JPS62262049A - Diazo photosensitive lithographic printing plate - Google Patents

Abstract

PURPOSE:To improve a shelf life and the stability to processing chemicals to be used by incorporating a photosensitive diazo resin, lipophilic high-polymer compd. and titanium coupling agent into a photosensitive layer. CONSTITUTION:This printing plate has the photosensitive layer consisting of the compsn. contg. the photosensitive diazo resin and lipophilic high-polymer compd. and further contg. the titanium coupling agent on a base. The titanium coupling agent is incorporated usually at 0.01-5wt%, more preferably 0.1-1.5wt% into the photosensitive compsn. The lipophilic high-polymer compd. is incorporated at usually 40-99wt%, more preferably 50-95wt% into the solid content of the photosensitive compsn. The photosensitive diazo resin is incorporated at usually 1-60wt%, more preferably 3-30wt% into said compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a diazo-sensitive lithographic printing plate, and more particularly, to storage stability and stability against processing chemicals used in the printing process, that is, chemical resistance. This invention relates to an improved diazo-sensitive lithographic printing plate.

[Prior art]

Planographic printing is a printing method that uses water and ink on a planographic printing plate, supplying ink to image areas and water to non-image areas. It is necessary that the image area and the support are firmly adhered. In addition, the image area must have good stability (chemical resistance) to various chemicals used in the plate-making process where the lithographic printing plate material is exposed and then subjected to development treatment to obtain the lithographic printing plate, as well as the various chemicals used in the printing process. It is. Furthermore, it is also required that no stains occur in non-image areas during the printing process.

As a means to meet the above requirements, conventionally, in lithographic printing plate materials having a photosensitive layer on a support, a non-photosensitive material containing a silane coupling agent between the support and the photosensitive layer has been used. A method is known (Japanese Unexamined Patent Publication No. 59-192250) in which a neutral intermediate layer is provided adjacent to the support. If the lithographic printing plates are stored under low temperature, there are disadvantages such as insufficient storage stability, such as stains occurring in non-image areas during the printing process and a significant decrease in printing durability and chemical resistance. In order to manufacture the intermediate layer, additional equipment is required to provide the intermediate layer, which is not economically preferable.

[Purpose of the invention]

An object of the present invention is to solve the above-mentioned problems and provide a diazo-sensitive lithographic printing plate which has excellent storage stability and improved stability against processing chemicals used, that is, chemical resistance. .

[Structure of the invention]

The above object of the present invention is achieved by a diazo-sensitive lithographic printing plate having, on a support, a photosensitive layer made of a composition containing a photosensitive diazo resin, a lipophilic polymer compound, and further containing a titanium coupling agent. be done.

[Specific structure of the invention]

As the titanium coupling agent used as a component of the photosensitive layer in the present invention, those represented by the following general formula are preferably used.

(RO), Ti-X.

In the formula, RO is an alkoxy group, m is a number from 1 to 4, X is a fatty acid group, an alkoxy group, a phenol group, a phenoxy group,
It represents a phosphite group, a phosphate group, etc., n is a number from 1 to 5, and when n is 2 or more, X may be the same or different.

Specific examples of such titanium coupling agents include the following.

CH30 11] CH3CHOTi+OCCrvH3s) xCH300 1II II CH, -CH-0-Ti+O-P -0-P-(0-C
,8,7)2) 3CH CH.

(CHi CHO÷4Ti・(Pro CaH+Jz
OH) z(C,H,, -0-), Tt・CPro
C+3Hzt)zOH) zCProC+xHzfu)z
OH)! CHI ○ CHx CHO'rt+o CC7H+s) 1C
Hs ○-C, 11hsCH3C)I
OTi double o-c~C-CHJ z :11 CHl C1h 0-C-C+tH3sl
/ CH, 0 :11 CH3CH0-Ti+o-p+〇-CsH+Jz):I
C1(3 □ CHlCHOTi+OCtHa NH-CzH7NH
z): 1CH.

0 CHs CH, u CHs : 1 In the present invention, the titanium coupling agent is generally 0.01 to 5% by weight, particularly 0.1 to 1.5% by weight, in the photosensitive composition constituting the photosensitive layer. It is preferable to contain it in a proportion.

