JPS63198046A - Photosensitive composition having excellent treating chemical resistant and ink forming properties - Google Patents

Abstract

PURPOSE:To obtain the titled composition having the excellent treating chemical resistant and ink forming properties by incorporating a specific high polymer compd., and a resin obtd. by condensing a substd. phenol and an aldehyde and/or an orthonaphthoquinone diazido sulfonate of the resin in the titled composition. CONSTITUTION:The titled composition comprises the high polymer compd. having a structural unit shown by formula I, the resin formed by the substd. phenol shown by formula II and the aldehyde, and/or the orthonaphthoquinone diazido sulfonate of the resin. In the formulas, R1-R6 are each hydrogen atom or alkyl group, etc., X is a bivalent org. group, (n) is an integer of 0-5, Y is a bivalent aromatic group which may be substd. Thus, the titled composition which has the excellent treating chemical resistant and ink forming properties and has less tendency for generating a stain at the time of printing, is obtd.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a photosensitive composition suitable for positive-working photosensitive lithographic printing plates, and more specifically, a photosensitive composition that has excellent processing chemical resistance and ink receptivity. The present invention relates to a photosensitive composition suitable for an excellent positive-working photosensitive lithographic printing plate.

(Prior Art) A positive-working photosensitive lithographic printing plate generally has an ink-receptive photosensitive layer formed on a hydrophilic support, which becomes solubilized by exposure to light. When this photosensitive layer is subjected to imagewise exposure and development, the non-image areas are removed while leaving the image areas, thereby forming an image. In printing, the difference in properties of image areas being lipophilic and non-image areas being hydrophilic is utilized.

Positive-working photosensitive lithographic printing plates have low resistance to various processing chemicals used during printing, such as isopropyl alcohol contained in fountain solution, ink, surface preparation liquid, plate cleaner, etc. However, it had the disadvantage of reduced printing durability. Japanese Patent Publication No. 43-28403 describes that the treatment chemical resistance was improved by using 0-naphthoquinodiazide sulfonic acid ester of a polycondensation resin of pilgallol and acetone as a photoreceptor. . It showed some good performance against the processing chemicals used in printing with conventional oil-based inks. However, in recent years, printing using ultraviolet curable UV ink has been increasing.

The above techniques are not sufficient for inks and processing chemicals (washing oil, plate cleaners, etc.) used in UV ink printing. Japanese Patent Publication No. 50-24641 describes a technique using 0-naphthoquinonediazide sulfonic acid ester, a polymeric compound containing p-hydroxymethacrylanilide or the like as a repeating structural unit, as a photoreceptor. This technology improves resistance to processing chemicals used in UV ink printing. However, it has the disadvantage that it has poor ink receptivity and poor gum removal properties at the start of printing, resulting in a large amount of waste paper.

In addition, in order to improve resistance to processing chemicals, a method of heat treatment at high temperature after exposure and development (hereinafter referred to as "burning treatment") is generally used. There is a problem in that monomer components of the resin come out and adhere to non-image areas, making it easy to cause scumming during printing.

(Problems to be Solved by the Invention) In order to solve the above-mentioned problems, the object of the present invention is to provide a photosensitive lithographic printing plate which has excellent processing chemical resistance and ink receptivity, and which does not cause scumming during printing. The object of the present invention is to provide a photosensitive composition suitable for.

(Means for solving the problems) In view of the above problems, the object of the present invention is to provide a polymer compound (A) having a structural unit represented by the following general formula [I],
A resin obtained by condensing substituted phenols and aldehydes represented by the following general formula [1F and/or an ortho-naphthoquinonediazide sulfonic acid ester compound of the resin (
It has been found that this can be achieved by a photosensitive composition containing B).

General formula [I] (wherein R1 and R2 each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a carboxyl group or a salt thereof, and R3 represents a hydrogen atom, a halogen atom, an alkyl group, or an aryl group, R4 represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group; Represents a group group.) General formula [
II] (In the formula, R5 and R6 each represent a hydrogen atom, an alkyl group, or a halogen atom, and R7 represents an alkyl group or a cycloalkyl group having 2 or more carbon atoms.) [Specific structure of the invention] Hereinafter, the present invention details.

In the general formula [E] of the present invention, R+ n and R2
each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a carboxyl group, or a salt thereof,
A hydrogen atom, an alkyl group such as a methyl group or an ethyl group, or a carboxyl group or a salt thereof (ammonium salt and alkali metal salt) is preferable, and a hydrogen atom is more preferable.

