JPS62275243A - Production of photosensitive material - Google Patents

Abstract

PURPOSE:To prevent the defective development of a photosensitive material, especially a negative type photosensitive lithographic printing plate by the lapse of time by adding N-heterocyclic carboxylic acid to a photosensitive composition by a specified amount based on the amount of photosensitive diazo resin and by applying the composition to a support. CONSTITUTION:N-heterocyclic carboxylic acid is added to a photosensitive composition by 1-100wt%, preferably 10-50wt% of the amount of photosensitive diazo resin and the composition is applied to a support. Diazo resin soluble in an org. solvent is especially suitable for use as the photosensitive diazo resin and the resin may be composed of p-diazodiphenylamine and formaldehyde. The N-heterocyclic carboxylic acid added is an N-heterocyclic compound having at least one carboxyl group and is preferably soluble in an org. solvent.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention [Field of the Invention] The present invention relates to a method for producing a photosensitive material, and particularly to a method for producing a negative photosensitive lithographic printing plate. More specifically, the present invention relates to a method for producing a negative photosensitive lithographic printing plate that prevents the occurrence of scumming over time.

[Conventional technology]

Photosensitive compositions for negative lithographic printing plates containing a photosensitive diazo resin and a polymer compound have been widely known (for example, Japanese Patent Publication Nos. 1167-1987, 9804-1984, 24404-1984). , No. 47-38302, No. 5
No. 0-306.04, No. 50-118802, No. 53
-120903).

However, photosensitive lithographic printing plates in which these photosensitive composition solutions are coated on a support with a hydrophilic surface, especially an aluminum plate that has been made hydrophilic, have the disadvantage that poor development occurs over time and non-image areas become smeared during printing. have.

In order to improve this drawback, attempts have been made to add various stabilizers. For example, phosphorous acid described in JP-A-54-151023, oxalic acid described in JP-A-53-3216, and halogen-containing organic phosphoric acid ester compounds described in JP-A-50-36207. , heterocyclic diazonium salts described in JP-A-51-143405 and other phosphoric acids as shown in U.S. Pat. No. 3,679,419, column 6, line 69 to 7 @ line 7,
Although it has been recognized that the aging property can be improved by adding sulfuric acid, organic sulfonic acid, polyacrylic acid, polyvinylphosphonic acid, or polyvinylsulfonic acid to the photosensitive layer, it is still not fully satisfactory. Also, the special request in Showa 6
No. 0-178716 discloses the use of at least 10% by weight of 1-methoxy-2-propanol as the solvent of the photosensitive composition and by coating the support with a polynuclear aromatic sulfonic acid as the stabilizer. Although it is described that a photosensitive material with improved staining in non-image areas over time can be obtained, further improvement is desirable.

[Problem that the invention seeks to solve]

The object of the present invention is to provide a photosensitive material comprising a support coated with a photosensitive composition containing a photosensitive diazo resin and a polymer compound;
In particular, it is an object of the present invention to provide a method for preventing poor development of negative photosensitive lithographic printing plates over time and thereby improving stains in non-image areas during printing.

[Means for solving problems]

The present invention includes a photosensitive diazo resin and a polymer compound,
1 to 100% by weight of the photosensitive diazo resin in a method for producing a photosensitive material by coating a support with a negative photosensitive composition in which at least 10% by weight of the solvent is 1-methoxy-2-propanol. This is a method for producing a photosensitive material, which comprises incorporating an N-heterocyclic carboxylic acid into the photosensitive composition and coating it on a support.

The photosensitive diazo resin used in the present invention is a diazo resin typified by a condensate of an aromatic diazonium salt and a compound containing an active carbonyl group, such as formaldehyde.

In particular, solvent-soluble diazo resins are preferably used.

Examples of the diazo resin include organic solvent-soluble diazo resin inorganic salts, which are reaction products of a condensate of P-diazodiphenylamine and formaldehyde or acetaldehyde, and hexafluorophosphate or tetrafluoroborate; The condensate and sulfonic acid salts as described in Japanese Patent No. 1167, such as P-)luenesulfonic acid or its salt, propylnaphthalenesulfonic acid or its salt, butylnaphthalenesulfonic acid or its salt, dodecylbenzenesulfonic acid or the salt,
Examples include organic solvent-soluble diazo resin organic salts that are reaction products with 2-hydroxy-4-methquine benzophenone-5-sulfonic acid or its salts.

Also, as shown in Japanese Patent Application Laid-open No. 58-27141
-methoxy-4-diazo-diphenylamine 4.4'
A condensed mesitylene sulfonate with -bis-methoxy-methyl-diphenyl ether is also suitable.

