JPH0721008B2 - Method for producing polymer compound for photosensitive composition having excellent storage stability - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a polymer compound used in a photosensitive composition, particularly a photosensitive composition of a photosensitive printing plate. More specifically, the present invention relates to a method for producing a polymer compound that improves the storage stability of a photosensitive printing plate, that is, the shelf life, by using it in the photosensitive composition of the photosensitive printing plate.

BACKGROUND OF THE INVENTION As a method for producing a polymer compound used in a photosensitive composition of a conventional photosensitive printing plate, for example, radical polymerization of radical polymerization and radical copolymerization, ionic polymerization of anionic polymerization and cationic polymerization, polycondensation, Synthesis is carried out by addition condensation, polymerization of carbonyl compound and ring-opening polymerization or elimination polymerization and polyaddition reaction, and the target polymer compound is used as a reaction liquid or a large amount of non-solvent (except for bulk polymerization). A method is known in which the mixture is put into water, alcohol or the like) with stirring and separated and purified.

As an example of the former, as described in JP-B-527364, an acrylic polymer compound having a hydroxyl group used together with a diazo compound is synthesized by radical polymerization in a solvent such as methyl cellosolve, and the photosensitive solution is used as it is. There is a method to use as a base.

As an example of the latter, as described in JP-B-56-30849, an acrylic polymer compound used for positive image is synthesized by radical polymerization, and then the reaction solution is poured into a large amount of isopropyl alcohol or water. And a method of obtaining the product by precipitation purification, and also JP-B-55-34929 or JP-B-57-4.
There is a method described in Japanese Patent No. 3890, in which an acrylic polymer compound having a hydroxyl group to be used together with a diazo compound is charged into a large amount of water after completion of the polymerization reaction and separated and produced by precipitation.

However, when a polymer compound produced by these conventional techniques is used in a photosensitive composition, particularly when it is used in a photosensitive composition of a photosensitive printing plate, a polymerization initiator and an unreacted monomer are contained in the polymer compound. However, since active substances that are considered to be due to catalysts, chain transfer agents, etc. remain, various problems have occurred such as poor development and fogging due to storage.

As a result of earnest studies, the inventors of the present invention have found that the above drawbacks can be improved by heat-treating a reaction solution after completion of a polymerization reaction in the production of a polymer compound used in a photosensitive composition, and thus have reached the present invention. is there.

[Object of the Invention] That is, an object of the present invention is to prevent a decrease in developability due to storage when used in a photosensitive composition, particularly a photosensitive composition of a photosensitive printing plate, that is, a photosensitive printing having excellent storage stability. Another object of the present invention is to provide a method for producing a polymer compound capable of obtaining a plate.

Another object of the present invention is that when used in a photosensitive composition, it causes less fogging (step tablets give a sharper leg).
That is, it is to provide a photosensitive composition free of scumming.

[Structure of the Invention] An object of the present invention is to provide a method for producing a polymer compound for a photosensitive composition, which comprises a step of synthesizing a polymer compound, wherein the synthesizing step is a polymerization reaction, and heat treatment of a reaction solution performed after completion of the polymerization reaction. It was achieved by a method for producing a photosensitive composition polymer compound comprising

[Specific Structure of the Invention] The present invention will be described in detail below.

The present invention provides various polymer synthetic methods, for example, ionic polymerization such as radical polymerization, anionic polymerization and cationic polymerization,
It is applied to a reaction solution by polycondensation, addition condensation, carbonyl compound polymerization and ring-opening polymerization, elimination polymerization and polyaddition reaction, but a reaction solution by radical polymerization is preferable. It is particularly effective for a reaction solution obtained by solution polymerization using a solvent.

As the radical polymerization monomer, the following compounds having unsaturated bonds are used.

(1) Monomers having hydroxyl group: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxypentyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, 2-hydroxyphenyl ( (Meth) acrylate monomers such as (meth) acrylate, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N- (hydroxyphenyl)-
(Meth) acrylamide, N- (hydroxynaphthyl)
-(Meth) acrylamide monomers such as (meth) acrylamide, o-, m- or p-hydroxystyrene monomers (2) (meth) acrylic acid ester or amide monomers other than (1): methyl (meth) Alkyl (meth) acrylates such as acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth) acrylamide, etc. (3) Monomers having a cyano group in the side chain: (meth) acrylonitrile, 2-pentenyltolyl, 2-methyl-
3-butenenitrile, 2-cyanoethyl acrylate,
o-, m- or p-cyanostyrene etc. (4) Monomers having a carboxylic acid in the side chain: (meth)
Acrylic acid, itaconic acid and its anhydride, maleic acid and its anhydride, crotonic acid, etc. (5) Vinyl ethers: propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether, etc. (6) Styrenes: α-methylstyrene, methyl Styrene, chloromethylstyrene, etc. (7) Vinyl ketones: methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, etc. (8) Monomers other than 1) to 7): olefins such as ethylene, propylene, isobutylene, butadiene, vinyl chloride, etc. Examples thereof include N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, and the like, and any other monomer capable of performing radical polymerization with these monomers may be used.