R3 represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group, preferably a hydrogen atom, a halogen atom such as bromine or chlorine, or an alkyl group such as a methyl group or an ethyl group, more preferably a hydrogen atom or a methyl group. be.

R4 represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.

Each group represented by R1 to R+ includes those having a substituent.

Y represents a divalent aromatic group which may have a substituent, preferably a phenylene group or a naphthylene group which may have a substituent, and any group can be used as the substituent. , typically alkyl groups such as methyl and ethyl groups, halogen atoms such as bromine and chlorine, carboxyl groups or their salts, alkoxy groups such as methoxy and ethoxy groups, hydroxyl groups, sulfo groups, cyano groups, and nitro groups. , acyl group, etc. More preferably, Y is an unsubstituted phenylene group or a naphthylene group having a methyl group.

X represents a divalent organic group, such as alkylene group, arylene group, aralkylene i, -co-1-NH8O2-1
-8O2NH-1 or any combination of these groups, etc., but an alkylene group is preferred.

n represents an integer of 0 to 5.

The polymer compound of the present invention is characterized by having a structural unit represented by the general formula [I] in its molecular structure,
A homopolymer type having a repeating structure of only the structural unit, or a copolymer having a repeating structure combining the structural unit and a structural unit having a structure in which an unsaturated double bond of another vinyl monomer is cleaved. It has a body structure. In the polymer compound of the present invention having a copolymer-type structure, the structural units used in rough combination with the structural units represented by the general formula [I] include the structural units represented by the general formula [I]. Ethylenically unsaturated olefins such as ethylene, propylene, butylene, imbutylene, butadiene, including those in which water 1 is introduced in place of the O-naphthoquinonediazide sulfonyl group, such as styrene, α-methylstyrene, p~chlorostyrene Styrenes such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, such as methyl acrylate, ethyl acrylate, acrylic 1lJn-
Butyl, isobutyl acrylate, dodecyl acrylate,
Acrylic 1in-octyl, acrylic M2-chloroethyl, phenyl acrylate, α-methyl chloroacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethyl ethacrylate, etc.
Methylene aliphatic monocarboxylic acid esters, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, α-ethylacrylamide, acrylanilide, p-chloroacrylanilide, m-nitroacrylanilide, m-methoxyacrylanilide, such as vinyl methyl ether, Vinyl ethers such as vinyl ethyl ether and vinyl isobutyl ether, vinyl esters such as vinyl chloride, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, etc.
Vinylidene chloride/vinylidene cyanide, such as 1-methyl-1-methoxyethylene, 1.1-dimethoxyethylene, 1.2-dimethoxyethylene, 1.1-
Ethylene derivatives such as dimethoxycarbonylethylene and 1-methyl-1-nitroethylene, N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidone, and N-vinylpyrrolidone; Examples include those having a structure in which the unsaturated double bond of a vinyl monomer is cleaved. Among these, preferred is a combination in which a hydroxyl group is introduced in place of the O-naphthoquinonediazide sulfonyl group in the structural unit represented by the general formula [I].

Next, typical examples of the polymer compound of the present invention will be given. In addition, in the following example compounds, MW is the weight average molecular weight, 1
:i :n or m:n respectively C) I,
CH.

There are various methods for synthesizing the polymer compound of the present invention. For example, α/β-unsaturated acid chlorides or α
・By reacting β-unsaturated acid anhydrides and primary or secondary amines having a phenolic hydroxyl group using a basic catalyst as necessary, a structural unit represented by the general formula [I] is obtained. After synthesizing a monomer having a structure corresponding to that in which a hydroxyl group is introduced in place of the O-naphthoquinonediazide sulfonyl group, the monomer is homopolymerized according to a conventional method, or the monomer and other A polymer compound having a phenolic hydroxyl group is obtained by copolymerizing it with at least one vinyl monomer, and then the obtained polymer compound is copolymerized with 0- By carrying out a condensation reaction with naphthoquinonediazide sulfonic acid chloride, an O-naphthoquinonediazide sulfonyl group can be introduced into the position of the phenolic water M1, thereby obtaining the polymer compound of the present invention.

In the polymer compound (hereinafter referred to as "photoreceptor of the present invention"), the condensation rate (reaction rate % per OH group) of 0-naphthoquinonediazide sulfonic acid chloride to the phenolic hydroxyl group is 15 to 80%. Preferably, it is more preferably 20 to 50%. The condensation rate is calculated by determining the content of sulfur atoms in the sulfonyl group by elemental analysis.

