JPS62134649A - Photosensitive lithographic printing plate material - Google Patents

Abstract

PURPOSE:To obtain a photosensitive lithographic printing plate material having high mechanical strength and print-resisting power by forming a photosensitive layer contg. a specific polymer and non-photosensitive high-polymer compd. on an Al base of which the sand blasted surface is anodized. CONSTITUTION:The photosensitive layer contg. the following polymer (A) and non-photosensitive high-polymer compd. is formed on the Al base of which the sand blasted surface is anodized. (A) is the o-naphthoquinone diazide sulfonate polymer which is the condensation-polymerized resin of the polyhydroxy phenol and ketone or aldehyde having >=4.10X10<3>wt. average mol. wt. of the backbone polymer and <=8.0 ratio Mw/Mn between the weight average mol. wt. Mw and number average mol. wt. Mn. The content of the polymer (A) is about 10-95(wt.)%, preferably 20-90%, more preferably 25-80%. An alkali- soluble novolak resin is more preferable as the non-photosensitive high-polymer compd. and the content thereof in the entire compsn. of the photosensitive layer is 5-90(wt.)%, more preferably 10-80%.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a photosensitive lithographic printing plate material, and more particularly to a photosensitive lithographic printing plate material with improved chemical resistance.

[Conventional technology]

A positive-working photosensitive lithographic printing plate has an ink-receptive photosensitive layer on a hydrophilic support, imagewise exposes this photosensitive layer, and then develops it, leaving the image area and removing the non-image area. Form an image. In actual printing, the difference between the lipophilicity of the image area and the hydrophilicity of the non-image area is utilized. In the case of positive-working lithographic printing plates, unlike negative-working plates, the image area does not undergo photochemical changes and the film strength does not change to that extent.
Chemical resistance is inferior to general negative planographic printing plates.

In particular, during film plate making, the photosensitive layer may be eroded by the opaque that is frequently used, the image area may be eroded by ballpoint pens that use glycol solvents, and the film may be stuck on the photosensitive lithographic printing plate with adhesive tape. When the tape is stored under pressure for a long period of time or under high temperature and pressure, erosion of the image area due to the plasticizer seeping out from the base of the tape has become a problem.

Conventionally, various attempts have been made to improve chemical resistance in terms of photosensitive materials, polymer compounds (binders), and supports, and techniques for these improvements have been proposed.

For example, JP-A-55-76346, JP-A-56-1044
No. 56-1045 and No. 60-143345 disclose polycondensation resins of relatively low-molecular polyhydroxyphenols and ketones or aldehydes. -A technology employing naphthoquinonediazide sulfonic acid ester was proposed, and was also disclosed in Japanese Patent Application Laid-Open No. 55-57841 and Japanese Patent Application No. 60-4.
No. 6116 proposes a technology that employs a chemical-resistant polymer compound such as formalin condensation resin of mixed cresol and phenol, and furthermore, patent application No. 59-2297
No. 91 proposes a technique in which chemical resistance is improved by combining the amount of anodized film on the support and a polymer compound.

[Problem that the invention seeks to solve]

However, these conventional techniques cannot solve the problems such as the above-mentioned erosion, and in particular, in UV printing using UV ink (ink containing an ultraviolet absorber), these problems due to the weak chemical resistance. There is a problem in that this problem further expands and becomes obvious, resulting in failures such as poor printing durability.

Therefore, an object of the present invention is to use various drugs such as opaque,
It is an object of the present invention to provide a photosensitive lithographic printing plate material in which the erosion of image areas by glycol-based solvents, plasticizers, etc. seeping out of tapes is improved.

Another object of the present invention is to provide a photosensitive lithographic printing plate material that has improved printing durability in UV printing using UV ink.

Still another object of the present invention is to provide a photosensitive lithographic printing plate material that is resistant to scratches, that is, has high mechanical strength and printing durability.

[Means for solving problems]

As a result of extensive studies, the present inventor has discovered a photosensitive lithographic printing plate characterized by having a photosensitive layer containing the following (A) and CB) on an aluminum support whose grained surface is anodized. The present invention was achieved by discovering that the object of the present invention could be achieved using a suitable material.

[A]: Weight average molecule m M w of the backbone polymer is -1,
A polycondensation resin of a polyhydroxyphenol and a ketone or an aldehyde, which has a weight average molecular weight Mw of 10×10 3 or more and a ratio M W /M n of weight average molecular weight Mw to number average molecular weight Mn of 8.0 or less. - Naphthoquinonediazide sulfonic acid ester polymer [B]: non-photosensitive polymer compound The present invention will be explained in detail below.