The monomers listed in (1) to (8) are similarly applied to polymer production methods by polymerization reactions other than radical weight, such as phenol resin, urea resin, melamine resin, xylene resin, toluene resin, guanamine resin. Resins produced by polycondensation reaction such as resins produced by addition condensation reaction, nylon resins, polyester resins, ionic polymerization resins produced by cationic polymerization, anion polymerization, etc., polymerization of carbonyl compounds such as aldehydes It is applicable to ring-opening polymerized resins such as resins, cyclic ethers and lactones.

Among these, the resin preferably used in the photosensitive composition is a polymer containing the monomers described in (1) to (8) in the case of radical polymerization, and phenols and cresols in the case of addition condensation. It is a novolak resin, a resole resin, which is a condensation resin with formalin, or a polyester resin in the case of a polycondensation resin. More preferably, it is a case of radical polymerization, and it is a polymer containing the monomers mentioned in (1) to (8), and most preferably (1) to (4).
It is a copolymer composed of the monomers listed in 1.

The method for producing the polymer compound used in the present invention will be described more specifically.

In the present invention, it is preferable to carry out the polymerization reaction using a solvent, but as the polymerization solvent, a solvent having a relatively low boiling point is preferably used, and specific examples thereof include ketones such as acetone and methyl ethyl ketone, benzene, and hexane. , Substituted or unsubstituted hydrocarbons such as heptane, cyclohexane, trichloroethane and dichloromethane, methanol,
Ethanol, n-propanol, iso-propanol,
alcohols such as t-butanol and sec-butanol,
Ethyl isobutyl ether, ethyl propyl ether,
Examples thereof include ethers such as propyl ether and tetrahydrofuran, esters such as methyl acetate and ethyl acetate, glycols such as ethylene glycol dimethyl ether, and water. If necessary, these solvents can be used in combination.

It is also possible to use a solvent having a relatively low boiling point and a solvent having a relatively high boiling point exceeding 100 ° C. in combination. Examples of the solvent having a boiling point of more than 100 ° C. include ketones such as cyclohexanone and 3-heptanone, hydrocarbons such as toluene, xylene and octane, alcohols such as n-butanol, pentanol and cyclohexanol, butyl acetate and pentyl acetate. Acetate esters such as propyl acetate and glycols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate are preferably used.

The molar ratio of the solvent and the charged monomer varies depending on the chemical and physical properties of the solvent and the monomer, and the physical properties of the polymer compound to be produced, particularly the viscosity, but
It is 0.1 mol / to 50 mol /, preferably 1 mol / to 20 mol /.

Various initiators are used in the present invention. In the radical polymerization, azobisisobutyronitrile, benzoyl peroxide, potassium persulfate, t-butyl hydroperoxide, di-t-butyl peroxide, azobiscyclohexanecarbonyl, etc. are used, and 0.01 mol% based on the total amount of monomers.
.About.10 mol%, preferably 0.1 mol% to 5 mol%.

In the addition condensation, in the case of novolac resin, hydrochloric acid, oxalic acid, phosphoric acid, sulfuric acid, phosphorus oxychloride, acetic acid, etc. are used, and 0.01 mol% to 10 mol% is added to the total amount of the monomers.

In ionic polymerization, sulfuric acid, tin tetraoxide, boron trifluoride,
A Grignard reagent or the like is used. With the polycondensation resin, the desired polymer compound can be easily obtained by heating without using an initiator.

The polymer compound or its solution in which the polymerization reaction has progressed,
Appropriate compounds are preferably added to terminate the polymerization reaction. For example, in radical polymerization, hydroquinone,
It is effective to use a polymerization inhibitor such as methoquinone, catechol, resorcin, water or the like, and an alkali agent such as sodium carbonate, potassium carbonate, triethylamine or the like as a polymerization inhibitor for addition condensation with an acid catalyst.