The molecular groups of the photoreceptor are measured by GPC (gel permeation chromatography) or osmotic pressure method.

The amount of the photoreceptor of the present invention in the photosensitive composition of the present invention is preferably 10 to 95% by weight, particularly preferably 40% by weight.
~90% by weight.

Next, a resin obtained by condensing a substituted phenol represented by the general formula [I[] and an aldehyde of the present invention, and an 0-naphthoquinonediazide sulfonic acid ester compound of the resin (
Hereinafter, these will be referred to as "the oil sensitizing agent of the present invention").

In the general formula [I[], R5 and R6 each represent a hydrogen atom, an alkyl group (including those containing 1 to 3 carbon atoms. Alkyl groups having 1 to 2 carbon atoms are particularly useful), or halogen. represents an atom (of fluorine, chlorine, bromine and iodine, chlorine and bromine are particularly preferred), and R7 is an alkyl group having 2 or more carbon atoms (preferably 15 or less carbon atoms; an alkyl group having 3 to 8 carbon atoms is ) or cycloalkyl groups (3 to 15
Includes those containing the number of carbon atoms. C3-C8cycloalkyl radicals are particularly useful. ).

Examples of the substituted phenols include isopropyl, phenol, tert-butylphenol, tert-amylphenol, hexylphenol, tert-octylphenol, cyclehexylphenol, 3-methyl-4-chloro-5-tert-butylphenol, isopropylcresol, tert-butyl cresol,
tert-amyl cresol, hexyl cresol, t
These include ert-octyl cresol and cyclohexyl cresol, among which tert-octylphenol and tert-butylphenol are particularly preferred.

Examples of the aldehydes include aliphatic and aromatic aldehydes such as formaldehyde, benzaldehyde, acetaldehyde, acrolein, crotonaldehyde, and furfural, including those having 1 to 6 carbon atoms. Among them, formaldehyde and benzaldehyde are preferred.

The resin obtained by condensing the substituted phenols and aldehydes of the present invention is synthesized by polycondensing the substituted phenols represented by the general formula [I] and aldehydes in the presence of an acidic catalyst. . The acidic catalyst used is hydrochloric acid,
Inorganic acids and organic acids such as oxalic acid, sulfuric acid, and phosphoric acid are used, and the blending ratio of substituted phenols and aldehydes is 0.7 to 1 part by mole of substituted phenols.
,0 mole part is used. Alcohols, acetone, water, tetrahydrofuran, etc. are used as the reaction solvent.

After reaction at a predetermined temperature (-5 to 120° C.) for a predetermined time (3 to 48 hours), the reaction product is obtained by heating under reduced pressure, washing with water and dehydration, or by causing water to precipitate.

The 0-naphthoquinonediazide sulfonic acid ester compound of the condensation resin of substituted phenols and aldehydes of the present invention can be obtained by dissolving the condensation resin in a suitable solvent such as dioxane, and adding 0-naphthoquinonediazide sulfonic acid chloride to the condensation resin. is added, and an alkali such as an alkali carbonate is added dropwise to a certain point while heating and stirring to esterify the product.

In the esterified product, the condensation rate of 0-naphthoquinonediazide sulfonic acid chloride with respect to the hydroxyl group of the phenol (reaction rate % with respect to one hydroxyl group) is 5 to 80%.
is preferable, more preferably 20 to 70%, still more preferably 30 to 60%. The condensation rate is calculated by determining the sulfur atom content m of the sulfonyl group by elemental analysis.

The amount of the fat-sensitizing agent in the photosensitive composition of the present invention is 0.
．． 05 to 15% by weight is preferred, particularly preferably 1 to 1% by weight.
It is 0 weight and 1%.

The fat sensitizing agent of the present invention preferably has a weight average molecular weight f1MW of 5. OX 102~5. OX I Q is in the range of 3, more preferably 7. OX 102~3.0×10
The range is 3. Its number average molecular (to) Mn is 3.0X
It is preferably in the range of 1Q2 to 2.5X1Q3,
More preferably 4. OX ranges from 102 to 2.0×103.

The molecular weight of the oil sensitizing agent of the present invention is measured by GPC (gel permeation chromatography). Calculation of number average molecular ffiMn and weight average molecular weight MW is as follows:
Morio Tsuge, Tatsuya Miyabayashi, Masayuki Tanaka, Journal of the Chemical Society of Japan, 8
By the method described on pages 00 to 805 (1972),
The test shall be performed by leveling the peaks of the oligomer region (connecting the centers of the peaks and valleys).

