd.
The film was exposed to light and developed using the following developer at 25°C for 30 seconds.

Photosensitive solution B Ester phthalic anhydride 0.08 parts by weight Methyl cellosolve acetate 20 parts by weight Methyl ethyl ketone 8 parts by weight Stock solution (used after diluting 1:1) Benzyl alcohol 10 parts by weight Heavy IR triethanolamine 20 parts by weight Monoethanolamine 5 parts by weight Perex NBL
30 parts by weight pure water
After developing 1000 parts by weight, printing was performed using the printing plate, and as a result, good printed matter without stains was obtained. This development process is 10m'/I! Even when 25% of the water in the fatigue fluid was forcibly evaporated at the location where this test was carried out, no sludge was observed. Furthermore, it was easy to dispose of this fatigue liquid by neutralizing it.

Comparative Example 2 On the other hand, photosensitive solution B was applied onto support B, and treated with a post-exposure developer.

Pellex NBL 10 parts by weight benzyl alcohol 2 When printing was carried out using the printing plate after heavy IH development, good printed matter was obtained, but when this development process was carried out at 10 m゛/Il, the fatigue was forced. When 25% of the liquid water was evaporated, sludge was observed at the bottom of the bath. In addition, when water evaporation was low (10% or less), no precipitates were observed, but when acid was added dropwise to this fatigue solution to neutralize it, precipitates were observed (precipitation in S10□), and the treatment It was difficult to dispose of it. This is also unfavorable from the standpoint of environmental conservation.

Comparative Example 3 Furthermore, photosensitive liquid A was applied onto the support A that had been subjected to the anodizing treatment in Example 1, and after exposure, it was treated with the developer of Example 1, and the developed printing plate was used. When printing was carried out, the printed matter was slightly stained. Also,
When this development treatment was carried out at 10 m'/j2, the development speed of the printing plate was significantly deteriorated, the treatment required a considerable amount of time, and the stain resistance during printing was also deteriorated.

Claims (1)

[Claims] After imagewise exposure of a positive-working photosensitive lithographic printing plate having a photosensitive layer containing an o-quinonediazide compound and an organic polymer on a hydrophilized support, an alkali metal hydroxide,
Developing with an aqueous solution containing at least one compound selected from the group consisting of ammonium hydroxide, an alkali metal salt of an inorganic acid other than silicic acid, an ammonium salt of an inorganic acid other than silicic acid, and a water-soluble organic amine compound. A method for making lithographic printing plates.