When used in a photosensitive printing plate, the polymer compound or a solution thereof may be dissolved in a coating solvent or the polymerization solvent may be replaced with a coating solvent. Solvents for dissolution or substitution include ethylene glycol alkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether and ethylene glycol diethyl ether, and ethylene glycol. Aryl ethers, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate and other ethylene glycol alkyl ether acetates and ethylene glycol aryl ether acetates, diethylene glycol dimethyl ether Diethylene glycol alkyl ethers such as ter, propylene glycol alkyl ethers such as propylene glycol monomethyl ether, propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, cyclohexanone, methyl butyl ketone, methyl isobutyl ketone, ketones such as 3-heptanone , Isobutyl acetate, isopropyl acetate,
Acetate esters such as isopentyl acetate, alcohols such as n-butanol, n-pentanol, cyclohexanol and benzyl alcohol, nitrogen-containing compounds such as dimethylformamide, and boiling points such as dimethylsulfoxide of 10
Solvents with a relatively high boiling point above 0 ° C. can be used. It is also possible to use a mixture of two or more of these relatively high boiling solvents.

The polymer compound solution in which the polymerization reaction is completed or the polymer compound solution substituted with the coating solvent is subjected to heat treatment which is a feature of the present invention. The temperature and time of heat treatment vary depending on the stability of the remaining active substance, but are generally 40 ° C to 150 ° C.
5 minutes to 30 days, preferably 45 ° C to 130 ° C for 10 minutes to 3
Day, more preferably 50 ° C to 100 ° C for 20 minutes to 24 hours. As a container used for the heat treatment, a three-necked flask equipped with a reflux condenser and a stirring device is preferably used. Further, in the case of a polymer compound that is easily oxidized, it is preferable to perform the treatment in a nitrogen stream.

The polymer compound solution that has been heat treated, depending on its application,
The following photosensitive composition and additives are added, and if necessary, the above coating solvent is added to provide a photosensitive liquid for a photosensitive printing plate.

The photosensitive composition contains a photosensitive substance as an essential component, and the photosensitive substance is one whose physical and chemical properties are changed by exposure or subsequent development treatment. Differences in solubility, differences in adhesion between molecules before and after exposure, differences in affinity for water and oil due to exposure or subsequent development, and electrophotographic image areas Those capable of forming a can be used.

Typical examples thereof include photosensitive diazo compounds,
Examples thereof include a photosensitive azide compound, a compound having an ethylenically unsaturated double bond, an epoxy compound which causes polymerization with an acid catalyst, and a compound having a C—O—C— group which decomposes with an acid.
Examples of the photosensitive diazo compound include o-naphthoquinonediazide compounds, which are positive compounds which change to be soluble in alkali upon exposure, and aromatic diazonium salts, which are negative compounds whose solubility is reduced by exposure.

As the aromatic diazonium salt, a diazo resin represented by a condensate of an aromatic diazonium salt and formaldehyde can also be used. Particularly preferably, a salt of a condensate of p-diazodiphenylamine and formaldehyde or acetaldehyde, for example, a diazo resin inorganic salt such as hexafluorophosphate, tetrafluoroborate, perchlorate or periodate, or a U.S. Pat. No. 3,300,309, wherein the condensate and a sulfonic acid such as paratoluenesulfonic acid or an acid salt thereof, a phosphinic acid such as benzenephosphinic acid or a salt thereof, a compound containing a phenolic hydroxyl group, for example, 2, Examples thereof include a diazo resin organic salt which is a reaction product with 4-dihydroxybenzophenone.

As the photosensitive azide compound, an aromatic azide compound in which an azido group is bonded to an aromatic ring directly or through a carbonyl group or a sulfonyl group is preferably used. For example,
Polyazidostyrene, polyvinyl-p-azidobenzoate, polyvinyl-p-azidobenzal, as described in U.S. Pat. No. 3,096,311, Japanese Patent Publication No. 45-
Reaction products of an azidoarylsulfonyl chloride and an unsaturated hydrocarbon-based polymer described in Japanese Patent Publication No. 9613, and Japanese Patent Publications No. 43-21017, No. 44-229, No. 44-22954, and No. 45-2.
Examples thereof include polymers having a sulfonyl azide or a carbonyl azide as described in Japanese Patent No. 4915.