The 0-naphthoquinonediazide sulfonic acid ester polymer, which is a polycondensation tree of polyhydroxyphenol and ketone or aldehyde, used in the present invention as component (A) is a compound as shown below.

As the polyhydroxyphenol which is a monomer of the backbone polymer, catechol, (methyl)resorcin, hydroquinone, pyrogallol, phloroglucin, etc. are preferably used. Further, more preferred is pyrogallol.

As the ketone or aldehyde, acetone, formaldehyde, acetaldehyde, benzaldehyde, crotonaldehyde, etc. are preferably used, and acetone is more preferable.

A generally known method is applied to synthesize the polycondensation resin of polyhydroxyphenol and ketone or aldehyde. Polyhydroxyphenol is dissolved in ketone or aldehyde, or an appropriate solvent if necessary, and hydrochloric acid,
A polymer is obtained by causing polycondensation in a suitable acid such as phosphorus oxychloride or oxalic acid. As for the polycondensation conditions, compared to known methods, a method is preferably used in which the polymerization reaction is carried out at a relatively low temperature, preferably at room temperature or lower, at the initial stage of polymerization. In particular, in order to obtain a high molecular weight polymer, it is preferable to carry out the polymerization reaction by cooling to maintain the temperature at a low temperature around θ° C. for several hours from the initial stage of polymerization. On the other hand, it is preferable to add a larger amount of the acid as a catalyst than in the known method. For example, as the acid, phosphorus oxychloride, hydrochloric acid, oxalic acid, sulfuric acid, or a mixture thereof is added at 2.5 mol per polyhydroquine compound. %~20 mol%,
Preferably it is 4 mol% to 10 mol%.

Further, examples of the solvent to be used as necessary include ethanol, dioxane, methanol, and tetrahydrofuran. The amount used is preferably small compared to conventionally known methods (amounts).

The molecular weight of the polyhydroxy polymer compound obtained by these methods is determined by the GPC method (according to the calculation method shown in Synthesis Example 1) as the weight average molecule HA M w4, lOX
10' or more, weight average molecule 4i and number average molecule 51 M
The ratio of n M w / M n, that is, the molecular weight dispersion ratio (hereinafter abbreviated as dispersion ratio) h (8.0 or less, preferably the weight average molecular weight Fvl v is 4.50X to 3 to 2.OX 1
0', dispersion ratio is 1.3 to 6.01, preferably weight average molecular weight Mw is 5.00x 10' to 1.5X 10'
, the dispersion ratio is 1.5 to 4.5.

The feature of the present invention is that the molecular weight of the polycondensation resin of polyhydroxyphenol and ketone or aldehyde is high as described above, and the degree of dispersion is relatively small for a condensation resin, and the weight average molecular weight Q M wh<4.10xlO'
If the dispersion ratio exceeds 8.0, the object of the present invention cannot be achieved.

Specific examples of these backbone polymers include the above molecules ff
l! pyrogallol/acetone resin, resorcinol/benzaldehyde resin, methylresorcinol/formaldehydonzaldehyde resin, resorcinol/acetone resin with a dispersion range of Specifically, it is a solrescine benzaldehyde resin, and more preferably a pyrogallol acetone resin.

The naphthoquinone diazide sulfonic acid esters of these polyhydroxyphenol polymers can be easily obtained by the following synthetic method.

It is easily synthesized by dissolving a polyhydroxyphenol polymer in a suitable solvent such as dioxane, adding naphthoquinonediazide sulfonic acid chloride, and adding alkali carbonate dropwise to the equivalence point for esterification.

The condensation rate of 0-naphthoquinonediazide sulfonic acid chloride with respect to the OH group of this esterified product (% with respect to one OH group) is preferably 4 to 30 mol%, more preferably 6 to 20 mol%. The condensation rate is lower compared to the

The molecular weight of this esterified product varies slightly depending on the condensation rate of OH groups, but in general, for esterified products with a condensation rate of OH groups of 4 mol% to 30 mol%, the weight average molecular weight iMw is determined to be the same. is 4.20X 1
0' or more, dispersion ratio is 10.0 or less, preferably weight average molecular weight M is 4.60 x 1.0' to 2.2 x 104,
The dispersion ratio is 1.3 to 8.0, more preferably the weight average molecule QMW is 5. lOX 103~1.6X 10',
The dispersion ratio is 1.5 to 5.0.

