JPH0756356A - Treatment of photosensitive planographic printing plate and developer used therefor - Google Patents

Abstract

PURPOSE:To provide a treating method and a developer improved in problems that a developer (as well as its waste liquid) for a positive photosensitive planographic printing plate having a photosensitive layer containing o-quinone diazide compd. is hazardous for a human body due to the high pH of the liquid, handling of the developer is difficult, and when lots of photosensitive planographic printing plates each having an aluminum supporting body are developed for a long time, sedimentaion is produced due to corrosion of aluminum supporting bodies. CONSTITUTION:(1) A photosensitive planographic printing plate having a photosensitive layer comprising a positive photosensitive compsn. containing an o- quinone diazide compd. formed on a supporting body is processed with a water- base alkali developer in an automatic developing machine. In this method, the pH of the developer is <12.0 at 25 deg.C. (2) The water-base alkali developer described in (1) contains alkali metal carbonate as the main alkali component.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating a photosensitive lithographic printing plate having a photosensitive layer comprising a positive type photosensitive composition containing an o-quinonediazide compound on a support and a developing solution.

[0002]

2. Description of the Related Art Conventionally, a positive-working photosensitive lithographic printing plate having a positive-working photosensitive layer containing an o-quinonediazide compound on a support is developed with an alkali metal silicate. Aqueous alkaline aqueous solution is used, and its pH is high because it is necessary to dissolve the binder resin (generally cresol novolac resin is used) contained in the photosensitive layer of the positive-type photosensitive lithographic printing plate. Is used.

On the other hand, a developing solution for a positive type photosensitive material having a photosensitive layer containing an o-quinonediazide compound has a pH of about 12.
It has been disclosed that a suitable alkali strength is obtained at 5 to 13.3 (JP-A-55-115039). JP-A-60-257449 discloses that an o-quinonediazide compound and p as a binder are used.
A positive-type photosensitive composition is described which comprises an organic polymer which is hardly soluble in weak alkaline water of less than H12 but is easily soluble in strong alkaline water.

Thus, conventionally, as a developer for a positive-working photosensitive lithographic printing plate having a positive-working photosensitive composition containing an o-quinonediazide compound as a photosensitive component provided on a support, an alkali metal having a pH of 12 or more is used. It is known that an aqueous solution of silicate is used.
A pH of 12.5 to less than 13.5 is common.

[0005]

[Problems to be Solved by the Invention]
The pH developing solution poses a work safety problem because it may come into contact with the skin of the hand or get into the eyes during preparation and disposal, and it is also difficult to dispose of the waste solution. Also high
Since it has a pH, aluminum of the support is likely to be corroded, and therefore, there is a drawback that precipitation is likely to occur when a large number of sheets are processed for a long period of time.

The first object of the present invention is to process a non-silver salt light-sensitive material with a developing solution (including its waste solution), in which the danger to the human body and the difficulty of handling due to its high pH are improved. A method and a developer are provided. Second
Another object of the present invention is to provide a processing method and a developing solution in which a large number of photosensitive lithographic printing plates using aluminum as a support are prevented from causing precipitation even if they are developed for a long period of time.

[0007]

The constitutions of the present invention for achieving the above-mentioned objects of the present invention are as follows.

In a processing method in which a photosensitive lithographic printing plate having a photosensitive layer made of a positive photosensitive composition containing an o-quinonediazide compound on a support is processed by an automatic processor using an aqueous alkaline developer, Of aqueous alkaline developer
A method for treating a photosensitive lithographic printing plate, which has a pH at 25 ° C. of less than 12.0.

The positive type photosensitive composition contains at least one resin selected from polyphenol-containing novolacs, carboxyl group-containing phenol novolacs, and hydroxyphenyl group- and / or carboxyl group-containing acrylic resins. Item 1. The processing method according to Item 1.

An aqueous alkaline developing solution for a photosensitive lithographic printing plate having a photosensitive layer comprising a positive type photosensitive composition containing an o-quinonediazide compound on a support, which contains an alkali metal carbonate as a main alkali. And a pH at 25 ° C. of less than 12.0, a developing solution for a photosensitive lithographic printing plate.

The present invention will be described in detail below.

Examples of the o-quinonediazide compound contained in the photosensitive layer of the photosensitive lithographic printing plate according to the present invention include o-quinonediazidesulfonic acid esters of polyhydric phenols, for example, o-quinonediazidesulfonic acid ester of trihydroxybenzophenone and pyrogallol. o-quinone diazide sulfonic acid ester, o-quinone diazide sulfonic acid ester of tartrate, etc., or o-quinone diazide sulfonic acid ester of polyhydric phenol novolac resin, for example, o-quinone diazide sulfonic acid ester of pyrogallol-acetone resin, resorcinol-benzaldehyde Resin o-quinonediazide sulfonate, 2-methylresorcin / acetone resin o-quinonediazide sulfonate, and the like are preferable.