The photosensitive composition of the present invention may contain an alkali-soluble resin as a binder in order to improve film strength, processing chemical resistance, and alkali solubility.

As the alkali-soluble resin, JP-A-54-98613
Monomers having an aromatic water R group as described in the publication No. 1, for example N-(4-hydroxyphenyl) acrylamide, N-(4-hydroxyphenyl) methacrylamide, 0-1m-1 or p -Hydroxystyrene, o
-1m + or copolymer of p-hydroxyphenyl methacrylate, etc. and other monomers, U.S. Patent No. 4,123
Copolymers of hydroxyethyl acrylate or hydroxyethyl methacrylate with other monomers as described in , No. 276, may be mentioned. Other monomers to be combined include ethylenically unsaturated olefins, styrenes, acrylic acids, unsaturated aliphatic dicarboxylic acids, esters of α-methylene aliphatic monocarboxylic acids, nitriles, amides, and anilides. , vinyl esters, vinyl ethers, and N-vinyl compounds. Furthermore, novolac resins can also be used.

Among these, preferred are copolymers of N-(4-hydroxyphenyl)acrylamide and other monomers.

The novolak resin is obtained by copolycondensing at least one selected from phenol, I-cresol (or O-cresol), and p-cresol with an aldehyde in the presence of an acidic catalyst. Examples of the aldehyde include formaldehyde. , acetaldehyde, benzaldehyde,
Aliphatic and aromatic aldehydes such as acrolein and furfural are mentioned. Among these, formaldehyde is preferred.

Specific examples of novolac resins include phenol/formaldehyde resin, m-cresol/formaldehyde resin, O-cresol/formaldehyde resin, phenol/cresol/formaldehyde copolycondensate resin, I
-Cresol/p-cresol/formaldehyde copolycondensate resin, 0-cresol/p-cresol formaldehyde copolycondensate resin, phenol/m-cresol/p described in JP-A-55-57841
Examples include -cresol/formaldehyde copolycondensate resin, phenol/0-cresol/p-cresol/formaldehyde copolycondensate resin, and the like.

In addition, a polycondensation resin of polyhydroxyphenol and aldehyde can also be used. For example, JP-A-57
Resorcinol/formaldehyde resin, resorcinol/benzaldehyde resin, pyrogallol/benzaldehyde resin described in JP-A-101833 and JP-A-57-101834, catechol/formaldehyde resin and hydroquinone described in JP-A-59-86046.・Formaldehyde resin etc. can be mentioned.

Among the above novolac resins, phenol/m-cresol/p-cresol/formaldehyde resins are preferred.

The content of the alkali-soluble resin in the photosensitive composition is preferably 30 to 95% by weight, more preferably 50 to 85% by weight based on the total solid content of the photosensitive composition.

The molecule m of the alkali-soluble resin preferably has a number average molecular weight 1yln of 3. OX 102~5.0x1o3,
Weight average molecular weight Mw Ka1.0x 1Q3~2, OX
10”, more preferably jvln is 1.0×102~
3. Ox i Q3 , Mw is 5.0XiQ3 to 1.5
It is X104. The molecular weight of the resin is measured in the same manner as for the oil-sensitizing agent.

In addition to the above-described materials, the photosensitive composition of the present invention can also contain other additives as necessary. Plasticizers include various low-molecular compounds such as phthalate esters, triphenyl phosphates, maleate esters, and coating properties improvers include surfactants such as fluorine surfactants and ethyl cellulose polyalkylene ether. Examples include nonionic activators and the like, as well as printout materials for forming visible images upon exposure to light. The printout material consists of a compound that generates an acid or a free radical when exposed to light, and a dye that changes its color tone by interacting with the compound. It is described in JP-A No. 50-36209. 0-Naphthoquinonediazide-4-sulfonic acid halide, trihalomethyl-2-pyrone and trihalomethyl-triazine described in JP-A-53-36223, O described in JP-A-55-6244 -Naphthoquinonediazide-4-sulfonic acid chloride and electron-withdrawing position S! Examples include ester compounds with phenols or anilines having groups, halomethyl-vinyl-oxadiazole compounds and diazonium salts described in JP-A-55-77742.