The content of 1 in the photosensitive layer of this esterified polymer varies depending on the type, but is generally 10% by weight to 9% by weight.
5% by weight, preferably 20% to 90% by weight, more preferably 25% to 80% by weight.

As the non-photosensitive polymer compound of component (B) used in the present invention, an alkali-soluble polymer compound is preferably used. Examples include novolak resin; vinyl polymerization type polymers having carboxyl groups, phenolic OH groups, sulfonic acid groups, and phosphoric acid groups.

Examples of the novolak resin include phenol formalin novolak resin, m-cresol formalin novolak resin, p-cresol formalin novolak resin, and m-cresol formalin novolak resin.
Cresol/p-cresol mixed formalin novolak resin, pt-butylphenol-formaldehyde resin, phenol-modified xylene resin, and JP-A-55-57
A formalin novolac resin containing a mixture of phenol, m-cresol and p-cresol, which is described in Japanese Patent No. 841, is preferably used.

Among the above novolac resins, m-cresol/p-cresol mixed formalin novolac resins, phenol/m-cresol/
A p-cresol mixed formalin novolak resin exhibits excellent overall performance and is preferably used. Even more preferred is a phenol m-cresol/p-cresol mixed formalin novolac resin.

The molecular weight (polystyrene standard) of the novolak resin is preferably a weight average molecular weight of 51 M w of 3. OOX 10
3 to 2.00X 10', more preferably a weight average molecular weight M (5,0OxlO' to 1.50X 10').

Carboxyl group, phenolic OH! , sulfonic acid group,
Specific examples of vinyl polymerizable monomers having a phosphoric acid group include (meth)acrylic acid, N-hydroquinphenyl (
meth)acrylamide, hydroxyphenyl(meth)acrylate, itaconic acid, crotonic acid, maleic acid, p
-Hydroxystyrene, p-vinylsulfonic acid, vinylphosphonic acid and the like. By copolymerizing these monomers with other generally known vinyl monomers,
Provided as a non-photosensitive polymer compound.

Other vinyl monomers to be copolymerized include (1) acrylonitrile, methacrylonitrile (2) (meth)acrylamide, N-ethylacrylamide, N-hexylacrylamide, N-phenylacrylamide, etc.
Acrylamides (3) Vinyl ethers such as propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether, etc. (4) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate, etc. (5) Styrene, α-methyl Styrenes such as styrene, methylstyrene, and chloromethylstyrene (6) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone (7) Olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene , N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, etc. (8) Methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, etc. ) Acrylic esters (9) Hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and the like.

As a method for synthesizing the non-photosensitive polymer compound used in the present invention, generally known radical polymerization methods etc. are used.
For example, it is easily synthesized by a solution polymerization method using an initiator (0.1 to 4.0 mol %) such as azobisisobutyronitrile or benzoyl peroxide.

The molecular weight of the polymer compound is the weight average molecule QMw
5. OOx to3 to 2.00x to' is preferred, more preferably 1. QQX 10'~1.5QX 1
0'.

The content of the above-mentioned non-photosensitive polymer compound in the total composition of the photosensitive layer varies depending on the type, but is 5% by weight to 9% by weight.
Preferably 0% by weight, more preferably 10 to 80% by weight
It is.

In addition to the above-mentioned materials, the photosensitive lithographic printing plate material of the present invention includes, if necessary, a printout material, a plasticizer, a coatability improver, an oil sensitivity improver, and an additive for forming a visible image by exposure. It can contain various additives such as sensitizers.

A printout material for forming a visible image upon exposure to light consists of a compound that generates an acid upon exposure and a dye that changes color tone by interacting with this compound.

As a compound that generates an acid upon exposure to light, the following general formula I is used.
A trihaloalkyl compound or a diazonium salt compound represented by (1) or (2) is preferably used.

General Formula I In the formula, Xa is a trihaloalkyl group having 1 to 3 carbon atoms, W is N, S, Se, and PSZ is 0, N15SSe.

PSY represents a group having a chromophore group and consisting of a group of nonmetallic atoms necessary for cyclizing W and Z.

General formula (2) In the formula, Ar represents an aryl compound, and X represents a counter ion of an inorganic compound.

Specifically, the tri/'%roalkyl compound represented by the general formula (2) includes compounds represented by the following general formulas (1), (2), and (2).

