JPH0577065B2 - - Google Patents

Description

[Detailed description of the invention]

FIELD OF THE INVENTION The present invention relates to a method for manufacturing photosensitive materials, and more particularly to a method for manufacturing negative photosensitive lithographic printing plates. 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. [Prior Art] 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 No. 1167-1971, Japanese Patent Application Laid-Open No. 1972-1167).
−9804, No. 47-24404, No. 47-38302, No. 50
-30604, 50-118802, 53-120903). However, with 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, poor development occurs over time, and non-image areas become smeared during printing. It has the following drawbacks. In order to improve this drawback, attempts have been made to add various stabilizers. For example, JP-A-54-151023
Phosphorous acid described in JP-A-53-3216, oxalic acid described in JP-A-53-36207, halogen-containing organic phosphoric acid ester compounds described in JP-A-50-36207, JP-A-51-143405 Heterocyclic diazonium salts described in US Pat. No. 3,679,419 and others
By adding phosphoric acid, sulfuric acid, organic sulfonic acid, polyacrylic acid, polyvinylphosphonic acid, or polyvinylsulfonic acid to the photosensitive layer as shown in column 6, line 69 to column 7, line 7 of the specification of the No. Although it has been recognized that the aging properties can be improved, it is still not fully satisfactory. Furthermore, Japanese Patent Application No. 178716/1984 discloses that at least 10% by weight of 1-methoxy-2-propanol is used as a solvent in the photosensitive composition.
It has been described that by coating a support with a polynuclear aromatic sulfonic acid as a stabilizer, a photosensitive material with improved staining in non-image areas over time can be obtained, but further improvement is possible. This is desirable. [Problems to be Solved by the Invention] The object of the present invention is to provide a photosensitive material prepared by coating a support with a photosensitive composition containing a photosensitive diazo resin and a polymer compound, particularly a negative photosensitive lithographic printing plate. It is an object of the present invention to provide a method for preventing poor development over time and thereby improving stains in non-image areas during printing. [Means for Solving the Problems] The present invention provides a negative photosensitive composition comprising a photosensitive diazo resin and a polymer compound, in which at least 10% by weight of the solvent is 1-methoxy-2-propanol, as a support. 1 to 100% by weight of N of the photosensitive diazo resin.
- A method for producing a photosensitive material, characterized in that the photosensitive composition contains a heterocyclic carboxylic acid and is coated 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, organic 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; 47
The above condensates and sulfonic acid salts as described in Publication No. 1167, such as P-toluenesulfonic acid or its salt, propylnaphthalenesulfonic acid or its salt, butylnaphthalenesulfonic acid or its salt, dodecylbenzenesulfonic acid or Salts thereof, organic solvent-soluble diazo resin organic salts which are reaction products with 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid or its salts are mentioned. Also, as shown in JP-A-58-27141, 3-methoxy-4-diazo-diphenylamine is condensed with 4,4'-bis-methoxy-methyl-diphenyl ether to obtain mesitylene sulfonate. is also appropriate. 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 JP-A-50
2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, acrylonitrile or methacrylonitrile, acrylic acid or methacrylic acid and optionally other copolymerizable monomers as described in Publication No. 118802. The copolymer has a hydroxyl group at the end as described in JP-A No. 53-120903,
and acrylic acid or methacrylic acid esterified with a group containing a dicarboxylic acid ester residue, a multicomponent copolymer of acrylic acid or methacrylic acid and, if necessary, other copolymerizable monomers, JP-A-1988- A monomer having an aromatic hydroxyl group at the end (for example, N-
(4-hydroxyphenyl)methacrylamide, etc.), acrylic acid or methacrylic acid, and optionally other copolymerizable monomers, as described in JP-A-56-4144. Examples include multi-component copolymers of alkyl acrylates, acronitrile or methacrylonitrile, and unsaturated carboxylic acids. In addition, acidic polyvinyl alcohol derivatives and acidic cellulose derivatives are also useful. Also, British Patent No. 1370316 which made polyvinyl acetal solubilized with alkali
The polymeric compounds described in this issue are also useful. The content of the diazo resin and the polymer compound in the photosensitive composition is 3 to 30% by weight of the diazo resin, and the content of the polymer compound is 3 to 30% by weight based on the total amount of both.
A suitable amount is 97 to 70% by weight. 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 diazo resin exceeds 30% by weight, the sensitivity decreases and practical difficulties arise. Therefore, a more preferable range is 5 to 20% by weight of diazo resin and 95 to 80% by weight of polymer compound.
It is. The N-heterocyclic carboxylic acid used in the present invention is an N-heterocyclic carboxylic acid having at least one carboxyl group.