Among these, halomethyl-vinyl-oxadiazole compounds are preferred, and in particular, 5-oxygen-containing heterocyclic groups such as the benzofuryl group described in JP-A-60-138539 are directly or via a vinyl group. 2 in position
-Heromethyl-1.3.4-oxadiazole compound is more preferred.

Further, as the organic dye, for example, Victoria Pure Blue BOH [Hodogaya Chemical Co., Ltd.], Oil Blue #6
03 [Orient Chemical], Patent Pure Blue [manufactured by Sumitomo Mikuni Chemical], Crystal Violet, Brilliant Green, Ethyl Violet, Methyl Green, Erythrosin B1 Basic Tsuksin, Malachite Green, Oil Red, m-Cresol Purple, Rhodamine B1 Auramine, 4 - Triphenylmethane type, diphenylmethane type, oxazine type, xanthine type, represented by p-diethylaminophenylimino naphthoquinone, cyano-p-diethylaminophenylacetanilide, etc.
Examples include iminonaphthoquinone-based, azomethine-based, and anthraquinone-based dyes. Among these, triphenylmethane dyes are preferred.

Further, a sensitizer for improving sensitivity can also be added to the photosensitive composition of the present invention. Examples of the sensitizer include gallic acid derivatives described in JP-A-57-118237, five-membered cyclic acid anhydrides as described in JP-A-52-80022, such as phthalic anhydride, Tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, succinic anhydride, pyromellitic acid, itaconic acid, etc., and 6-membered cyclic acid anhydrides such as those described in JP-A-58-11932, e.g. , glutaric anhydride and its derivatives. Among these, cyclic acid anhydrides are preferred, and 6-membered cyclic acid anhydrides are particularly preferred.

A positive-working photosensitive lithographic printing plate can be formed by dissolving the photosensitive composition of the present invention in a solvent that dissolves each of the above-mentioned components, applying it to the surface of a suitable 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, cyclohexanone, trichloroethylene, and methyl ethyl ketone. These solvents may be used alone or in combination of two 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.

The support provided with the photosensitive layer using the photosensitive composition of the present invention may be a metal plate made of aluminum, zinc, copper, copper, etc., or a metal plated or vapor-deposited with chromium, zinc, copper, nickel, aluminum, iron, etc. Examples include board, paper, plastic film, paper coated with resin, paper covered with metal foil such as aluminum, and plastic film treated to make it hydrophilic. Among these, aluminum plates are preferred. When an aluminum plate is used as a support, it is preferably subjected to surface treatments such as graining, anodizing, and, if necessary, sealing. Known methods can be applied to these treatments.

Examples of methods for graining include a mechanical method, a chemical etching method, an electrolytic etching method, and a combination of the three methods. 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. Preferred is electrolytic etching.

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 performed by electrolyzing using an aluminum plate as an anode using a solution containing one or more of sulfuric acid, chromic acid, oxalic acid, phosphoric acid, malonic acid, etc. as an electrolytic solution. The amount of anodic oxide film formed was 1 to 59 mg/d
12 is suitable, preferably 10 to 4011 cl/
dt'. The amount of anodized film can be determined by, for example, applying phosphoric acid ROM W1 solution (85% phosphoric acid solution: 35i
+2, chromium oxide (■): 20 (prepared by dissolving J in 12 water) to dissolve the oxide film, and it is determined by measuring the change in weight of the plate before and after the film is dissolved.

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

In addition, when contact-baking a film original onto a photosensitive planographic printing plate, the printing frame is generally vacuumed, but a method for improving this vacuum adhesion is also a positive photosensitive planar printing plate using the photosensitive composition of the present invention. Can be applied to printing plates. 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 a method of improving the vacuum adhesion of the photosensitive layer as described in JP-A-50-125805. Method of providing a matte layer on the surface and JP-A-55-
Examples include a method of heat-sealing a solid powder onto the surface of a photosensitive layer, as described in Japanese Patent No. 12974.

A positive-working photosensitive lithographic printing plate to which the photosensitive composition of the present invention is applied can be used in the same manner as those conventionally used. For example, an ultra-high pressure mercury lamp is passed through a transparent film,
It is exposed to light using a light source such as a metal halide lamp, xenon lamp, or tungsten lamp, and then developed with an alkaline developer, leaving only the unexposed portions on the surface of the support, creating a positive relief image.

Examples of alkaline developers include sodium hydroxide,
Examples include aqueous solutions of alkali metal salts such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium metasilicate, potassium metasilicate, sodium diphosphate, and sodium triphosphate.