The content of these aromatic diazonium salt compounds and aromatic azide compounds is preferably 2 to 60% by weight, and particularly preferably 4 to 40% by weight based on the total solid content of the photosensitive resist forming composition.
% By weight.

Examples of the compound having an ethylenically unsaturated double bond include a compound that causes a photodimerization reaction and a compound that causes a photopolymerization reaction.

As an example of the former, as a photosensitive group on the polymer main chain or side chain Those containing a photosensitive polymer as a main component such as polyesters, polyamides, and polycarbonates containing are also suitable. For example, as described in JP-A-55-40415, a photosensitive polyester obtained by condensation of phenylenediethyl acrylate with hydrogenated bisphenol A and triethylene glycol, US Pat. No. 2,956,
Examples include photosensitive polyesters derived from (2-properidene) malonic acid compounds such as cinnamylidene malonic acid and bifunctional glycols as described in Japanese Patent No. 878.

Examples of the latter include acrylic acid or methacrylic acid ester derivatives such as acrylic acid or methacrylic acid esters of polyols described in JP-B Nos. 35-5093 and 35-14719, such as diethylene glycol (meth) acrylate and triethylene glycol ( Examples thereof include (meth) acrylate.

The content of these compounds having an ethylenically unsaturated double bond is 5 to the total solid content of the photosensitive resist forming composition.
100 weight percent.

The o-quinonediazide compound is at least one o-quinonediazide group, preferably an o-benzoquinonediazide group or o-naphthoquinonediazide compound, and compounds having various known structures, for example, J. Kosar, "Light-Sensitive".
-Systeme "(John Wiley & Sons, Inc. 1965) 33rd
Contains compounds detailed in pages 9-353. Particularly preferred are esters or amides of various hydroxyl compounds or amino compounds with o-naphthoquinonediazidosulfonic acid. Preferred hydroxyl compounds include condensation resins of phenols and carbonyl group-containing compounds, particularly resins obtained by condensation in the presence of an acidic catalyst. Examples of the phenols include phenol, resorcin, cresol, and pyrogallol, and examples of the carbonyl group-containing compound include aldehydes such as formaldehyde and benzaldehyde, and ketones such as acetone.

Especially phenol / formaldehyde resin, cresol /
Formaldehyde resin, pyrogallol / acetone resin,
Resorcinol-benzaldehyde resin is preferred.

Representative specific examples of the o-quinonediazide compound include:
Esters of benzoquinone- (1,2) -diazide sulfonic acid or naphthoquinone- (1,2) -diazide sulfonic acid with phenol-formaldehyde resin or cresol-formaldehyde resin, described in US Pat. No. 3,635,709 Naphthoquinone- (1,2) -diazide sulfonic acid and sulfonate ester of pyrogallol-acetone resin, naphthoquinone- (1,2) -diazide- (2) described in JP-A-56-1044 Condensation product of -5-sulfonic acid and resorcin benzaldehyde resin, naphthoquinone- (1,2) -diazide- (2) -5-sulfonic acid and resorcin pyrogallol described in JP-A-55-76346 Ester compounds with acetone copolymerization condensation and other useful o-quinonediazide compounds are described in JP-A-50-117503. And it is,
An ester of a polyester having a hydroxyl group at the terminal and o-naphthoquinone diazide sulfonic acid, JP-A-50-
Examples thereof include an ester of o-naphthoquinone diazide sulfonic acid with a homopolymer of p-hydroxystyrene or a copolymer of the homopolymer of p-hydroxystyrene with another copolymerizable monomer as described in JP-A-113305.

The content of these o-quinonediazide compounds is preferably 5 to 60% by weight, particularly preferably 10 to 50% by weight based on the total solid content of the photosensitive resist forming composition.

In addition to the materials described above, the photosensitive composition may contain other additives as required.

Various low molecular weight compounds as plasticizers such as phthalic esters, triphenyl phosphates, maleic acid esters, acids as storage stabilizers for diazonium salts, such as oxalic acid and phosphoric acid, and surfactants as coating improvers. , Fluorine-based surfactants, nonionic surfactants represented by ethyl cellulose polyalkylene ether, etc.,
An acid anhydride or the like as a sensitizer for the positive photosensitive composition,
Examples include printout materials for forming a visible image by exposure. The printout material is composed of a compound that generates an acid or a free radical upon exposure to light and an organic dye that changes its color tone by interacting with the compound. Examples of the compound that generates an acid or a free radical upon exposure to light include O-naphthoquinonediazide-4-sulfonic acid halogenide described in JP-A-50-35209, trihalomethyl-2-pyrone and trihalomethyl-triazine described in JP-A-53-36223, JP-A-55-6244 An ester compound of o-naphthoquinonediazide-4-sulfonic acid chloride with an electron-withdrawing substituent or an aniline described in JP-A-55-
Examples thereof include halomethyl-vinyl-oxadiazole compounds and diazonium salts described in JP-A 77742.