- A heterocyclic compound soluble in an organic solvent is preferred. N-heterocycles include 5- or 6-membered rings containing at least one nitrogen atom;
For example, pyridine ring, quinoline ring, pyrazine ring,
Such as a pyrrole ring. Specific N-heterocyclic carboxylic acids include picolinic acid, dipicolinic acid, nicotinic acid, isonicotinic acid, quinolinic acid, lutidic acid, dinicotinic 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. Also 100% by weight
When the amount increases, the coating strength of the photosensitive layer tends to decrease and the printing durability tends to deteriorate. The proportion of 1-methoxy-2-propanol in the coating solvent in the present invention is 10 to 100% by weight,
Preferably 20-100%, most preferably 25-80%
It is. Preferred solvents that can be used in combination include methanol, ethanol, butanol, ethylene chloride, chlorobenzene, tetrahydrofuran, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, ethyl lactate, ethylene glycol monomethyl ether,
Examples include ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, dimethyl formamide, dimethyl sulfoxide, γ-butyrolactone, water, diacetone alcohol, and the like. 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 surfactants to improve coating properties, plasticizers (e.g. tricresyl phosphate, dimethyl phthalate) to impart flexibility and abrasion resistance to the coating film. , dibutyl phthalate,
trioticle phosphate, tributyl phosphate, tributyl citrate, polyethylene glycol, polypropylene glycol), acridine dye, cyanine dye, styryl dye, triphenylmethane dye, and phthalocyanine as coloring substances to visualize the image area after development. pigments such as and other common stabilizers for diazo resins (phosphoric acid,
Phosphorous acid, pyrophosphoric acid, oxalic acid, boric acid, benzenesulfonic acid, toluenesulfonic acid, polyacrylic acid and its copolymers, polyvinylphosphonic acid and its copolymers, polyvinylsulfonic acid and its copolymers, 5- Nitronaphthalene-1-phosphonic acid, 4-chlorophenoxymethylphosphonic acid, sodium phenyl-methyl-pyrazolone sulfonate, 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 of use, but is generally 0.5 to 0.5 to
It is 30% by weight. Suitable supports for the photosensitive materials of the invention are dimensionally stable plates. Such dimensionally stable plate-like materials 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. Plastic films, paper or plastic films laminated or vapor-deposited with metals such as those mentioned above are included. Among 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 that roughens the surface with a nylon brush while pouring slurry of abrasive particles, ball graining, chemical graining, electrolytic graining, and composite graining that combines these roughening methods. Twist and grain the surface. Next, sulfuric acid, phosphoric acid,
It is preferable to perform anodization in oxalic acid, boric acid, chromic acid, sulfamic acid, or a mixed acid thereof using a direct current or alternating current power source to form a strong passive film on the aluminum surface. Such a passive film itself makes the aluminum surface hydrophilic, but if necessary, silicate treatment (sodium silicate, sodium silicate, potassium silicate), potassium fluorozirconate treatment as described in U.S. Pat. No. 2,946,638, U.S. Pat. No. 3,201,247
The phosphomolybdate treatment described in the specification of German Patent No. 1091433, the polyacrylic acid treatment described in the specification of German Patent No. 1134093 and the specification of British Patent No. 1230447. Polyvinylphosphonic acid treatment, Special Publication No. 44-6409
Phosphonic acid treatment described in US Pat. No. 3,307,951, hydrophilic acid treatment described in JP-A-58-16893 and JP-A-58-18291. Particularly preferred are those which have been subjected to a hydrophilic treatment by a composite treatment consisting of a divalent organic polymer compound and a divalent metal, or by undercoating with a water-soluble polymer having a sulfonic acid group. Other hydrophilic treatment methods include silicate electrodeposition described in US Pat. No. 3,658,662. In the present invention, the coating amount of the photosensitive composition applied onto the roughened aluminum plate is preferably 0.3 to 5 g/m ² as solid content, more preferably
It is 0.5-3.5g/ ^m2 . The solid content concentration of the photosensitive composition that provides such a coating amount is suitably 1 to 50% by weight, preferably 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. . Suitable light sources for exposure include carbon arc lamps, mercury lamps, xenon lamps, metal halide lamps, strobes, ultraviolet laser beams, and the like. The alkaline aqueous developer used in the photosensitive lithographic printing plate of the present invention refers to one having a pH of 8 to 13 and containing 75% by weight or more of water, and if necessary, a small amount of an organic solvent, a surfactant, and an antifouling agent. , water softeners, etc. can be added. For example, JP-A-51-
No. 77401, JP-A-51-80228, JP-A-53-44202
Organic solvents (benzyl alcohol, ethylene glycol monophenyl ether) with solubility in water of 10% by weight or less at room temperature, alkaline agents (triethanolamine, monoethanolamine), anionic surfactants (aromatic sulfonates, dialkyl sulfosuccinates, alkylnaphthalene sulfonates,