The photosensitive layer containing the o-quinonediazide compound in the processing method of the present invention contains an alkali-soluble binder resin, and the binder resin is disclosed in JP-A-57-101833.
Nos. 57 and 101834 and the polyhydric phenol novolac resins described in JP-A-58-134631, and the novolac resins having a phenolic hydroxyl group and a carboxyl group described in JP-A-58-134631, JP-A-63-183441. Issue 64-46759
It is preferable to use a resin containing a phenolic hydroxyl group-containing vinyl polymer as a main component described in JP-A Nos. 1-114841 and 1-116537.

The photosensitive layer preferably contains an alkali-soluble or sparingly soluble alkylphenol novolac resin or an o-quinonediazide sulfonic acid ester thereof as a sensitizing component, and additionally, a dye, a carboxylic acid or an anhydride thereof. It is preferable to include a development accelerator such as, a photoacid generator, a nonionic surfactant, and the like.

In the present invention, when the support is an aluminum (including aluminum alloy) support or an aluminum-coated support, the effect of improving the disadvantage that the developing solution corrodes aluminum and causes precipitation is remarkable. The surface of the aluminum support is preferably roughened (graining) and anodized. Further, it is preferable that a hydrophilic coating layer is provided on the anodized layer (alumite layer). Examples of the hydrophilic coating layer include alkali silicates described in US Pat. No. 3,181,461;
Polyvinylphosphonic acid described in 6-35685; JP-B-36-22
Alkali fluorinated zirconates described in 063; nickel nitrate, nickel acetate, alkali nitrite; JP-A-60-149491
And amino acids and polyamino acids described in JP-A-63-56498; CMC, etc., and a hydrophilic coating layer containing an alkali silicate treatment is particularly preferable.

The aqueous alkaline developer of the present invention may contain components contained in a known developer used for a positive photosensitive lithographic printing plate having a photosensitive layer containing an o-quinonediazide compound. That is, the developer can contain the following components.

Alkali metal silicates such as potassium silicate, sodium silicate, sodium metasilicate, potassium metasilicate, etc., ammonium silicate, alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, lithium hydroxide. Alkali metal carbonates, for example,
Sodium bicarbonate, sodium carbonate, potassium carbonate, etc.,
Inorganic alkaline agents such as ammonium carbonate, potassium triphosphate, dibasic potassium phosphate, tribasic ammonium phosphate, dibasic ammonium phosphate, etc., organics such as mono-, di- or triethanolamine and tetraalkyl hydroxide Alkaline agent.

Nonionic surfactants such as polyethylene glycol, polyoxyethylene lauryl ether,
Polyoxyethylene nonyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene behenyl ether, polyoxyethylene polyoxypropylene cetyl ether, polyoxyethylene polyoxypropylene behenyl ether, polyoxy Ethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene stearyl amine, polyoxyethylene oleyl amine, polyoxyethylene stearic acid amide, polyoxyethylene oleic acid amide, polyoxyethylene castor oil, polyoxyethylene abiethyl ether, Polyoxyethylene lanolin ether, polyoxyethylene monolaurate, polyoxye Ren monostearate, polyoxyethylene glyceryl monooleate, polyoxyethylene glycer monostearate, polyoxyethylene propylene glycol monostearate, oxyethylene oxypropylene block polymer, distyrenated phenol polyethylene oxide adduct, tribenzylphenol polyethylene oxide adduct Substance, octylphenol polyoxyethylene polyoxypropylene adduct, glycerol monostearate, sorbitan monolaurate,
Polyoxyethylene sorbitan monolaurate etc.

Anionic surfactants such as higher alcohol (C ₈ -C ₂₂ ) sulfate ester salts [eg sodium salt of lauryl alcohol sulfate, sodium salt of octyl alcohol sulfate, ammonium salt of lauryl alcohol sulfate, “Teepol- 81 ''
(Trade name, manufactured by Ciel Chemical Co., Ltd.), secondary sodium alkyl sulfate, etc.], aliphatic alcohol phosphate ester salts (eg, cetyl alcohol phosphate ester sodium salt), alkylaryl sulfonates (eg, dodecylbenzene sulfonic acid) Sodium salt, isopropylnaphthalenesulfonic acid sodium salt, dinaphthalenedisulfonic acid sodium salt, metanitrobenzenesulfonic acid sodium salt, etc., alkylamide sulfonates (for example, C ₁₇ H ₃₃ CON (CH ₃ ) CH ₂ SO ₃ Na, etc.), sulfonates of dibasic fatty acid ester (for example, dioctyl sodium sulfosuccinate, dihexyl sodium sulfosuccinate, etc.) and the like.