Examples of the photosensitive diazo resin used as a component of the photosensitive layer in the present invention include those manufactured by Photographic Science and Engineering (Photo).

Sci, Eng,) Volume 17, Page 33 (1973)
, U.S. Patent No. 2,063,631, U.S. Patent No. 2,679,
No. 498, specifications of No. 3,050,502, JP-A-5
It is obtained by condensing a diazo compound whose manufacturing method is described in Publication No. 9-78340 etc. with an active carbonyl compound such as formaldehyde, acetaldehyde or benzaldehyde in an acidic medium such as sulfuric acid, phosphoric acid or hydrochloric acid. Diazo resins, diazo resins obtained by condensation reaction of diazo compounds and diphenyl ether derivatives whose production method is described in Japanese Patent Publication No. 49-4001, and others can be mentioned.

Considering the sensitivity, storage stability, and film strength of the finally obtained photosensitive layer, in the present invention, the following general formula (+)
Use a photosensitive diazo resin represented by, especially a photosensitive diazo resin containing a resin in which n in the general formula (1) is 5 or more in a proportion of 20 mol% or more, particularly preferably 20 to 60 mol%. is preferred.

General formula (1) In the formula, R1-RZ and R1 are each the same or different,
A hydrogen atom, an alkyl group or an alkoxy group, R represents a hydrogen atom, an alkyl group or a phenyl group, X represents a counter anion, and n represents a number from 1 to 200. and R
, , R, and R1 include, for example, an alkyl group having 1 to 5 carbon atoms and an alkoxy group having 1 to 5 carbon atoms. -5 alkyl groups may be mentioned.

Such photosensitive diazo resins can be prepared by known methods such as Photographic Science and Engineering (Photo, Sci, Eng.) Vol. 17, No. 3.
4 pages (1973), U.S. Patent No. 2,063,631;
It can be obtained by polycondensing a diazonium salt with an aldehyde such as paraformaldehyde, acetaldehyde, or benzaldehyde in sulfuric acid, phosphoric acid, or hydrochloric acid according to the method described in No. 2,679.498.

In normal cases, the molar ratio of diazonium salt and aldehyde is t:o, 6 to 1:2, preferably t+o, 7 to 1:2.
A photosensitive diazo resin with a high degree of anger can be obtained by charging at a ratio of t:t, S and reacting at a low temperature for a short time, for example, at a temperature of 10° C. or less for about 3 hours.

The counter anion of the diazo resin described above includes an anion that forms a stable salt with the diazo resin and solubilizes the resin in an organic solvent. These include organic carboxylic acids such as decanoic acid and benzoic acid, stepped phosphoric and sulfonic acids such as phenyl phosphoric acid, and typical examples include methanesulfonic acid, chloroethanesulfonic acid, dodecanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, mesitylenesulfonic acid and anthraquinonesulfonic acid,
Aliphatic and aromatic sulfonic acids such as 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, hydroquinonesulfonic acid, 4-acetylbenzenesulfonic acid, dimethyl-5-sulfoisophthalate, 2,2°, 4,4
Hydroxyl group-containing aromatic compounds such as °-tetrahydroxyhenzophenone, 1,2.3-trihydroxyhenzophenone, 2.2°,4-trihydroxyhenzophenone, and halogens such as hexafluorophosphoric acid and tetrafluoroboric acid. Examples include, but are not limited to, perhalogen acids such as C10-104 and C10-104.

Particularly preferred among these is hexafluorophosphoric acid.

In the present invention, the lipophilic polymer compound used as a component of the photosensitive layer includes polyamide, polyether, polyester, polycarbonate, polystyrene, polyurethane,
Examples include polyvinychloride and its copolymers, polyvinyl butyral resins, polyvinyl formal resins, shrinks, epoxy resins, phenolic resins, acrylic resins, and others.

More preferable examples include copolymers having a molecular weight of usually 20,000 to 200,000, which are obtained from the seven polymers shown in (1) to (12) below.