The polymer compound used in the present invention is one that can dissolve or swell in an alkaline aqueous developer and photocure in the coexistence of the photosensitive diazo resin to become insoluble or non-swellable in the developer. Good to have.

Particularly suitable organic polymer compounds include copolymers containing acrylic acid, methacrylic acid, crotonic acid, or maleic acid as an essential component, such as 2-hydroxyethyl acrylate as described in JP-A-50-118802. or a multicomponent copolymer of 2-hydroxyethyl methacrylate, acrylonitrile or methacrylonitrile, acrylic acid or methacrylic acid, and optionally other copolymerizable monomers, JP-A-53-12090
Acrylic acid or methacrylic acid, acrylic acid, which has a hydroxyl group at the end and is esterified with a group containing a dicarboxylic acid ester residue, as described in Publication No. 3.
Or a multi-component copolymer with methacrylic acid and other copolymerizable monomers as necessary, JP-A-54-98614
A monomer having an aromatic hydroxyl group at the end as described in the above publication (for example, N-(4-hydroxyphenyl)methacrylamide, etc.), acrylic acid or methacrylic acid, and other copolymerizable as necessary. Examples include multi-component copolymers of alkyl acrylate, acronitrile or methacrylonitrile, and unsaturated carboxylic acids as described in JP-A-56-4144. In addition, acidic polyvinyl alcohol derivatives and acidic cellulose derivatives are also useful. Also useful is a polymer compound described in British Patent No. 1370316 in which polyvinyl acecool is solubilized with an alkali.

The content of these diazo resin and polymer compound in the photosensitive composition is suitably 3 to 30% by weight of the diazo resin and 97 to 70% by weight of the polymer compound, based on the total amount of both. . The smaller the content of the diazo resin, the higher the sensitivity, but if it is less than 3% by weight, it will be insufficient to photocure the polymer compound, and the photocured film will swell with the developer during development, weakening the film. On the other hand, if the content of the diazo membrane exceeds 30% by weight, the sensitivity decreases and this becomes a practical problem. Therefore, a more preferable range is 5 to 20% by weight of the diazo resin and 95 to 80% by weight of the polymer compound.

The N-hedrocyclic carboxylic acid used in the present invention is preferably an N-heterocyclic compound having at least one carboxyl group and is soluble in an organic solvent. The N-heterocycle includes a 5- or 6-membered ring containing at least one nitrogen atom, such as a pyridine ring, a quinoline ring, a pyrazine ring, and a pyrrole ring. Specific N-heterocyclic carboxylic acids include picolinic acid, dipicolinic acid, nicotinic acid, isonicotinic acid, quinolinic acid, lutidic acid, sinicotinic acid, isocincomeronic acid, cinchomeronic acid, quinaldic acid, and 4-hydroxypicolinic acid. , 3-hydroxypicolinic acid, 2-pyrazinecarboxylic acid, 2,3-pyrazinedicarboxylic acid, pyrrole-2-carboxylic acid, 6-hydroxynicotinic acid, chelidamic acid, and the like.

These compounds may be used alone or in combination of two or more, and the amount added is 1 to 100% by weight, more preferably 10 to 50% by weight, based on the diazo resin. If the amount added is less than 1% by weight, the ability to prevent staining will not be sufficient. Moreover, if the amount exceeds 100% by weight, the coating strength of the photosensitive layer tends to decrease and the printing durability tends to deteriorate.

1-Methoxy-2- occupied in the coating solvent in the present invention
The proportion of propanol is between 10 and 100% by weight, preferably between 20 and 100%, most preferably between 25 and 80%. Preferably, the solvents that can be used in combination include methanol, ethanol, butanol, ethylene chloride,
Chlorbenzene, tetrahydrofuran, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, ethinobe lactate ethylene glycol monomethyl ether, ethylene glycol dimethyl ether ethylene glycol monoethyl ether, dimethylformamide, dimethyl sulfoxide, T-butyrolactone, water,
Examples include diacetone alcohol.