[ka]

〔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. [Examples] Hereinafter, the present invention will be explained in more detail based on Examples. Note that % indicates weight %. Synthesis example 1 1-methoxy-2-propanol under nitrogen stream
Heat 100g to 100℃, and add 23g of 2-hydroxyethyl methacrylate and acronitrile.
A mixed solution of 27.5 g of benzyl methacrylate, 43 g of benzyl methacrylate, 6.5 g of methacrylic acid, and 0.4 g of benzoyl peroxide was added dropwise over 2 hours. 15 minutes after completion of dripping, add 100g of 1-methoxy-2-propanol and benzoyl peroxide.
0.1 g was added and 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. This 2-
The acid value of the hydroxyethyl methacrylate copolymer was 40. Synthesis Example 2 Same as Synthesis Example 1, 2-hydroxyethyl methacrylate/acronitrile/ethyl methacrylate/methacrylic acid = 50/20/25/5% by weight
A copolymer of (monomer charge ratio) was obtained. The acid value of this copolymer was 31. Example 1 A 2S aluminum plate with a thickness of 0.24 mm was degreased by immersing it in a 10% aqueous solution of tertiary sodium phosphate kept at 80°C for 3 minutes, grained using the brush graining method, and then soaked in aluminic acid at 60°C. It was desmatted with a 3% sodium aqueous solution. The aluminum plate was anodized in 20% sulfuric acid at a current density of 2 A/dm ² for 2 minutes and then treated with a 3% aqueous solution of potassium silicate at 70° C. for 1 minute. The following photosensitive composition solution [1] was applied onto the thus obtained aluminum support using a whiler and dried at 100°C for 2 minutes. The applied amount after drying was adjusted to 1.5±0.1 g. Photosensitive composition solution [1] Copolymer of Synthesis Example 1 5.0g Diazo resin (1) 0.5g Victoria Piure Blue BOH 0.15g Dipicolinic acid 0.15g Phosphorous acid 0.1g Water 5.0g 1-methoxy-2-propanol 45.0g Methyl ethyl ketone 50.0g The diazo resin (1) used here was prepared by adding an aqueous solution of NaPF ₆ to an aqueous sulfate solution of a condensate of p-diazodiphenylamine and paraformaldehyde to precipitate it, and then taking it out and drying it. This diazo resin
The PF ₆ substitution rate was 89 mol%. 45 photosensitive lithographic printing plates created using the above method.
After being left under forced conditions of ℃ and 75% humidity for 7 days,
Image exposed 30g benzyl alcohol, 10g triethanolamine, 10g sodium isopropylnaphthalene sulfonate, 2g sodium sulfite, 0.5g trisodium nitrilotriacetic acid salt and 950g tap water.
The film was developed with a developing solution of 25° C. for 60 seconds, washed with water, and a protective gum made of gum arabic was applied. 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 plate obtained in this way was attached to a printing machine and printed, and the stains in the non-image areas were examined.
The printing plates of Examples of the present invention had significantly less staining in non-image areas than those of Comparative Examples. 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 5.0g Diazo resin (2) 0.5g Victoria Piure Blue BOH 0.15g Dipicolinic acid 0.15g Phosphorous acid 0.1g Water 5.0g 1-methoxy-2-propanol 45.0g Methyl ethyl ketone 50.0g The diazo resin (2) used here was synthesized using a condensate of p-diazodiphenylamine and paraformaldehyde and 2-methoxy-4-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. Comparative Examples The photosensitive composition solution of Example 1, the photosensitive composition solution containing no N-heterocyclic carboxylic acid in Example 1 (Comparative Example 1), 1- in Example 1
A photosensitive composition solution in which methoxy-2-propanol was replaced with ethylene glycol monomethyl ether (Comparative Example 2), a photosensitive composition solution containing no N-heterocyclic carboxylic acid in Comparative Example 2, and a photosensitive composition solution containing no N-heterocyclic carboxylic acid were prepared. The staining of non-image areas over time was evaluated under similar conditions. The results are shown in <Table-1>. The results show that the combination of 1-methoxy-2-propanol and N-heterocyclic carboxylic acid significantly improves the staining of non-image areas over time.

【table】

Claims (1)

[Claims] 1 Contains a photosensitive diazo resin and a polymeric compound, and at least 10% by weight of the solvent is 1-methoxy-2
- In a method for producing a photosensitive material by coating a negative photosensitive composition, which is propanol, on a support, 1 to 100% by weight of N-
A method for producing a photosensitive material, which comprises incorporating a heterocyclic carboxylic acid into the photosensitive composition and coating the composition on a support.