(1) Monomers having aromatic hydroxyl groups, such as N-(4
-hydroxyphenyl)acrylamide or N-(4
-Hydroxyphenyl) methacrylamide, 0-1m-
1p-hydroxystyrene, o-.

m-1p-hydroxyphenyl-acrylate or monomethacrylate (2) Monomers having aliphatic hydroxyl groups, such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate (3) α, β of acrylic acid, methacrylic acid, maleic anhydride, etc. -Unsaturated carboxylic acids (4) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, acrylic acid-
(Substituted) alkyl acrylates such as 2-chloroethyl, 2-hydroxyethyl acrylate, glycidyl acrylate, N-dimethylaminoethyl acrylate (5) Methyl methacrylate, ethyl methacrylate,
Propyl methacrylate, butyl methacrylate, amyl methacrylate, cyclohexyl methacrylate, 2
- (Substituted) alkyl methacrylates such as hydroxyethyl methacrylate, 4-hydroxyethyl acrylate, glycidyl methacrylate, and N-dimethylaminoethyl methacrylate (6) Acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-ethylacrylamide , N-1 hexyl methacrylamide, N-cyclohexyl acrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl-N-phenylacrylamide and other acrylamides or methacrylamides (7) Ethyl Vinyl ethers such as vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, 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) Styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, etc. (10) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, phenyl vinyl ketone, etc. (11) Ethylene, propylene, isobutylene , butadiene, isoprene and other olefins (12). It may also be a copolymer.

It also includes (but is not limited to) copolymers obtained by copolymerizing the above monomers and further modified with, for example, glycidyl methacrylate, glycidyl acrylate, etc.

More specifically, a copolymer obtained from the monomers listed in (1) and (2) above and having a hydroxyl group is preferable, and a copolymer having an aromatic hydroxyl group is more preferable.

Further, polyvinyl butyral resin, polyurethane resin, polyamide resin, epoxy resin, noporafuku resin, natural resin, etc. may be added to the above copolymer, if necessary.

In the present invention, the lipophilic polymer compound is contained in the solid content of the photogenic composition [usually 40 to 99% by weight, preferably 50 to 99% by weight].
The content is 95% by weight. Also (8 light-related direzo...
The fat content is usually 1 to 60%, preferably 3 to 30%.

In the present invention, the photophobic composition for forming the photosensitive layer may further contain a color change agent (pigment) that changes color tone by reacting with free radicals or acids. The color change agent is used for the purpose of obtaining a visible image by exposure (exposed visible image) or a visible image after development.

As such a color change agent, any color change agent can be used as long as it reacts with free radicals or acids to change color tone. Here, "change in tone" includes both a change from colorless to a colored tone and a change from colored to colorless or a different colored tone. Preferred color changing agents are those that change color tone by forming a salt with an acid.

Examples of such a color change agent include Victoria Pure Blue Bol+ (Hodogaya Chemical Co., Ltd., Oil Blue 160).
3 (manufactured by Orient Chemical Industry Co., Ltd.), patent vinyl blue (manufactured by Sumitomo Mikuni Chemical Co., Ltd.), crystal violet, brilliant green, ethyl bioleft, methyl violet, methyl green, erythrosin B1 basinokufuchsin, malachite green, oil red, m -Cresol purple, rhodamine B1 auramine, 4-p
- Triphenylmethane-based, diphenylmethane-based, oxazine-based, xanthine-based, iminonaphthoquinone-based, azomethine-based, or anthraquinone-based dyes such as diethylaminophenyliminonaphthoquinone, cyano-p-diethylaminophenyl acetanilide, etc., ranging from colored to colorless. Alternatively, it can be cited as an example of a color change agent that changes to a different colored tone.

On the other hand, examples of color changing agents that change from colorless to colored include leuco dyes and, for example, triphenylamine, diphenylamine, 0-chloroaniline, 1.2.3-) liphenylguanidine, naphthylamine, diaminodiphenylmethane, p, p "-bis-dimethylaminodiphenylamine, 1,2-dianilinoethylene, p, ρ°, ρ"
-tris-dimethylaminotriphenylmethane, p, p
'- and sudimethylaminodiphenylmethylimine, p
, p', p''-triamino-0-methyltriphenylmethane, p, p-bis-dimethylaminodiphenyl-4-
Examples include primary or secondary arylamine dyes typified by anilinonaphthylmethane and p, ρ゛, p''-triaminotriphenylmethane.