The concentration of the alkali gold R salt is preferably 0.1 to 10% by weight. In addition, an anionic surfactant, if necessary, is added to the developer.
Amphoteric surfactants and organic solvents such as alcohols can be added.

(Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these embodiments.

Example 1 [Synthesis of photoreceptor] p-hydroxyaniline 40og, hydroquinone monomethyl ether 49, acetone 41 and pyridine 36
Mix 0g of methacrylic acid chloride, cool it from the outside using a cryogen, and when the internal temperature drops to 110℃, add methacrylic acid chloride 420.
g was added dropwise while stirring. The dropping rate was adjusted so that the reaction temperature was 0°C or less, and after the dropwise addition was completed, the mixture was stirred at 0 to 3°C for about 2 hours.

Next, after stirring at 25°C for 2 hours, the reaction solution was concentrated to 1/3, poured into 102 dilute hydrochloric acid (pH about 1.0), and the resulting precipitate was suction-filtered to obtain a white solid. Obtained.

This white solid was dissolved in 21 parts of warm methanol, 22 parts of a 5% aqueous sodium carbonate solution was added, and the mixture was stirred at 40°C for 30 minutes.

This dark red solution was then poured into 5% aqueous hydrochloric acid solution 81 to form a large amount of precipitate, which was filtered with suction and dried to give a pale pink solid. This was recrystallized from a mixed solvent of ethanol and water to obtain 450 g of colorless needle-like crystals of p-hydroxy methacrylanilide with a melting point of 155-156°C.

The obtained p-hydroxymethacrylanilide (HMl)
M A ) 88.6 (J , and 1.64Q of α・α′-azobisisobutyronitrile in 166i of ethanol
(After dissolving in 2 and purging with nitrogen gas, heating at 80°C for 2 hours to obtain a polymer solution.
% HCl aqueous solution, the resulting white precipitate was filtered and dried to give a white polymer (polyHMl) MA) 79
(] was obtained.

Next, the above white polymer (1)01'/HVIIM A)
44.25Q was dissolved in a mixed solvent of dioxane 300-d and ethylene glycol monomethyl ether 300-d, 0-naphthoquinonediazide-5-sulfonyl chloride 16,75 (l) was added, and after dissolving, 5.
160% dissolved potassium carbonate aqueous solution was added dropwise, 40~
The condensation reaction was carried out at 50°C for 40 minutes. After the reaction, the reaction solution was poured into dilute hydrochloric acid (40 hQ of water, 1.8 g of II hydrochloric acid), and the precipitated resin was collected by filtration and dried.

In this way, 0-naphthoquinonediazide sulfonic acid ester compound 53 (7) of polyHypM A was obtained. As a result of analysis, the condensation rate of OH groups was 25%.

Hereinafter, this obtained ester compound will be referred to as "photoreceptor of the present invention [■]".

[Synthesis of oil sensitizing agent] Novolac resin (weight average molecular weight M
W-1200> 200 was dissolved in 2401 g of dioxane, 10.8 g of O-naphthoquinonediazide-5-sulfonyl chloride was added, and after dissolving, 3.8 g of O-naphthoquinonediazide-5-sulfonyl chloride was added to 22 g of water.
Add 3g of dissolved potassium carbonate aqueous solution dropwise,
The condensation reaction was carried out at 0°C for 40 minutes.

After the reaction, the reaction solution was diluted with diluted hydrochloric acid (380 g of water, M1.2 m of salt)
j2), and the precipitated resin was collected by filtration and dried.

In this way, 25 g of an 0-naphthoquinonediazide sulfonic acid ester compound of p-tert-octylphenol formaldehyde resin was obtained.

As a result of analysis, the condensation rate of OH groups was 50%.

Hereinafter, this obtained ester compound will be referred to as the "liposensitizing agent [I] of the present invention".

[Synthesis of alkali-soluble resin J N-(4-hydroxyphenyl)acrylamide 106
．． 4 (1, 32 g of acrylonitrile, 7.2 G of ethyl acrylate, 13.2 g of methyl methacrylate and 6.56 (l) of α・α′-azobisisobutyonitrile
was dissolved in ethanol 3001Q, purged with nitrogen gas, and then heated at 80° C. for 4 hours to obtain a polymer solution. This polymer solution 32 was poured into a 5% HCl aqueous solution, and the resulting white precipitate was filtered and dried to obtain a white polymer 1959.