General II ■ General Formula ■ General Formula ■ Xa In the formula, Xa has the same meaning as General Formula I, B represents a hydrogen atom or a methyl group, A represents a substituted or unsubstituted aryl group or a heterocyclic group, and n represents 011 or It is 2.

Specific example compounds of General 2) include oxadiazole compounds having a benzofuran ring such as JP-A No. 54-7
Examples include 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole compound described in Japanese Patent No. 4728.

In addition, as compounds of general formulas (■) and (■),
4-(2,4-ditomixy-4styryl)-6-)dichloromethyl-2-pyrone compound, 2,4-bis-(trichloromethyl)-6-p described in Publication No. 223
-methoxystyryl-5-triazine compound, 2.4-
Examples include bis-(trichloromethyl)-6-p-dimethylaminostyryl-5-triazine compound.

On the other hand, the diazonium salt compound is preferably a diazonium salt that generates a strong Lewis acid upon exposure to light, and the counter ion moiety is preferably a counter ion of an inorganic compound.

As a specific example, the anion part of the diazonium salt is a phosphorus fluoride ion, an arsenic fluoride ion, an antimony fluoride ion, an antimony chloride ion, a tin chloride ion, a bismuth chloride ion or a 41).
is an aromatic diazonium salt, preferably a diazophenylamine salt.

The amount of the exposure visible image imparting agent contained in the total photosensitive layer composition is 0.01 to 20% by weight, preferably 0.1 to 20% by weight, and more preferably 0.2 to 10% by weight.

On the other hand, as the pigment, any compound that forms a salt with a generally known acid can be used, such as Victoria Pure Blue B OH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue #603 (manufactured by Orient Chemical Co., Ltd.), and Patent. Pure Blue (manufactured by Sumitomo Mikuni Chemical Co., Ltd.), Crystal Violet, Brilliant Green, Ethyl Violet,
Triphenyl represented by methyl green, erythrosin B1 basic tsuksin, malachite green, oil red, m-cresol purple, rhodamine B1 auramine, 4-p-noethylaminophenylimino naphthoquinone, cyano-p-diethylaminophenyl acetanilide, etc. Examples include methane-based, nophenylmethane-based, oxazine-based, xanthine-based, iminonaphthoquinone-based, azomethine-based, and anthraquinone-based dyes. The amount of this dye added is approximately 0.01-10% of the total composition of the photosensitive material.
% by weight is preferred, more preferably 0.05-8% by weight
It is.

Plasticizers include various low-molecular compounds, such as phthalate esters, triphenyl phosphates, and maleate esters; coatability improvers include surfactants, such as fluorosurfactants, ethyl cellulose polyalkylene ether, etc. Examples include nonionic activators such as .

As the sensitizer, gallic acid derivatives described in JP-A-57-118237, JP-A-52-80022;
5-membered cyclic anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, succinic anhydride, pyromellitic acid, itaconic acid, etc., as described in JP-A-5111 -119
Examples include 6-membered acid anhydrides such as those described in Japanese Patent No. 32, such as glutaric anhydride and its derivatives. Among these, cyclic acid anhydrides are preferred, and 6-membered cyclic acid anhydrides are particularly preferred.

The content of these additives varies depending on their type and purpose, but in general, the amount added is 0 to the total composition of the photosensitive layer.
．． 01-20% by weight, preferably 0.05-10% by weight
is appropriate.

Furthermore, in order to improve oil sensitivity, a lipophilic substituted phenol formaldehyde resin and a substituted phenol formaldehyde resin are used. - A photosensitive resin obtained by condensing quinonediazide with sulfonic acid chloride can be added. These finger sensitizers should be added in an amount of 0.1 to 5 in the photosensitive color composition.
It is preferable that the content is n% by weight.

The photosensitive lithographic printing plate material of the present invention can be formed by dissolving the photosensitive composition described above in a solvent, applying it to the surface of a support and drying it.

Examples of solvents that can be used include cellosolves such as methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, and ethyl cellosolve acetate, dimethyl formamide, dimethyl sulfoxide, dioxane, acetone, nclohexanone, trichloroethylene, and methyl ethyl ketone. These solvents may be used alone or in combination.
Use by mixing N or more.

As the coating method, conventionally known methods such as spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating, and curtain coating can be used. Application insects vary depending on the application, but photosensitive planographic printing til1
For plate materials, the solid content is 0.5 to 5.09/m'
is preferred.

The aluminum support used in the present invention is an aluminum plate that has been subjected to a graining treatment or anodizing treatment, or an aluminum plate that has been subjected to a surface treatment such as a sealing treatment in addition to these treatments.