Particularly preferably, triphenylmethane and diphenylmethane dyes are effectively used, more preferably triphenylmethane dyes, and Victoria Pure Blue BOH is particularly preferred.

The above-mentioned color changing agent is usually added in the photosensitive composition from about 0.5 to about 10
It is preferably contained in a proportion of 1% to 5% by weight, more preferably about 1 to 5% by weight.

In the present invention, various additives can be further added to the photosensitive composition for forming the photosensitive layer.

Examples of additives include alkyl ethers (e.g., ethyl cellulose, methyl cellulose), fluorine-based surfactants, and nonionic surfactants (e.g., Pluronic L-64 (Asahi Denka Co., Ltd.) to improve coating properties. company)], plasticizers to impart flexibility and wear resistance to the coating film (e.g., butyl phthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, diptyl phthalate, dihexyl phthalate, dioctyl phthalate,
tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, oligomers and polymers of acrylic or methacrylic acid),
Lipid-sensitizing agents to improve the greasiness of the image area (for example,
Stabilizers [e.g., phosphoric acid, phosphorous acid, organic a (citric acid, phosphoric acid, henzensulfone, etc.), stabilizers [e.g., phosphoric acid, phosphorous acid, organic a acid, naphthalenesulfonic acid, 4-methoxy-2-hydroxybenzophenone-5-sulfonic acid, tartaric acid, etc.). The amount of these additives added varies depending on the composition and purpose of use, but is 0.01 to 30% by weight based on the total solid content of the -113 to 8 photosensitive composition.

In order to form a photosensitive layer on a support using such a photosensitive composition, the above-mentioned photosensitive diazure resin, oil-based polymer compound, titanium coupling agent, and various additives added as necessary are added. A photosensitive composition is prepared by dissolving a predetermined amount of each additive in a suitable solvent (such as methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, acetone, methyl ethyl ketone, methanol, dimethyl formamide, dimethyl sulfoxide, water, or a mixture thereof). It is sufficient to prepare a coating solution, apply it onto a support, and dry it. It is desirable that the concentration of the photosensitive composition in the coating solution at the time of coating is in the range of 1 to 50% by weight, and in this case, The coating amount of the photosensitive composition is approximately 0.2~
It may be about 10 g/m.

In the present invention, as the support, for example, paper, plastic, metal, etc. can be used. Examples of metals include aluminum, magnesium, zinc, chromium,
Mention may be made of iron, nickel, and alloys of these metals, among others.

It is desirable that at least the surface of the support is made of these materials.

In other words, the back side of the support is combined with other base materials, such as paper, plastic, or other metal base materials pasted on the back side of a thin metal plate, or paper or plastic with metal on one or both sides. It may be vapor-deposited or plated, a metal foil pasted together, or a metal plate plated with another metal.

Furthermore, the surface of the support is preferably roughened.

Various conventionally known methods can be used to roughen the surface of the metal support, including mechanical methods such as ball polishing and brush polishing, and solutions containing acids or alkalis. Examples include chemical methods such as etching methods and electrochemical methods such as electrolytic etching methods.

Preferred supports in the present invention include aluminum minilum supports, and more preferably aluminum supports with roughened surfaces, particularly those whose roughened surfaces have been anodized and hydrophilized. Preferably.

Aluminum plate used as a support in the present invention (
To roughen the surface of aluminum (including laminates of other metals, paper, plastic, etc.), the same applies below), for example, brush polishing, ball polishing, honing, chemical polishing after degreasing the surface. Polishing method, electrolytic etching method, or a combination of two or more of these polishing methods can be applied. The anodizing treatment is performed, for example, in a single aqueous solution of an inorganic salt such as phosphoric acid, chromic acid, boric acid, or sulfuric acid or a japonic acid such as oxalic acid, or in a mixed aqueous solution of two or more of these acids, and preferably in sulfuric acid. water?
This is done by passing an electric current through an aluminum plate as an anode in 8 liquid.