Hereinafter, the above polymer will be referred to as "alkali-soluble resin [■]".

@When the weight average molecular weight was measured, Mw = 1.7×
It was 104.

[Support] An aluminum plate with a thickness of 0.24 nv was prepared in a 5% aqueous sodium hydroxide solution at a temperature of 25°C and a current density of 60 A/df.
Electrolytic etching treatment was carried out for a treatment time of 30 seconds. Next, a desmut treatment was performed with a 5% aqueous sodium hydroxide solution, and then an anodization treatment was performed in a sulfuric acid solution. When the amount of anodic oxide film was measured using the method described above,
It was 20ma/di2. Next, it was immersed in a hot aqueous solution at 90°C for pore sealing treatment.

Subsequently, a photosensitive coating solution having the composition shown below was coated on the aluminum support using a spin coater and dried at 100° C. for 4 minutes to obtain a photosensitive lithographic printing plate (A).

(Photosensitive coating liquid composition) - The above photoreceptor [I] 3.40
2.6g of the above alkali-soluble resin [I], 2.6g of the above oil sensitizing agent [Eco 0.06Q, Victoria Pure Blue BOH (manufactured by Odugaya Chemical Co., Ltd.) 0.06f
J.2-trichloromethyl-5-[β-(2-benzofuryl) vinyl] 1,3.4-oxadiazole (exemplified compound (1) described in JP-A-60-138539) 0.084 g - Methyl cellosolve l OOd The coating weight after drying was approximately 24111 M (K).

A step tablet for sensitivity measurement (N manufactured by Eastman Kodak Company) was placed on the thus obtained photosensitive lithographic printing plate (A).
0, 2, densitometer (21 levels of gray scale with densitometers of 0 and 15) and a 2KW metal halide lamp (Idol Fin 2000 manufactured by Iwasaki Electric) with the positive original film in close contact.
was exposed for 70 seconds at 8.0 mW/Cf as a light source, and then exposed at 25°C using a 5-fold dilution of positive PS plate developer "5DR-1" (manufactured by Konishiroku Photo Industry ■). When development was performed for 45 seconds, a lithographic printing plate in which the non-image areas were completely removed was obtained. When the sensitivity was measured, the above concentration difference was 0.
．． 15. The 3K step was completely developed (clear) with 21 steps of gray scale.

In order to examine resistance to processing chemicals, durability against plate cleaner and washing oil, which are used as cleaning liquid to remove background stains that occur in non-image areas during printing, was investigated.

FD plate cleaner (manufactured by Toyo Ink Co., Ltd.)
, immersed in the stock solution of UV plate cleaner (manufactured by Moroboshi Ink Co., Ltd.) at air temperature for one day, and similarly, UV plate cleaning liquid Best Cure (manufactured by Toka Shiki Kagaku-sha Co., Ltd.) and UV plate cleaning liquid Tsurfit (manufactured by Clarei Sobrene Chemical Co., Ltd.). After immersing in the stock solution for 15 minutes, the image area was washed with water and compared with the image area before immersion to measure the degree of corrosion of the image area against the processing chemicals.

In addition, in order to examine ink receptivity, the number of waste sheets at the start of printing was measured. exposing through the positive original film;
Plate wash gum solution 5 is applied to the developed planographic printing plate.
Apply GW-1 (manufactured by Konishiroku Photo Industry ■) using a sponge and dry it, then apply it to a sheet-fed printing machine (Hamadata Star-900CD).
Regarding X), the gum removability immediately after the start of printing was evaluated.

The results of sensitivity, processing chemical resistance, and ink receptivity are shown in Table 1.

Comparative Example 1 The photosensitive coating solution of Example 1, except for the above-mentioned sensitizing agent [I], was coated and dried in the same manner as in Example 1, and a photosensitive planographic printing plate (8 ) was obtained.

The coating weight after drying was approximately 24 mg/6f.

Using this photosensitive lithographic printing plate (B), sensitivity, processing chemical resistance, and ink receptivity were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2 A photosensitive coating solution having the following composition was applied to the support of Example 1 and dried in the same manner as in Example 1 to obtain a photosensitive lithographic printing plate (C).