Various additives can be further added to the photosensitive composition used in the present invention. For example, alkyl ethers (e.g., ethyl cellulose, methyl cellulose) and fluorine-based surfactants to improve coating properties, plasticizers (e.g., tricresyl phosphate, dimethyl phthalate, dibutyl phthalate, trioticle phosphate, tributyl phosphate, tributyl citrate, polyethylene glycol, polypropylene glycol), acridine dye, cyanine dye, styryl dye, triphenylmethane dye, etc. as coloring substances to visualize the image area after development. Common stabilizers for pigments such as phthalocyanine and diazo resins (phosphoric acid, phosphorous acid, pyrophosphoric acid, oxalic acid, boric acid, pencenesulfonic acid, toluenesulfonic acid, polyacrylic acid and their copolymers) , polyvinylphosphonic acid and its copolymer, polyvinylsulfonic acid and its copolymer, 5-
Nitronaphthalene-1-phosphonic acid, 4-chlorophenoxymethylphosphonic acid, sodium phenylmethyl-pyrazolone sulfone), 2-phosphonobutanetricarboxylic acid-1,2,4,1-phosphonoethanetricarboxylic acid-1,2, 2,1-hydroxyethane-1,1-disulfonic acid) can be added. The amount of these additives added varies depending on the purpose for which they are used, but is generally 0.5 to 30% by weight based on the total solid content of the photosensitive layer.

Suitable supports for the photosensitive materials of the invention are dimensionally stable plates. Such dimensionally stable plate-like objects include:
These include those conventionally used as supports for printing plates, and they can be suitably used in the present invention. Such supports include paper, paper laminated with plastics (eg, polyethylene, polypropylene, polystyrene, etc.), aluminum (including aluminum alloys),
Metal plates such as zinc, copper, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc. Examples include plastic films, paper or plastic films laminated or vapor-deposited with the metals mentioned above. Of these supports,
Aluminum plates are particularly preferred because they are extremely dimensionally stable and inexpensive.

A particularly preferred support for use in the present invention is a roughened aluminum plate, which can be manufactured in a variety of ways. For example, wire brush graining, brush graining in which the surface is roughened using a nylon brush while pouring slurry of abrasive particles, boulder graining, chemical graining, electrolytic graining, and composite graining that combines these roughening methods. Grain the surface. Next, if necessary, perform anodization in sulfuric acid, phosphoric acid, oxalic acid, boric acid, chromic acid, sulfamic acid, or a mixed acid thereof using a DC or AC power source to form a strong passive film on the aluminum surface. is preferred.

Although the aluminum surface is made hydrophilic by such a passive film itself, if necessary, it may be necessary to
6 and U.S. Pat. No. 3,181,461 (sodium silicate, potassium silicate), as described in U.S. Pat. No. 2,946,638. Potassium fluorozirconate treatment, phosphomolybdate treatment described in U.S. Pat. No. 3,201.247, Kyokoku Patent No. 1.091.433
The polyacrylic acid treatment described in the patent specification, Kyokoku Patent No. 1, 134.093 specification and British Patent No. 1.23
Polyvinylphosphonic acid treatment described in Japanese Patent No. 0.447, phosphonic acid treatment described in Japanese Patent Publication No. 44-6409, and phytic acid treatment described in U.S. Patent No. 3.307.951. , Japanese Patent Publication No. 58-16
Hydrophilic treatment by composite treatment of a hydrophilic organic polymer compound and divalent metal as described in No. 893 and JP-A-58-18291, or by undercoating with a water-soluble polymer having a sulfonic acid group. Particularly preferred are those that have undergone the following steps.

Other hydrophilic treatment methods include U.S. Patent No. 3.658
．． Mention may also be made of silicate electrodeposition as described in No. 662.

In the present invention, the coating amount of the photosensitive composition applied on the roughened aluminum plate is 0.3 to 0.3 as solid content.
5 g/m' is preferable, more preferably 0.5-3
．． 5g/m''.The solid content concentration of the photosensitive composition that provides such a coating amount is suitably 1 to 50% by weight,
Preferably it is 2 to 20% by weight. Conventionally known methods such as roll coating, bar coating, spray coating, curtain coating, and spin coating can be used to apply the photosensitive composition solution onto the aluminum plate. The applied photosensitive composition solution is preferably dried at 50 to 120°C. The drying method may be performed by starting at a low temperature and drying at a high temperature after preliminary drying, or by directly drying at a high temperature.

A lithographic printing plate having a photosensitive composition layer coated and dried on a roughened aluminum plate can be developed with an alkaline aqueous developer after image exposure to obtain a negative relief image of the original image. .

Light sources suitable for exposure include carbon arc lamps, mercury lamps, xenon lamps, metal halide lamps, strobes,
Examples include ultraviolet laser beams.

The alkaline aqueous developer used in the photosensitive lithographic printing plate according to the present invention is l1188-13 and contains 75% by weight of water.
or more, if necessary, a small amount of organic solvent,
Surfactants, antifouling agents, water softeners, etc. can be added. For example, JP-A No. 51-77401, JP-A No. 51-Sho.
-80228, JP-A No. 53-44202 and JP-A No. 5
5-52054, which have a solubility in water of 10% by weight or less at room temperature, organic solvents (penzylalconopeethylene glycol monophenyl ether), alkaline agents (triethanolamine, monoethanol), etc. amines), anionic surfactants (aromatic sulfonates, dialkyl sulfosuccinates, alkylnaphthalene sulfonates, branched alkyl sulfates), water and, if necessary, antifouling agents (sodium sulfite, sodium salt of sulfopyrazolone). Examples include weak alkaline aqueous solutions consisting of water softeners and water softeners (ethylenediaminetetraacetic acid sodium salt, nitrilotriacetic acid trisodium salt).