The amount of anodized film is preferably 5 to 60 .mu./dlSz, more preferably 5 to 30 .mu./dI112.

Examples of hydrophilic treatment include hot water sealing treatment and sodium silicate treatment, but sodium silicate treatment is preferred because it provides good adhesion and storage stability. The treatment is carried out by immersing the object to be treated overnight in 7 volumes of sodium metasilicate having a concentration of 0.1 to 5% at a temperature of 50 to 95°C for 10 seconds to 5 minutes. Preferably, it is then treated by immersion in water at 60°C to 100°C for 10 seconds to 5 minutes.

The photosensitive layer formed on the support is subjected to conventional methods to produce a lithographic printing plate. That is, a negative relief image is formed on the original image by exposing the photosensitive layer to light through a transparent original image such as a line image or halftone image, and then developing with an aqueous developer. Light sources suitable for exposure include carbon arc lamps, mercury lamps, xenon lamps, metal halide lamps, strobes, and the like.

The developer used in the development of the diazo-sensitive lithographic printing plate according to the present invention may be any known developer, but the following are preferred.

That is, a developer suitable for developing the diazo-sensitive lithographic printing plate according to the present invention contains a specific organic solvent, an alkaline agent, and water as essential components.

Here, the specific organic solvent is one that can dissolve or swell the non-exposed area (non-image area) of the photosensitive layer made of the above-mentioned photosensitive composition when it is contained in the developer, and that can be used at room temperature ( The organic solvent is not particularly limited as long as it is an organic solvent having the above-mentioned characteristics, which refers to an organic solvent having a solubility in water of 10% by weight or less at 20° C.). Therefore, the organic solvent to be used is not limited, but examples thereof include ethyl acetate, propyl acetate, butyl acetate, amyl acetate, benzyl acetate, ethylene glycol motuptylacetate, butyl lactate, and butyl levulinate. carboxylic acid esters; ketones such as ethyl butyl ketone, methyl isobutyl ketone, and cyclohexanone; ethylene glycol monobutyl ether, ethylene glycol benzyl ether, ethylene glycol monophenyl ether, benzyl alcohol, methylphenyl carbinol, n-amyl alcohol, methyl These include alcohols such as amyl alcohol; alkyl-substituted aromatic hydrocarbons such as xylene; and halogenated hydrocarbons such as methylene dichloride, ethylene dichloride, and monochlorobenzene. One or more of these organic solvents may be used. Among these organic solvents, ethylene glycol monophenyl ether and benzyl alcohol are particularly effective. The content of these organic solvents in the developer is generally 1 to 20% by weight, particularly 2 to 10% by weight.
More preferable results can be obtained when the amount is % by weight.

On the other hand, alkaline agents contained as essential components in the developer include (A) sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium dibasic or tertiary phosphate, or Inorganic alkaline agents such as ammonium salts, sodium metasilicate, sodium carbonate, ammonia, etc.; (B) mono-, di- or trimethylamine, mono-, di- or triethylamine, mono- or triethylamine, n-butylamine, mono-, di- or triethanolamine; mono-, di- or tri-isopropanolamines,
Examples include organic amine compounds such as ethyleneimine and ethylenediamine.

The content of these alkaline agents in the developer is usually 0.
05 to 4% by weight, preferably 0.5 to 2% by weight.

Furthermore, in order to further improve the storage stability, rigidity resistance, etc. of the printing plate finally obtained, it is preferable to include a water-soluble sulfite in the developer. Such water-soluble sulfites are preferably alkali metal salts or alkaline earth metal salts of sulfite, such as sodium sulfite, potassium sulfite, lithium sulfite, magnesium sulfite, and others. The content of these sulfites in the developer composition is usually 0.05 to 4% by weight, preferably 0.1 to 1% by weight.

Certain solubilizers may also be included to aid in the dissolution of the organic solvents mentioned above in water.