Examples of cationic surfactants such as amine type include polyoxyethylene alkyl amine, N-alkyl propylene amine, N-alkyl polyethylene polyamine, N-alkyl polyethylene polyamine dimethyl sulfate, alkyl biguanide, long chain amine. Oxide, alkylimidazoline, 1-hydroxyethyl-2-alkylimidazoline, 1-acetylaminoethyl-2-alkylimidazoline, 2-alkyl-4-methyl-4-hydroxymethyloxazoline and the like. Examples of the quaternary ammonium salt type include long-chain primary amine salt, alkyl trimethyl ammonium salt,
Dialkyldimethylethylammonium salt, alkyldimethylammonium salt, alkyldimethylbenzylammonium salt, alkylpyridinium salt, alkylquinolinium salt, alkylisoquinolinium salt, alkylpyridinium sulfate, stearamidomethylpyridinium salt,
Acylaminoethyldiethylamine salt, acylaminoethylmethyldiethylammonium salt, alkylamidopropyldimethylbenzylammonium salt, fatty acid polyethylene polyamide, acylaminoethylpyridinium salt, acylcholaminoformylmethylpyridinium salt, stearooxymethylpyridinium salt, fatty acid triethanol Amine, fatty acid triethanolamine formate, trioxyethylene fatty acid triethanolamine, fatty acid dibutylaminoethanol, cetyloxymethylpyridinium salt, p-isooctylphenoxyethoxyethyl dimethylbenzylammonium salt and the like.

Inorganic reducing agents, for example, sodium sulfite, potassium sulfite, ammonium sulfite, sodium bisulfite, sulfites such as potassium bisulfite, sodium phosphite, potassium phosphite, sodium hydrogen phosphite, phosphorous acid Phosphates such as potassium hydrogen, sodium dihydrogen phosphite and dipotassium hydrogen phosphite, hydrazine, sodium thiosulfate and sodium dithionite.

Organic reducing agents such as hydroquinone,
Phenol compounds such as metol and methoxyquinone, amine compounds such as phenylenediamine and phenylhydrazine.

Organic carboxylic acids, for example having 6 to 2 carbon atoms
0 aliphatic carboxylic acids and aromatic carboxylic acids in which a benzene ring or a naphthalene ring is substituted with a carboxyl group.

Aliphatic carboxylic acids such as caproic acid,
Enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, mistyric acid, palmitic acid, stearic acid, etc.

Aromatic carboxylic acids such as benzoic acid, o-
Chlorobenzoic acid, p-chlorobenzoic acid, o-hydroxybenzoic acid, p-hydroxybenzoic acid, p-tert-butylbenzoic acid, o-aminobenzoic acid, p-aminobenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, gallic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 2-hydroxy-1 -Naphthoic acid, 1-naphthoic acid, 2-naphthoic acid and the like.

Solvents, such as organic solvents having a solubility in water at 20 ° C. of not more than 10% by weight, such as ethyl acetate, propyl acetate, butyl acetate, benzyl acetate, ethylene glycol monobutyl acetate, butyl lactate, and butyl repurinate. Carboxylic acid ester; ethyl butyl ketone,
Ketones such as methyl isobutyl ketone and cyclohexanone; alcohols such as ethylene glycol monobutyl ether, ethylene glycol benzyl ether, ethylene glycol monophenyl ether, benzyl alcohol, methylphenyl carbinol, n-amyl alcohol and methyl amyl alcohol; xylene Alkyl-substituted aromatic hydrocarbons such as; methylene dichloride,
Halogenated hydrocarbons such as ethylene dichloride and monochlorobenzene.

The pH of the aqueous alkaline developer of the present invention is
Preferably 10 or more and less than 12, more preferably 10.5 or more and 11.8
It is the following. The developer preferably contains a surfactant (nonionic surfactant, anionic surfactant, etc.). The developer preferably contains substantially no organic solvent, the amount of the organic solvent is preferably 1% or less, and most preferably no organic solvent. The developer may contain a salt of an organic carboxylic acid, a chelating agent, a defoaming agent and the like in addition to the above components. The developer may contain an organic carboxylic acid or the like in addition to the anionic surfactant and the sulfite in order to impart suitability to a negative photosensitive lithographic printing plate.