〔Effect of the invention〕

The photosensitive material produced by the method of the present invention exhibits very little staining in non-image areas even when subjected to imagewise exposure and development processing after a period of time, and provides printed matter without printing stains.

〔Example〕

Hereinafter, the present invention will be explained in more detail based on examples.

Note that % indicates weight %.

Synthesis Example 1 100g of 1-methoxy-2-propanol under nitrogen stream
was heated to 100° C., and a mixed solution of 23 g of 2-hydroxyethyl methacrylate, 27.5 g of acronitrile, 43 g of benzyl methacrylate, 6.5 g of methacrylic acid, and 0.4 g of benzoyl peroxide was added dropwise thereto over 2 hours. 15 minutes after the completion of the dropwise addition, 100 g of 1-methoxy-27propanol and 0.1 g of benzoyl peroxide were added.
The reaction was continued 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 was 40.

Synthesis Example 2 A copolymer of 2-hydroxyethyl methacrylate/acronitrile/ethyl methacrylate/methacrylic acid=50/20/2515% by weight (monomer charge ratio) was obtained in the same manner as in Synthesis Example 1. The acid value of this copolymer was 31.

Example 1 A 23 aluminum plate with a thickness of 0.24 mm was degreased by immersing it in a 10% aqueous solution of tribasic sodium phosphate kept at 80° C. for 3 minutes, grained by the Brassida raining method, and then polished.
It was desmutted with a 3% aqueous solution of sodium aluminate at 0°C. This aluminum plate was heated at 2A/dm2 in 20% sulfuric acid.
The sample was anodized for 2 minutes at a current density of , and then treated with a 3% aqueous solution of potassium silicate at 70° C. for 1 minute.

The following photosensitive composition solution [1] was coated on the aluminum support thus obtained using a whiler, and 1
It was dried at 00°C for 2 minutes. Application amount after drying is 1.5±
The weight was adjusted to 0.1 g.

Photosensitive Composition Solution [1] The diazo resin (1) used here was obtained by adding an aqueous NaPF5 solution to a sulfate aqueous solution of a condensate of p-diazodiphenylamine and paraformaldehyde to precipitate it, and then taking it out and drying it. The PF and substitution rate of this diazo resin was 89 mol%.

The photosensitive lithographic printing plate prepared by the above method was left under forced conditions of 45°C and 75% humidity for 7 days, and then imagewise exposed to 30 g of benzyl alcohol and 10 g of reethanolamine.
, 10g of sodium isopropylnaphthalene sulfonate
The film was developed in a developer containing 0.5 g of trisodium triacetate and 950 g of tap water at 25° C. for 60 seconds, washed with water, and coated with a protective gum made of gum arabic.

A printing plate was prepared in the same manner as in the above example except that sodium orbutylnaphthalene sulfonate was used instead of dipicolinic acid (comparative example).

The printing plates thus obtained were installed in a printing machine and printed, and the stains in the non-image areas were examined. The printing plates of the examples of the present invention had significantly more stains in the non-image areas than those of the comparative examples. There weren't many.

Example 2 On an aluminum support treated in the same manner as in Example 1, the following photosensitive composition solution [2] was applied and dried in the same manner as in Example 1.

Photosensitive composition solution [2] (Copolymer of Synthesis Example 2 5.0 g Diazo resin (2) 0.5 g The diazo resin (2) used here is a condensate of p-diazodiphenylamine and paraformaldehyde. 2-methoxy-4-
It was synthesized using hydroxy-5-benzoylbenzenesulfonic acid.

After forced aging in the same manner as in Example 1, a printing plate was obtained by image exposure, development, and gumming. This printing plate was attached to a printing machine and printed, and stains in non-image areas were examined.

As in Example 1, there was almost no staining in the non-image area.

Claims (1)

[Claims] In a method for producing a photosensitive material by coating a support with a negative photosensitive composition containing a photosensitive diazo resin and a polymer compound, in which at least 10% by weight of the solvent is 1-methoxy-2-propanol, 1-1 of the photosensitive diazo resin
1. A method for producing a photosensitive material, which comprises incorporating 00% by weight of N-heterocyclic carboxylic acid into the photosensitive composition and coating the composition on a support.