As such a solubilizing agent, in order to achieve the desired effect of the present invention, it is preferable to use alcohols and ketones that are more easily soluble in water and have lower molecular weight than the organic solvent used, and also include anionic activators and amphoteric activators. etc. can also be used. Examples of such low-molecular alcohols and ketones include methanol, ethanol, propatool, butanol,
Acetone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methoxybutanol, ethoxybutanol, 4-
Methoxy-4-methylbutanol, N-methylpyrrolidone, etc. can be preferably used. Examples of the activator include sodium isoprobylnaphthalenesulfonate, sodium n-butylnaphthalenesulfonate, and sodium N-butylnaphthalenesulfonate.
Sodium methyl-N-pentadenylaminoacetate, sodium lauryl sulfate and the like are preferred. There is no particular restriction on the amount of solubilizing agents such as alcohols and ketones used, but generally about 30% of the total developer solution is used.
It is preferable that the amount is less than % by weight.

After the diazophotographic lithographic printing plate according to the present invention has been imagewise exposed, it can be brought into contact with the above-mentioned developer at a temperature of approximately room temperature to 40°C, or further rubbed for 10 to 60 seconds. Later, the unexposed areas of the photosensitive layer can be completely removed without adversely affecting the exposed areas of the photosensitive layer, resulting in excellent developability. In addition, the printing plate obtained in this way has good developability over time (storage stability).
It also has excellent rigidity resistance, does not cause any deterioration in finish, and is free from pollution and occupational health problems.

Examples of producing lipophilic polymer compounds, photosensitive diazo resins, and supports used in the practice of the present invention are shown below.

S A a's 8N-(4-hydroxyphenyl) methacrylamide 10
．． 0 g, acrylonitrile 25 g, ethyl acrylate 60 g 1 methacrylic acid 5 g and azobisisobutyronitrile 1.642 g in acetone and methanol 1:1
After dissolving in 112 mJ of mixed solvent and purging with nitrogen, the temperature was 6.
Heated at 0°C for 8 hours.

After the reaction was completed, the reaction solution was poured into water 51 with stirring, and the resulting white precipitate was filtered and dried to obtain 90 g of lipophilic polymer compound a.
I got it.

The molecular weight of this lipophilic polymer compound a was determined by gel permeation chromatography (hereinafter abbreviated as rGPcJ).
As a result of measurement, the weight average molecular weight was 85,000.

Oil Him b no mu 50.0 g of 2-hydroxyethyl methacrylate.

Acrylonitrile 20g, methyl methacrylate 25g
A mixture of 5 g of methacrylic acid and 1.2 g of benzoyl peroxide was added dropwise over 2 hours to 300 g of ethylene glycol monomethyl ether heated to 100°C.
After dropping, add ethylene glycol monomethyl ether 3
0.00 g and benzoyl peroxide 0.3 g were added and allowed to react for 4 hours.After the reaction was completed, diluted with methanol and water 57.0 g. The resulting white precipitate was collected by filtration and dried to obtain 90 g of a lipophilic polymer compound.

When the molecular weight of this lipophilic polymer compound was measured by GPC, the weight average molecular weight was 65,000.

, Diazo a 4p-diazodiphenylamine sulfate 14.5 g (5
0 mmol) was dissolved in 40.9 g of concentrated sulfuric acid under water cooling. 1.5 g (50 mmol) of paraformaldehyde was slowly added dropwise to this solution. At this time, the reaction temperature was 10
I made sure not to exceed ℃. After that, stirring was continued for 2 hours under water cooling.

This reaction mixture was added dropwise to 500I111 ethanol under water cooling, and the resulting precipitate was filtered off. After washing with ethanol, this precipitate was dissolved in 100+mf pure water, and to this solution was added a cold concentrated aqueous solution in which 6.8 g of zinc chloride was dissolved. The resulting precipitate was filtered, washed with ethanol, and dissolved in 150 ml of pure water.

To this liquid was added a cold concentrated aqueous solution in which 8 g of ammonium hexafluorophosphate was dissolved. The resulting precipitate was collected by filtration, washed with water, and then dried at a temperature of 30° C. for one day and night to obtain photosensitive diazo resin a.

When the molecular weight of this photosensitive diazo resin a was measured by CPC, it was found that it contained about 50 mol% of hexamers or more.