The developer according to the second aspect of the invention contains an alkali metal carbonate as a main alkali. here,
The main alkali is 50% of the alkaline components in the developer.
It means at least wt%, more preferably at least 70 wt%.
The developer may be used in combination with alkali other than alkali metal carbonate such as silicate. By incorporating an alkali metal carbonate as a main alkali, the object of the present invention can be achieved to a higher degree.

[0029]

EXAMPLES The present invention will be described in more detail below with reference to examples.

Example 1 A JIS # 1050 aluminum alloy plate having a thickness of 0.24 mm was degreased with a NaOH aqueous solution, and then electrochemically roughened in a dilute hydrochloric acid aqueous solution.
After desmutting treatment in an aqueous NaOH solution, anodizing treatment was performed in dilute H ₂ SO ₄ , and finally sealing treatment was performed in hot water to obtain a support. Surface roughness Ra is 0.4 μm, amount of anodized film is 20 mg
It was / dm ² .

Next, by the method described in Example 1 of JP-A-55-73591, treatment with an aqueous sodium silicate solution and C
Treatment with an aqueous solution containing MC and nickel acetate was performed to obtain a support (I).

Next, a photosensitive solution having the following composition is applied,
A positive photosensitive lithographic printing plate was obtained by drying. The thickness of the photosensitive layer was 15 mg / dm ² .

Photosensitive solution o-quinonediazide sulfonic acid ester of pyrogallol-acetone resin (Mw 1000, esterification rate 30 mol%) 100 parts by weight resorcin benzaldehyde resin (used in Example 1 of JP-A-57-101833) 400 parts by weight pt-Butylphenol novolac resin o-quinonediazide sulfonic acid ester (esterification rate 20 mol%) 2 parts by weight Victoria Pure Blue BOH (Dye, Hodogaya Chemical Co., Ltd.) 1 part by weight 2-trichloromethyl-5- [Β- (2-benzofuryl) vinyl] -1,3,4-oxadiazole 1 part by weight Glutaric anhydride 20 parts by weight Methyl cellosolve 5000 parts by weight Next, a developing solution and a replenisher having the following composition are automatically developed. The positive type photosensitive lithographic printing plate was placed in a machine, imagewise exposed, and then developed at 27 ° C. for 20 seconds.

Developer (pH is 11.5 at 25 ° C.) Potassium carbonate 50 parts by weight Emulgen 147 (Kao Corporation, nonionic surfactant) 1 part by weight Water 1000 parts by weight Replenisher (pH 12.1 at 25 ° C.) Carbonate Potassium 50 parts by weight Potassium hydroxide 3 parts by weight Emulgen 147 2 parts by weight Water 1000 parts by weight The developer replenishment rate is 100 ml / m ^{2 for} processing replenishment, 150 ml over time.
/ Hour, daily replenishment (replenishment during non-operating period of automatic processor) 10
It was 0 ml / hour.

A large number of the positive working photosensitive lithographic printing plates were processed under the above conditions and gummed to obtain a lithographic printing plate. As a result, even after processing 1000 sheets, a stable printing plate without stains was obtained as with the first plate, and when printed on a printing machine, high quality printed matter was obtained without stains on any printing plate. . Further, the developer was exchanged after one month, but neither the stain of the developing tank nor the problem of precipitation was observed.

Example 2 The same procedure as in Example 1 was carried out except that the surface treatment after the anodizing treatment was carried out by the method described in Example 1 of JP-A No. 2-185493, which was treated with a No. 3 sodium silicate 2.5% aqueous solution. Support (II)
Got A positive photosensitive lithographic printing plate was obtained in the same manner as in Example 1 except that the photosensitive solution was changed to the following using this support.

Photosensitive liquid o-quinonediazide sulfonic acid ester of resorcin / benzaldehyde resin (used in Example 1 of JP-B-63-13528) 80 parts by weight gallic acid-resorcin-formaldehyde resin (JP-A-58-134631) Used in Example 1) 400 parts by weight o-quinonediazide sulfonic acid ester of pt-butylphenol novolac resin (esterification rate 20 mol%) 2 parts by weight Victoria Pure Blue BOH (Dye, Hodogaya Chemical Co., Ltd.) 1 Parts by weight 2-trichloromethyl-5- [β- (2-benzofuryl) vinyl] -1,3,4-oxadiazole 1 part by weight glutaric anhydride 20 parts by weight methyl cellosolve 5000 parts by weight The developing solution and the replenishing solution were charged into an automatic developing machine, and the positive photosensitive lithographic printing plate was imagewise exposed and then developed at 27 ° C for 20 seconds.