As the aluminum plate, a pure aluminum plate or an aluminum alloy plate containing aluminum as a main component (hereinafter simply referred to as an aluminum plate) is used.

Is the aluminum surface free from oil, rust, dirt, etc.? -) It is desirable to wash the aluminum plate with grease according to the usual method. Examples include solvent degreasing using trichlene, thinner, etc., emulnoyon degreasing using crocin and triethanolamine, and immersion treatment in a caustic soda aqueous solution having a concentration of 1 to 10% at 20 to 70° C. for 5 seconds to 10 minutes.

Examples of the graining treatment include a mechanical method and an electrolytic etching method.

Examples of mechanical methods include ball polishing, brush polishing, liquid honing, and puff polishing. The various methods described above can be used alone or in combination depending on the composition of the aluminum material.

Electrolytic etching is carried out in a bath containing one or a mixture of two or more inorganic acids such as phosphoric acid, sulfuric acid, hydrochloric acid, and nitric acid.

After the graining process, desmutting is performed using an alkali or acid aqueous solution as necessary to neutralize the material, followed by washing with water.

The anodic oxidation treatment is carried out by using an electrolytic solution containing one or more of sulfuric acid, chromic acid, oxalic acid, phosphoric acid, malonic acid, etc., and using an aluminum plate as an anode. Specifically, the concentration of sulfuric acid or phosphoric acid is 10 to 50.
% aqueous solution at a current density of 1 to IOA/dm.
Preferably, the method described in No. 8, conducted in sulfuric acid at high current density, and the method using sulfuric acid, described in U.S. Pat. No. 3,511,661, are used. Preferred is a method using a phosphoric acid bath as the main component.

The amount of anodic oxide film formed is 1 to 50 m9/dm”
is appropriate, preferably lO~40 m9/di'
It is. The amount of anodized film can be determined by, for example, applying an aluminum plate to a phosphoric acid chromic acid solution (85% phosphoric acid solution: 35 mQ).

Chromium oxide (VT): 209 is immersed in 1 (prepared by dissolving in water in 2) to dissolve the oxide film, and it is determined by measuring the change in weight before and after dissolving the slope film.

Specific examples of the sealing treatment include boiling water treatment, steam treatment, sodium silicate treatment, and dichromate aqueous solution treatment. In this case, the aluminum plate support can be subjected to a subbing treatment using an aqueous solution of a water-soluble polymer compound or a metal salt such as fluorinated zirconate.

In addition, when contact printing a film original onto a photosensitive planographic printing plate material, the printing frame is generally vacuumed, but a method for improving this vacuum adhesion can also be applied to the photosensitive planographic printing plate material of the present invention. can. Methods for improving vacuum adhesion include a method of mechanically creating irregularities on the surface of the photosensitive layer, a method of scattering solid powder on the surface of the photosensitive layer, and JP-A-50-1258.
A method of providing a matte layer on the surface of the photosensitive layer as described in Japanese Patent Application No. 05, a method of heat-sealing a solid powder on the surface of the photosensitive layer as described in Japanese Patent Application Laid-Open No. 12974/1980, etc. Can be mentioned.

The photosensitive lithographic printing plate material of the present invention can be used in the same manner as those conventionally used. For example, a transparent positive film is exposed to light using a light source such as an ultra-high-pressure mercury lamp, metal halide lamp, xenon lamp, or tungsten lamp, or scanned with a laser beam, and then developed with a developer, leaving only the unexposed areas on the surface of the support. , a positive-positive relief image is created.

The developer used in the present invention is preferably an aqueous alkaline developer, and examples of the aqueous alkaline developer include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium metasilicate, potassium metasilicate, and sodium diphosphate. , aqueous solutions of alkali metal salts such as trisodium phosphate. The concentration of the alkali metal salt is preferably used in a range of 0.05 to 20% by weight, more preferably o, 1-to% by weight.

Furthermore, an anionic surfactant, an amphoteric surfactant, and an organic solvent such as alcohol can be added to the developer as required.

Ethylene glycol monophenyl ether, benzyl alcohol, n-propyl alcohol, etc. are useful as organic solvents. The content of the organic solvent in the developer composition is preferably from 0.5 to 15% by weight, and more preferably from 1 to 5% by weight.