Aluminum plate a 1 + □ & 0.2 fin thickness aluminum plate is immersed in a 3% sodium hydroxide aqueous solution to degrease it, washed with water, and then treated with a salt i2 concentration of 1%.
Then, electrolytic etching was performed for 5 minutes at 3 A/da'' at 25°C in an aqueous solution with a boric acid concentration of 1%, and after washing with water, electrolytic etching was performed at 1.5 A at 30°C in a 40% sulfuric acid aqueous solution.
/dm” for 2 minutes, washed with water, and 1%
It was immersed in an aqueous solution of sodium metasilicate for 37 seconds at a temperature of 85° C., then immersed in water (pH 8.5) at a temperature of 90° C. for 25 seconds, washed with water, and dried to obtain an aluminum plate a.

Attach an aluminum plate with a thickness of 0.24 mm to a rotating drum and rotate it at a circumferential speed of 12 m/min. ) was sprayed using a centrifugal sprayer. After washing with water,
25 parts of 2000 mesh alumina abrasive and 75 parts of water (
(volume ratio) was sprayed in the same manner as above. After washing with water, place in a 1% aqueous sodium hydroxide solution at a temperature of 50°C.
After soaking at 90° C. for 9 seconds, it was anodized in the same manner as aluminum plate a, treated with sodium silicate, washed with water, and dried to obtain an aluminum plate.

Production of Aluminum Plate C An aluminum plate with a thickness of 0.3 mm was ball-polished for 15 minutes with an alundum abrasive having a grain size of 1000 mesh, and then washed with water, with a sodium hydroxide concentration of 2% and a sodium gluconate concentration of 0.5%. After chemical etching at a temperature of 60°C for 2 minutes with an aqueous solution of Ta.

Production of aluminum plate d An aluminum plate produced in the same manner as aluminum plate a was further prepared in Example 1 of JP-A-59-192250.
Silane coupling agent N11□ (CH
z) JH(C1(z)isi(OCII+)z's 0.2
% aqueous solution for 60 seconds at a temperature of 25°C, and the coating amount was 0.
An aluminum plate d was obtained by providing an intermediate layer of 10 .mu./dm''.

〔Example〕

Preparation of inflammatory composition 10 g of the lipophilic polymer compound of the type shown in Table 1, the titanium coupling agent of the type and amount shown in Table 1, and the following substances were added to methyl cellosolve 180mj+. A coating solution for forming a photosensitive layer was prepared by dissolving each of the five types of photosensitive compositions A to E.

Photosensitive diazo resin a Ig “Victoria Pure Blue BOHJ [Manufactured by Hodogaya Chemical ■] 0.2 g Jurimer AC-1OL [Polyacrylic acid manufactured by Niki Pure Chemical ■] 0.6 g
1. The coating solution obtained as shown in Table 2 was coated with aluminum 15. A photosensitive layer was formed by coating each of a - d using a whirler with a dry weight of 1.5 g/m and then drying at a temperature of 85 °C for 3 minutes to form a photosensitive layer. Ten types of diazo-sensitive lithographic printing plates were obtained. These are designated as samples 1 to 10.

After storing each of sample 1 to sample IO for 7 days at a temperature of 40°C and a relative humidity of 80%, they were exposed to heat from a distance of 60 cjn using an ultra-high pressure mercury lamp with a power consumption of 3.
Exposure for 0 seconds, and apply developer A having the composition shown below at a temperature of 25°C.
A lithographic printing plate is prepared by immersing it in water for 45 seconds and developing it, which is then installed on a printing press, and a printing test is performed to observe the presence or absence of contamination, and the chemical resistance and printing durability are simultaneously tested. For this purpose, use Ultra Plate Cleaner (ABC Chemical Co., Ltd.) every 2000 sheets.
Printing was continued while the plate was washed using a printing press (manufactured by Co., Ltd., Ltd.), and the number of prints until defects appeared in the image area and the printed matter became incomplete was determined as the stiffness resistance.

In the current phenomenon, C2p.

Claims (1)

[Claims] (1) In a diazo-sensitive lithographic printing plate having a photosensitive layer on a support, the photosensitive layer comprises a) a photosensitive diazo resin, b)
A diazo-sensitive lithographic printing plate comprising a composition containing a lipophilic polymer compound and c) a titanium coupling agent.