(Photosensitive coating liquid composition) Naphthoquinone-(1,2)-diazide-(2)-5-
Ester compound of sulfonic acid chloride and m-cresol formaldehyde novolak resin (condensation rate 25 mol%, weight average molecular weight MW = 1800) 3.
60・4.8g of the above-mentioned alkali-soluble resin
・The aforementioned oil sensitizing agent [I] 0.084
(+・Victoria Pure Blue BOHO, 084 (1
(Made by Udougaya Kagaku Kyoku) ・2-Trichloromethyl-5-[β-(2-benzofuryl)vinyl 1 1.3.4-oxadiazole (Exemplary compound (1) described in JP-A-60-138539) ) > 0.084 Q.Methyl Cellosolve 1001fi The coating weight after drying was about 24 mQ/df.

Using this photosensitive lithographic printing plate (C), sensitivity, processing chemical resistance, and ink receptivity were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 3 The photosensitive coating solution of Comparative Example 2, except for the above-mentioned sensitizing agent [I], was applied to the same support as in Example 1 and dried in the same manner as in Example 1 to obtain a photosensitive lithographic printing plate (D). I got it.

The coating weight after drying was approximately 24 Ql (+/dt2).

Using this photosensitive lithographic printing plate (D), sensitivity, processing chemical resistance, and ink receptivity were evaluated in the same manner as in Example 1. The results are shown in Table 1.

As mentioned above, the sensitivity performed for Example 1 and Comparative Examples 1 to 3,
In Table 1, the results of processing chemical resistance and ink receptivity are shown. Mark A indicates slight erosion in the image area.

Mark B shows erosion as above, and the grains of the support below the photosensitive layer are slightly exposed.

Mark C shows significant erosion as above, and the grains of the support below the photosensitive layer are completely exposed.

It means that.

In addition, ink receptivity is judged by the number of pieces of waste paper required from the start of printing until the gum is completely removed, the ink is sufficiently attached to the image area, and a complete print is obtained. Ta. The smaller the number, the better the gum removability and the better the ink receptivity.

From the results of the above Examples and Comparative Examples, the following is clear. That is, from the comparison between Example 1 and Comparative Example 1 and the comparison between Comparative Example 2 and Comparative Example 3, it was found that the oil sensitizing agent [I
] The effect of improving the ink receptivity of the photoreceptor [I] of the present invention
It is larger when used in combination with the conventional photoreceptor of Comparative Example 2.3.

The photosensitive lithographic printing plate (A) of Example 1 of the present invention has excellent processing chemical resistance and ink receptivity.

Example 2 In the photosensitive coating liquid of Example 1, the following alkali-soluble resin [II] was used instead of the alkali-soluble resin [I].
A photosensitive coating solution containing the same amount of the above was applied to the support of Example 1 and dried in the same manner as in Example 1 to obtain a photosensitive lithographic printing plate (E).

・Alkali-soluble resin [I[] Copolycondensation resin of phenol, I-cresol, p-cresol, and formaldehyde (ratio of phenol and cresol during synthesis is 60:40, Example of JP-A-55-57841) 1, number average molecular weight Mn −1,25×103, weight average molecular weight Mw −1,03xlo” > 2.6
a The coating weight after drying was approximately 24g/df.

Next, using this photosensitive lithographic printing plate (E), sensitivity, processing chemical resistance, and ink receptivity were evaluated in the same manner as in Example 1. As a result, the sensitivity has a clear stage number of 4, and the processing chemical resistance is evaluated as shown in Table 1: FD plate cleaner and U■ plate cleaner are rated A, and Best Cure and Trufit are rated C and B, respectively. , and the ink receptivity was 7 sheets. As described above, it was found that the photosensitive lithographic printing plate (E), like the photosensitive lithographic printing plate (A) of Example 1, was excellent in both processing chemical resistance and ink receptivity.

(Effects of the Invention) As explained above in detail, by using the photosensitive composition of the present invention, it has excellent resistance to processing chemicals, especially resistance to plate cleaners and cleaning solutions used in U-ink printing, Moreover, it was possible to provide a photosensitive lithographic printing plate that has excellent ink receptivity.

Claims (1)

[Scope of Claims] A resin obtained by condensing a polymer compound (A) having a structural unit represented by the following general formula [I] with a substituted phenol and an aldehyde represented by the following general formula [II], and and/or an ortho-naphthoquinonediazide sulfonic acid ester compound (B) of the resin. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. Represents an atom, alkyl group or aryl group, R_4 represents a hydrogen atom, alkyl group, aryl group or aralkyl group, X represents a divalent organic group, n represents an integer from 0 to 5, Y represents a substituent ) General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. are available. , R_7 represents an alkyl group or cycloalkyl group having 2 or more carbon atoms.)