〔Effect of the invention〕

As is clear from the above description and the examples described below, according to the present invention, a 0-naphthyl resin of a polycondensation resin of a high molecular weight polyhydroxyphenol and a ketone or an aldehyde is coated on an aluminum plate whose grained surface is anodized. By using a quinonediazide sulfonic acid ester polymer and a non-photosensitive polymer compound, a photosensitive lithographic printing plate material that is resistant to special chemicals such as opaques, plasticizers, and UV inks, has high mechanical strength, and has stiffness resistance. can be provided.

〔Example〕

The present invention will be described in detail below, but the present invention is not limited to these Examples.

Photoreceptor synthesis example-1 Pyrogallol 1009 and distilled acetone 4009 were placed in a three-headed Kolben set in a constant temperature bath equipped with a cooling device, and nitrogen gas was blown into the tank to replace the nitrogen. 209 was added and the polycondensation reaction was carried out for 48 hours while stirring and keeping the temperature below 5°C. After the reaction was completed, the mixture was gradually poured into 5Q of water with strong stirring, and the resulting precipitate was filtered and dried.

The precipitated resin was collected by filtration and washed with water until the pH became approximately neutral (7). The filtered material was dried at 40°C or lower. In this way, a pale brown polyhydroxy resin 1009 was obtained.

The molecular weight of the polyhydroxy resin was measured by GPC (gel permeation chromatography). The number average molecule Q M n and the weight average molecule Q Mw were calculated by calculating the peaks in the oligomer region by the method described in Morio Takuue, Tatsuya Miyabayashi, and Masayuki Tanaka in "Journal of the Chemical Society of Japan," pages 800 to 805 (1972). This was done using the leveling method (connecting the center of the peak and the center of the valley).

As a result, Mw is 7.10X 103, dispersion ratio is 2.1
Met.

Next, this resin 609 was dispersed and dissolved in 720 ml of dioxane, 0-naphthoquinonediazide-5-sulfonyl chloride 459 was added, and after dissolving, potassium carbonate aqueous solution (20 Wt/wt%) 659 was added dropwise at 40 to 50°C. After carrying out the condensation reaction for 1 hour, the reaction solution was poured into a large amount of diluted hydrochloric acid (13 m of a hydrochloric acid (!).

The precipitated resin was collected by filtration and dried. 54 g of a yellow powder resin of 0-naphthoquinonediazide sulfonic acid ester of pyrogallol acetone resin was obtained. As a result of elemental analysis, the condensation rate of OH groups was 15 mol%. When the molecular weight was measured in the same manner as the polyhydroxy resin, the Mw was 7.42×10 3 and the dispersion ratio was 2.3. In this way, photoreceptor-1 was obtained.

Photoreceptor Synthesis Examples-2, 3, 4, 5 Pyrogallol, acetone, phosphorus oxychloride, reaction temperature, and reaction time of Photoreceptor Synthesis Example 1 were changed as shown in Table 1, and the resulting resin was used as Photoreceptor Synthesis Example-1. In the same manner as 0-naphthoquinone diazide ester, photoreceptor-2,3,4
,5 was obtained. Table 2 shows the molecular weight of the backbone polymer, the molecular weight of the photoreceptor, and the condensation rate.

Table 1 Photoreceptor Synthesis Examples 6, 7, 8 Using the polyhydroxy resin of the backbone polymer synthesized in Photoreceptor Synthesis Example 1, the amount of 0-naphthoquinonediazide-5-sulfonyl chloride and the amount of potassium carbonate aqueous solution were determined. Synthesis was carried out in the same manner as in Photoreceptor Synthesis Example 1, except as shown in Table 3. The analytical values are shown in Table 4.

Table 3 Photoreceptor Synthesis Example-9 43.69 g of resorcinol and 130 g of methanol were put into a 3-headed Kolben set in 1 g of IMLI equipped with a cooling device, nitrogen gas was blown in, and nitrogen T was replaced. Add 399% of benzaldehyde and 0.0% of concentrated hydrochloric acid.
15+t+l;j was added, and the reaction was carried out with stirring at a temperature of 25-35°C.

After reacting for about 24 hours, the mixture was poured into 2Q water with strong stirring, collected by filtration, and washed with water to obtain light brown powder resin 549.

GPC analysis value is Mw 4.20X to 3, variance ratio 3
, 5.

Next, 60 g of this tree M'ft was mixed with 720 m of dioxane.
C, 0-naphthoquinonediazide-5-sulfonyl chloride 219 was added, and potassium carbonate aqueous solution (2
0wt/wt%) 329 was added dropwise, and synthesis was performed in the same manner as in Synthesis Example-1. Table 2 shows the analytical values of the produced photoreceptor-9.