Examples of the organic dyes include Victoria Pure Blue BOH [Hodogaya Chemical], Oil Blue # 603 [Orient Chemical Co., Ltd.], Patent Pure Blue [Sumitomo Mikuni Chemical], Crystal Violet, Brilliant Green, Ethyl Violet, Methyl. Trilete represented by violet, methyl green, erythrosine B, basic phthalucine, malachite green, oil red, m-cresol purple, rhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, cyano-p-diethylaminophenylacetanilide and the like. Examples thereof include phenylmethane-based, diphenylmethane-based, oxazine-based, oxaten-based, iminonaphthoquinone-based, azomethine-based or anthraquinone-based dyes.

The photosensitive solution thus produced is applied as a photosensitive lithographic printing plate by coating it on a suitable support. Examples of the support include aluminum plate, zinc plate,
Examples include an iron plate, a plastic plate, or a composite material thereof, such as an aluminum-plated iron plate, a chrome-plated iron plate, and an aluminum-laminated plastic sheet, and the aluminum plate is preferable. The surface of the support is generally preferably grained.

Examples of the method of forming the grain shape include a mechanical method and an electrolytic etching method. Examples of mechanical methods include a ball polishing method, a brush polishing method, a liquid honing polishing method, and a buff polishing method.

To apply the photosensitive solution to the support, the photosensitive solution is filtered in advance with an appropriate filter material such as No. 2 filter paper to remove dust and foreign matters, and then the wire bar coater, whaler coater,
A roller coater such as a double roller coater and a bead coater such as an extrusion type coater are used.
A roller coater such as a double roller coater and a bead coater such as an extrusion type coater are preferably used. Appropriate drying conditions after application are about 30 to 100 ° C for about 1 to 60 minutes, preferably about 60 to 90 ° C for about 2 minutes.
Minutes to 30 minutes.

The photosensitive printing plate thus produced is exposed by a mercury lamp, a metal halide lamp or the like, and developed by an appropriate developing solution to be used as a printing plate.

[Effects of the Invention] The photosensitive composition containing the polymer compound obtained by the method of the present invention is excellent in that it has less fog (the foot is easily cut by a step tablet), that is, it does not cause scumming. In particular, a photosensitive printing plate having a photosensitive composition containing the above-mentioned polymer compound exhibits remarkably excellent storability that the developability does not deteriorate during storage.

[Examples] Hereinafter, the present invention will be described in more detail with reference to Examples, but the embodiments of the present invention are not limited thereto.

[Synthesis Example 1] N- (4-hydroxyphenyl) methacrylamide 17.9
g, acrylonitrile 16.1g, ethyl acrylate 74.4
g, 8.7 g of methacrylic acid (each molar ratio 8: 24: 60: 8) was dissolved in 180 ml of distilled acetone and 180 ml of distilled methanol (total monomer concentration: 3.5 mol /), and 6.2 g of azobisisobutyronitrile (3 (Mol%), and the polymerization reaction was carried out for 8 hours under reflux in a nitrogen stream. After completion of the reaction, 0.05 g of hydroquinone, 200 ml of methyl cellosolve, and 0.3 g of an antioxidant (Yoshinox 2246G, manufactured by Yoshitomi Pharmaceutical Co., Ltd.) were added, and then the polymerization solvent was distilled off under reduced pressure with an aspirator.

It was distilled off for 10 minutes, and when the distillation temperature reached about 40 ° C, the distillation was stopped and the mixture was cooled to room temperature.

After cooling, the pressure was returned to normal pressure, the temperature was raised, and heat treatment was carried out at 95 ° C. ± 5 ° C. for 2 hours with stirring. Then, the temperature was lowered to room temperature and the solid content was measured under the following conditions. The solid content was 36% by weight.

Temperature: 100 ° C. (reduced pressure: 1 × 10 ⁻² mmHg) Time: 1 hour Next, methyl cellosolve was added so that the solid content was 20% by weight to obtain a polymer solution-1. The yield was 510 g as a 20% by weight solution.