Developer (pH 11.3 at 25 ° C.) Potassium carbonate 20 parts by weight Perex NBL (Kao Corporation, anionic surfactant) 2 parts by weight Water 1000 parts by weight Replenisher (pH is 11.9 at 25 ° C.) Carbonate Potassium 30 parts by weight Potassium hydroxide 2 parts by weight Perex NBL (manufactured by Kao Corporation, anionic surfactant) 2 parts by weight Water 1000 parts by weight The developer replenishment amount is 120 ml / m ^{2 for} processing replenishment, 100 ml for replenishment over time.
/ Hour, daily replenishment (replenishment during non-operating period of automatic processor) 70
The same experiment as in Example 1 was carried out except for ml / hour. As a result, good results were obtained as in Example 1.

Example 3 A positive type photosensitive lithographic printing plate was obtained in the same manner as in Example 2 except that the photosensitive liquid was changed to the following.

Photosensitive liquid o-quinonediazide sulfonic acid ester of trihydroxybenzophenone (esterification rate: 33 mol%) 90 parts by weight Acrylic copolymer (Compound of Synthesis Example f-2 of JP-A-63-18344) 400 Parts by weight pt-Butylphenol novolac resin o-quinonediazide sulfonic acid ester (esterification rate 20 mol%) 2 parts by weight Victoria Pure Blue BOH (Dye, Hodogaya Chemical Co., Ltd.) 1 part by weight 2-trichloromethyl-5- [ β- (2-benzofuryl) vinyl] -1,3,4-oxadiazole 1 part by weight Glutaric anhydride 20 parts by weight Methyl cellosolve 5000 parts by weight Next, a negative photosensitive lithographic printing plate is disclosed in JP-A-1-102457. It was prepared according to the method of Example 1 of.

Next, a developing solution and a replenishing solution having the following compositions were charged in an automatic developing machine, and the negative photosensitive lithographic printing plate was imagewise exposed and then developed at 27 ° C. for 20 seconds.

Developer (pH is 11.6 at 25 ° C.) Potassium carbonate 65 parts by weight Emulgen 147 1 part by weight Perex NBL 20 parts by weight Potassium sulfite 2 parts by weight Water 1000 parts by weight Replenisher (pH is 12.2 at 25 ° C.) Potassium carbonate 65 Parts by weight Emulgen 147 2 parts by weight Perex NBL 20 parts by weight Potassium sulfite 3 parts by weight Potassium hydroxide 3 parts by weight Water 1000 parts by weight The developer replenishment rate is 100 ml / m ^{2 for} process replenishment, 140 ml for replenishment over time.
/ Hour, day replenishment (replenishment during non-operating period of automatic processor) 90
The same experiment as in Example 1 was carried out except for ml / hour. As a result, good results were obtained as in Example 1.

[0043]

INDUSTRIAL APPLICABILITY According to the present invention, the danger of the developing solution (including the waste solution) of a positive-working photosensitive lithographic printing plate having a photosensitive layer containing an o-quinonediazide compound to the human body due to its high pH. And the difficulty of handling are improved,
Further, there are provided a processing method and a developing solution in which the occurrence of precipitation due to corrosion of aluminum is improved when a large number of the photosensitive lithographic printing plates having aluminum as a support are developed for a long period of time.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yutaka Adachi Konica Stock Company, 1 Sakura-cho, Hino-shi, Tokyo In-house

Claims (3)

[Claims] 1. A processing method in which a photosensitive lithographic printing plate having a photosensitive layer made of a positive photosensitive composition containing an o-quinonediazide compound on a support is processed by an automatic processor using an aqueous alkaline developer. , Of the aqueous alkaline developer
A method for treating a photosensitive lithographic printing plate, which has a pH at 25 ° C. of less than 12.0. 2. The positive photosensitive composition contains at least one resin selected from polyphenol-containing novolacs, carboxyl group-containing phenol novolacs, and hydroxyphenyl group- and / or carboxyl group-containing acrylic resins. The processing method according to claim 1. 3. A water-based alkaline developing solution for a photosensitive lithographic printing plate, comprising a support and a photosensitive layer comprising a positive-type photosensitive composition containing an o-quinonediazide compound, wherein the alkali metal carbonate is an alkali. And a pH at 25 ° C. of less than 12.0, a developer for a photosensitive lithographic printing plate.