Photoreceptor Synthesis Example-10 Synthesis was carried out in the same manner as in Synthesis Example-9 except that 47 g of pyrogallol was used instead of 43.69 g of resorcinol in the recipe of Synthesis Example-9. Polyhydroxy resin 509 was obtained. GPC analysis value is Mw5,01x103, variance ratio is 3
．． It was 1.

Next, the same esterification reaction as in Photoreceptor Synthesis Example-9 was carried out.
Photoreceptor-10 was obtained. The results are shown in Table 2.

Comparative Photoreceptor Synthesis Example-1 According to the method described in Japanese Patent Publication No. 43-28403, 50 g of pyrogallol was dissolved in 3509 acetone, 59 phosphorus oxychloride was added, and the reaction was carried out at room temperature for 24 hours. After the reaction, the reaction solution was dropped into the water at the fire level, filtered,
I washed it with water.

When molecular weight was measured by GPC, Mw was 4.0.
1x to', dispersion ratio was 2.0.

Next, this resin was subjected to a condensation reaction with O-naphthoquinonediazide-5-sulfonyl chloride using the same recipe as in Synthesis Example 1 to obtain O-naphthoquinonediazide sulfonic acid ester of pyrogallol acetone resin. This is referred to as Comparative Photoreceptor-1. - When the molecular weight was measured by GPC, the Mw was 4.9.
0X 103, dispersion ratio was 1.8. Analysis values are shown in Table 2
It was shown to.

Comparative Photoreceptor Synthesis Example-2 In the synthesis recipe of Photoreceptor Synthesis Example-1, after carrying out the reaction for 8 hours while maintaining the temperature at 5°C, pyrogallol 50
Add 8 g of
A time reaction was performed. The subsequent treatments were carried out in exactly the same manner as in Synthesis Example 1.

As a result, the Mw was 4.50X to' and the dispersion ratio was 8.2.

Thereafter, condensation was carried out in the same manner as in Synthesis Example 1 to obtain Comparative Photoreceptor-2. As a result of analysis, the condensation rate of 0) 1 group was 15 mol %, MW was 4.75×10', and dispersion ratio was 8.5.

Example 1 Aluminum plate with a thickness of 0.24 mm (material 1050, g
Quality H16) was de-fingered in a 5% aqueous solution of caustic soda at 60°C for 1 minute, and then de-fingered in a 0.3 mol/η aqueous nitric acid solution.
Electrolytic polishing treatment was performed at 0°C for 30 seconds at an alternating current density of 50 A/dm.
After desmutting at 0°C for 10 seconds, anodizing was performed at 30°C and 4A/dm' for 1 minute in a 40% phosphoric acid solution. Then, hot water sealing treatment was performed for 20 seconds with hot water at 80° C. to obtain an aluminum plate as a support for lithographic printing plate material.

Next, the following photosensitive solution was applied to this aluminum plate using a hoarer and dried.

(Photosensitive coating liquid composition) - Photoreceptor = 1 1 part by weight - Phenol, m-cresol, p-cresol and formaldehyde copolycondensation resin (M nl, 25X 10', M guest 1
．． 3.5 parts by weight 2-trichloromethyl-5-[β-(2-benzofuryl)vinyl)-1,3, 4-oxadiazole 0.0
3 parts by weight/Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) 0.1 parts by weight/p-
0-naphthoquinonediazide sulfonic acid ester of butylphenol-benzaldehyde novolac resin (condensation rate of OH group 50 mo1%, Mn 9.50X 10", Mw
lJ9X 103) 0,09 parts by weight・Dimethyl sulfoxide 50 parts by weight・Methyl cellosolve 20 parts by weight・Dimethylformamide
The coating thickness of the photosensitive layer after drying 30 parts by weight is 24
It was m9/dm2.

A Kodak Step Tablet No. 2 manuscript and a film manuscript coated with "Opaque" (manufactured by Chugai Yakuhin Co., Ltd.) were brought into close contact with the photosensitive lithographic printing plate material obtained in this way, and a 2 kW metal halide lamp was used to produce 8 mW/dm. Exposure was performed at a distance of 1 m and a time of 92 seconds.

On the other hand, in order to evaluate the erosion dust caused by the tape, 30 sheets of cellophane tape (manufactured by Chiban Co., Ltd.) pasted on the membrane surface were stacked and stored in a thermostat at 50° C. for one week, and the erosion chamber was visually observed.