Next, GPC measurement was performed and the following results were obtained.

Weight average molecular weight (Mw): 3.90 × 10 ⁴ Dispersion ratio: 1.98 GPC measurement conditions GPC device: Hitachi 635 type GPC device Column: Shodex A 802 × A 803 × A 804 Flow rate: THF 1.5 ml / min Detector: Differential Refractometer Molecular weight conversion: conversion by standard polystyrene (manufactured by Toyo Soda Co., Ltd.) [Synthesis Example 2] 2-hydroxyethylmethacrylamide 56.7 g, acrylonitrile 9.91 g, ethyl acrylate 54.9 g, methacrylic acid 6.54 g (each molar ratio) 35: 15: 44: 6) was dissolved in 120 ml of distilled acetone and 120 ml of distilled ethanol (total monomer concentration: 5.25 mol /), 4.1 g (2 mol%) of azobisisobrotinitrile was added, and the mixture was refluxed in a nitrogen stream. The polymerization reaction was carried out for 8 hours in this state. After completion of the reaction, after adding 0.05 g of hydroquinone, 150 ml of methyl cellosolve, and 0.3 g of antioxidant (Yoshinox 2246G, Yoshitomi Pharmaceutical Co., Ltd.),
The polymerization solvent was distilled off under reduced pressure with an aspirator.
It was distilled off for about 1 hour, and when the distillation temperature reached about 40 ° C, the pressure was returned to normal pressure, the temperature was raised to 80 ° C under normal pressure, and then heat treatment was performed for 6 hours. Next, the solid content was measured in the same manner as in Example 1. The solid content was 33% by weight. A polymer solution-2 was prepared by diluting with a solution of methyl cellosolve and methanol (mixing ratio 5: 1) so that the solid content was 20% by weight. The yield was 512 g as a 20% by weight solution.

Mw: 5.50 × 10 ⁴ Dispersion ratio: 1.71 [Synthesis 3] N- (4-hydroxyphenyl) methacrylamide 22.1
g, 2-hydroxyethyl methacrylate 56.7 g, acrylonitrile 6.63 g, ethyl acrylate 49.8 g, methacrylic acid 5.33 g (each molar ratio 10: 35: 10: 40: 5) was dissolved in distilled acetone 120 ml, distilled methanol 120 ml ( After adding total monomer concentration: 5.25 mol /) and azobisisobutyronitrile 4.09 g (2 mol%), the synthesis was performed in the same manner as in Synthesis 1 to obtain a polymer solution-3.

The yield and molecular weight are shown below.

Yield: 613 g (as a 20% by weight solution) Mw: 6.70 × 10 ⁴ Dispersion ratio: 1.91 [Synthesis example 4] 12.1 g of p-hydroxystyrene, 18.5 acrylonitrile
g, ethyl methacrylate 78.1 g, methacrylic acid 9.6 g (molar ratio of each 8: 28: 55: 9) distilled methyl ethyl ketone 1
Dissolve 25 ml of distilled methanol in 125 ml (total monomer concentration: 5 mol /), azobisisobutyronitrile 2.
04 g (1 mol%) was added, and thereafter, synthesis was carried out in the same manner as in Synthesis Example 1. The diluted solution was a mixed solution of methyl cellosolve / butyl cellosolve = 2/1 so that the solid content was 20% by weight. This was Polymer Solution-4. The yield and molecular weight are shown below.

Yield: 515 g (as a 20 wt% solution) Mw: 7.80 × 10 ⁴ Dispersion ratio: 1.52 [Synthesis examples 5, 6, 7, 8, 9, 10, 11, 12] Table 1 shows the heat treatment conditions after completion of the polymerization reaction. The same operation as in Synthesis Example 1 was performed except that the above-mentioned procedure was performed. The yield and molecular weight are shown in Table 1.

The polymer solutions-11 and 12 were colored in brown, which is considered to be due to the high temperature.

[Synthesis Example 13] To 60 g of m-cresol, 40 g of p-cresol and 84 g of 37% aqueous formaldehyde solution, 0.1 ml of 35% concentrated hydrochloric acid was added as a catalyst, and the mixture was refluxed under heating to carry out the addition condensation reaction for about 1.5 hours. After the reaction was completed, 5% potassium carbonate solution was added dropwise until the pH became 5 to 6, 20 g of water and 100 g of ethyl cellosolve were added, and water and ethyl cellosolve were distilled off under reduced pressure at 95 ° C for 2.5 hours. It was done. Next, ethyl cellosolve was added to prepare a 20% by weight liquid to obtain a polymer solution-13.

Yield: 108 g (as a 20% by weight solution) Mw: 1.05 × 10 ⁴ Dispersion ratio: 2.13 [Comparative Synthesis Example 1] Same as Synthesis Example-1 except that the heat treatment after distilling off the polymerization solvent was not performed in the formulation of Synthesis Example 1. Was carried out to obtain a comparative polymer solution-1 as a 20% by weight solution of methyl merosolve.

Yield: 510 g (as a 20% by weight solution) Mw: 3.90 × 10 ⁴ Dispersion ratio: 1.98 Example 1 An aluminum plate having a thickness of 0.24 mm was immersed in a 3% sodium hydroxide aqueous solution to be degreased, washed with water and then washed with 1% hydrochloric acid. And 3 A / dm ^{2 in} a 1% aqueous solution of boric acid at 25 ° C. for 5 minutes, followed by washing with water. Next, soak in 0.9% sodium hydroxide aqueous solution,
After washing with water, it was anodized in 40% sulfuric acid aqueous solution at 30 ° C. for 1.5 minutes at 1.5 A / dm ² , and washed with water. Furthermore, it was treated with a 1% solution of sodium metasilicate at 90 ° C. for 30 seconds, then washed with water and dried to prepare a grained aluminum plate.

Next, a photosensitive solution having the following composition was applied to the aluminum plate with a roll coater. Further, it was dried at 90 ° C. for 4 minutes to obtain a photosensitive lithographic printing plate.

[Photosensitive solution-1] Polymer solution-1 3 kg Hexafluorophosphate salt of a condensation resin of p-diazodiphenylamine and paraformaldehyde (molar ratio 1: 0.9) 48 g DURIMER AC-10L (manufactured by Nippon Pure Chemical Co., Ltd.) 36g Victoria Puyour Blue BOH (Hodogaya Chemical Co., Ltd.) 9
g Methyl cellosolve 3.1 The coating amount after drying was 1.6 g / m ² .

Next, the photosensitive lithographic printing plate was exposed and developed under the conditions shown below, and ink was added with the developing ink SPO-1 (manufactured by Konishi Rokusha Kogyo Co., Ltd.) to check clear sensitivity and development stains. Was done. Next, printing was performed under the following printing conditions.

<Exposure conditions> Exposure material: Metal halide lamp "Eidfin 2000"
(Manufactured by Iwasaki Electric Co., Ltd.) Distance: 1 m Time: 30 seconds Film original: 150-dot halftone original with Kodak step tablet No. 2 <Development conditions> Developer-1 Phenylcellosolve 480 g Diethanolamine (80% ) 159g Paionin A4413 (manufactured by Takemoto Yushi Co., Ltd.) 180g Water 12 Developer-2 Developer-1 was developed by repeatedly developing an unexposed negative PS plate "SWN" (manufactured by Konishi Roku Photo Co., Ltd.) to fatigue. What (15m ² per mother liquor) Developing machine: Sakura PS plate developing machine "PSP-860" (manufactured by Konishi Rokusha Kogyo Co., Ltd.) Gum solution: SGW-2 Development temperature: 25 ° C Development time: 30 seconds <Printing conditions> Printing machine: Heidel GTO Paper: Semi-coated paper Ink: Toyo Bright Beni (manufactured by Toyo Ink Co., Ltd.) Dampening solution: SEU-1 (manufactured by Konishi Rokusha Kogyo Co., Ltd.) 50 times dilution ) Printing speed: 5000 sheets / hour Further, after the photosensitive lithographic printing plate was stored under the following conditions and forced deterioration {dry thermo (DT)}, clear sensitivity, developability and print stain were examined in the same manner. . The results are shown in Table 2.

<Storage Conditions> Temperature: 55 ° C. Humidity: 2 to 5% Time: 5 days to 7 days Examples 2 to 12 Polymer Solution-2 in place of Polymer Solution-1 of Photosensitive Solution-1
.About.12 (corresponding to Examples-2 to 12) were used and tested in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 1 Instead of Polymer Solution-1 of Photosensitive Solution-1, Comparative Polymer Solution-
The test was conducted in the same manner as in Example 1 except that 1 was used.
The results are shown in Table 2.