In addition, in order to examine the mechanical strength of the photosensitive layer, a continuous loading type scratch strength test 1a 'IIEIDON-18'1. −
We examined how easy it is to get scratched.

Further, using the developed printing plate, printing with UV ink and marking 11WI+ with oil-based ink were performed under the following printing conditions.

(Printing conditions using UV ink) Printing machine: Hamada Star CDl-900 Printing ink:
Toyo Flash Dry-0L-Beni Ap (manufactured by Toyo Ink Co., Ltd.) Reducer: Toyo Flash Dry Reducer-OP
(manufactured by Toyo Ink Co., Ltd.) Plate cleaner: Toyo Flash Dry Plate Cleaner (manufactured by Toyo Ink Co., Ltd.) Paper: High quality paper printing Speedonia 000 sheets/hour (printing conditions with oil-based ink) Printing machine: Heidel GTO Printing ink: Toyo King New Bright Red (manufactured by Toyo Ink Co., Ltd.) Paper: High quality Paper The results of printing speed +8 o o o sheets/hour or more are shown in Table 4.

Examples 2, 3, 4.5 In the photosensitive coating liquid used in Example 1, photoreceptors-2, 3, 4, and 5 (respectively Example 2.3) were used instead of photoreceptor-1.
．． 4.5)) was used to perform the same experiment.

The results are shown in Table 4.

Example 6 Photoreceptor-1 in the photosensitive coating liquid used in Example 1.
- An experiment was conducted in exactly the same manner as in Example 1, except that 0.6 parts by weight of Photoreceptor-6 was used instead of 1 part by weight. The results are shown in Table 4.

Example 7 In the photosensitive coating liquid used in Example 1, photoreceptor-1...
- An experiment was conducted in exactly the same manner as in Example 1, except that 2.6 parts by weight of Photoreceptor-7 was used instead of 1 part by weight. The results are shown in Table 4.

Example 8 In the photosensitive coating liquid used in Example 1, photoreceptor-1...
・[Instead of parts by weight, photoreceptor-8...0.8 parts by weight,
Instead of phenol/m-cresol/p-talesol formalin novolak resin, m-cresol which does not contain phenol
An experiment was conducted in exactly the same manner as in Example 1, except that a cresol/p-cresol formalin novolak resin (m/p charge weight ratio of 6/4) was used. The results are shown in Table 4.

Example 9 In the photosensitive coating liquid used in Example 1, phenol and
Instead of m-cresol/p-cresol formalin novolac resin, Example 1 of Japanese Patent Publication No. 1983-43890
The same procedure as in Example 1 was used except that the polymer compound (N-(4-hydroxyphenyl) methacrylamide; acrylonitrile: methyl methacrylate: methacrylic acid = 10:48:32:10 (charged molar ratio)) was used. We conducted an experiment. The results are shown in Table 4.

Examples io, tt In the photosensitive coating liquid used in Example 1, photoconductor-9 (Example-10) and photoconductor-10 (Example-11) were used instead of photoconductor-1. Ike conducted an experiment completely similar to Example 1. The results are shown in Table 4.

Comparative Example 1 Comparative photoreceptor-1 was used in place of photoreceptor-1 used in Example 1.
An experiment was conducted in exactly the same manner as in Example 1, except that Example 1 was used. The results are shown in Table 4.

Comparative Example 2 Comparative photoreceptor-1 was used instead of photoreceptor-1 used in Example 1.
The same experiment as in Example 1 was conducted for the pond using No. 2. The results are shown in Table 4.

As is clear from Table 4, by using the 0-naphthoquinonediazide sulfonic acid ester polymer of high molecular weight polyhydroxyphenol and ketone or aldehyde polycondensation resin of the present invention, chemical resistance, mechanical strength, and physical properties are improved. It can be seen that we have succeeded in developing a photosensitive lithographic printing plate material that has excellent printing durability and printing durability when printing with U■ printing and oil-based ink.

Claims (1)

[Claims] (1) A photosensitive planographic printing plate material comprising a photosensitive layer containing the following [A] and [B] on an aluminum support whose grained surface is anodized. [A]: The weight average molecular weight Mw of the backbone polymer is 4.10×
Weight average molecular weight Mw and number average molecular weight Mn at 10^3 or more
O-naphthoquinonediazide sulfonic acid ester polymer [B] of polycondensation resin of polyhydroxyphenol and ketone or aldehyde having a ratio Mw/Mn of 8.0 or less: non-photosensitive polymer compound