<Clear sensitivity> Film tablet step tablet (Kodak No. 12)
Thus, the number of clear steps was obtained, and so-called foot break was evaluated.

<Developability> The developability (development stain) was evaluated on the basis of the halftone dots (150 lines) of the film original in the following three stages.

◯: The photosensitive layer in the non-image area was completely dissolved and removed.

Δ: The photosensitive layer in the non-image area is almost dissolved and removed.

X: A considerable amount of the photosensitive layer in the non-image area remains. (Especially on dyeing) <Staining during printing> The reproducibility of halftone dots during printing was evaluated.

○: The shadow part is reproduced.

X mark: The shadow part is entangled and dirty.

As is clear from Table 2, in Comparative Example-1 using the polymer compound that was not heat-treated, the number of clear steps was large, and so-called cutting of legs was insufficient. Further, it can be seen that the developability is deteriorated from the fact that the printing plate after development is already stained after 5 days of forced deterioration, and that when it is used for printing, stains occur, which is a practical problem.

On the other hand, Examples 1 to 12 of the present invention are excellent in cutting of the foot, and even after 7 days of forced deterioration, the developability is hardly deteriorated in the development using the fatigue developing solution (Developer-2), and printing is possible. No dirt is generated even when used.

Further, the photosensitive lithographic printing plate was actually stored at room temperature for 1.5 years, and plate making and printing were carried out in the same manner as in Example 1. As a result, in Comparative Example 1, the shadow portion of the mesh portion became entangled when subjected to printing. Although it became dirty, the samples of Examples 1 to 12 of the present invention did not cause any particular problems. From the above, when the heat-treated polymer compound of the present invention is used in the photosensitive composition of the photosensitive lithographic printing plate, so-called shelf life is excellent, and the legs are cut well and the effect of being hard to stain even when subjected to printing is exhibited. To do.

Example 13 An aluminum plate having a thickness of 0.30 mm was immersed in a 3% aqueous solution of sodium hydroxide for degreasing, washed with water, and then 3A in a 2% aqueous solution of nitric acid.
/ dm ² , electrolytically etched for 4 minutes and washed with water. Next 0.9%
It was immersed in an aqueous solution of sodium hydroxide, washed with water, anodized in a 40% aqueous solution of sulfuric acid at 30 ° C. for 1.5 minutes at 1.5 A / dm ² , and washed with water. Further, after sealing treatment with hot water of 80 ° C for 30 seconds, washing with water and drying,
A grained aluminum plate was created.

Then, a photosensitive solution having the following composition was applied to an aluminum plate with a roll coater and further dried at 90 ° C. for 4 minutes to obtain a photosensitive lithographic printing plate.

[Photosensitive solution-2] Polymer solution-133.5 kg Condensation product of o-naphthoquinonediazide-5-sulfonyl chloride and pyrogallolacetone resin (Japanese Patent Application No. 58-2498).
Compound described in No. 49) 90 g o-naphthoquinonediazide-5-sulfonyl chloride condensate of p-octylphenol formalin novolac resin 9 g 2-trichloromethyl-4-p-butoxystyryl-1,
3,4-Oxadiazole 6 g Oil blue # 603 2 g Methyl cellosolve 1.5 kg The coating amount after drying was 2.0 g / m ² . Next, under the conditions of Example 1, the developer-1 was diluted with a 6-fold diluted solution of the developer SDR-1 for Sakura PS plate (manufactured by Konishi Rokusha Kogyo Co., Ltd.) and the PS plate for fatigue was SWN.
To SLP (manufactured by Konishi Rokusha Kogyo Co., Ltd.) and fatigue fluid is 5
The test was conducted in the same manner as in Example 1 except that the gum solution was changed from SGW-2 to SGW-1 at m ² /. As a result, save the thermo 5
Even after about 7 days, no stains on the development or prints were observed, which was a good result.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication location G03F 7/039 501 (72) Inventor Yoshihiro Maeda 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Sanryo Kasei Industry Research Institute (72) Inventor Hiromi Hirasawa 1000 Kamoshida-cho, Midori-ku, Yokohama, Kanagawa Sanryo Kasei Co., Ltd.

Claims (1)

[Claims] 1. A method for producing a polymer compound for a photosensitive composition, which comprises a step of synthesizing a polymer compound, wherein the synthesizing step comprises a polymerization reaction and a heat treatment of a reaction solution carried out after the completion of the polymerization reaction. A method for producing a polymer compound for a photosensitive composition, comprising: