TW591339B - Photo-polymerisable unsaturated resin, their process for producing it and alkali-soluble radiation-sensitive resin component using it - Google Patents

Abstract

The present invention provides an alkali-soluble radiation-sensitive resin and the component comprising it. The present invention provides a photo-polymerisable unsaturated resin, which the quantitative average molecular weight is upon 1,500, wherein is obtained by the reaction from the mole ratio of dicarboxylanhydride and tetracarboxylanhydride of 1:99 to 65:35, formula (1): (wherein, X repressed bisphenol (or bismethylphenol) fluorene-type epoxyacrylic acid derivate, n is a number from 1 to 20, Y is the residue except the anhydride of dicarboxylanhydride, Z is the residue except the anhydride of tetracarboxylanhydride), and the alkali-soluble radiation-sensitive resin component having the resin thereof. The coating filter consisting of the components thereof has the excellent properties of heat-resistance, transparency, exposure-developing, chemical resistance etc.

Description

591339 明, -Ming said (the description of the invention should be stated ... the technical field to which the invention belongs, the prior art, the content, the embodiments and the drawings are briefly explained) 技术 The technical field to which the invention belongs The present invention relates to a novel photopolymerizable unsaturated Resin, preparation method thereof, and alkali-soluble radiation-sensitive resin composition using the same. More specifically, the present invention relates to an alkali-soluble radiation-sensitive resin composition suitable for use in various applications. The present invention relates to a photopolymerizable unsaturated resin useful as a photopolymerizable component and the like, an effective production method, and Containing this photopolymerizable unsaturated resin can provide a cured film with excellent heat resistance, transparency, adhesion, chemical resistance, etc., and is suitable for use as a color filter, liquid crystal display element, integrated circuit element, solid-state imaging element, etc. Forming materials for protective films or interlayer insulating films, adhesive compositions for color photoresist, or alkali-soluble radiation-sensitive resin compositions such as soldering photoresist used in the manufacture of printed wiring boards. ㈡In the past, screen printing was used to form protective films or interlayer insulating films for color filters, liquid crystal display elements, integrated circuit elements, and solid-state imaging elements, or to form photoresist patterns on printed wiring boards. However, the screen printing method cannot cope with the recent high-density devices. Therefore, although a dry film type photoresist or a liquid photoresist is proposed, in the case of a dry film type photoresist, the solution will generate bubbles during hot-pressing, so the heat resistance or adhesion is insufficient, and there will be The problem of increasing costs. In addition, the “liquid photoresist has adhesiveness after pre-baking, which is the cause of the contamination of the photomask”, which has the disadvantage of not being able to improve the contrast of the pattern shape. 7-591339 Adhesive exposure method. Secondly, since commercial solvents are currently used by marketers as a developing solution, the solvents are expensive in terms of air pollution. Furthermore, Japanese Patent Application Laid-Open No. 6 1-24 3 8 6 9 discloses a radiation-sensitive resin composition containing a phenol novolak lacquer resin as a main component and capable of developing a weak alkaline aqueous solution. It does not have sufficient resistance under alkaline conditions, and there is a problem that the adhesion to the substrate is reduced after processing. Therefore, in order to solve this problem, the cured product has recently been proposed as a photopolymerizable compound having a fluorene structure which is excellent in transparency and heat resistance. In addition, the photopolymerizable compound can solve the above-mentioned problems to some extent by using it, but cannot fully meet the required performance. For example, Japanese Unexamined Patent Publication No. 4-345673, Japanese Unexamined Patent Publication No. 4-345608, Japanese Unexamined Patent Publication No. 4-3 5 5 450, and Japanese Unexamined Patent Publication No. 4-3 63 3 11 disclose the use of a ring having a bisphenol hydrazone structure. The heat-resistant liquid photoresist and color filter material of the reactant of oxyacrylic acid ester and acid anhydride have the same adhesion after pre-baking, which is the cause of photomask contamination. It may not be used to improve the pattern. The problem of the close-contact exposure method in which the shapes are contrasted, and because the carboxyl group content is too high, there are problems that the alkali solubility of the hardened product becomes high, and the developability is poor. In addition, the epoxy resin disclosed in Japanese Unexamined Patent Publication No. 4-3 4 5 6 7 3 has a low degree of resolution for general organic solvents, and the solvent is limited when used as a liquid photoresist. The disadvantage of difficult film thickness formation. In addition, when these coating films produced by full-coating by printing or roller coating are thermally cured, there may be sticking and remaining after removing the solvent by pre-baking, and there is a problem of poor workability. -8-591339 In addition, Japanese Patent Application Laid-Open No. 5-3 3 9 3 5 6, Japanese Patent Application Laid-Open No. 6-1 9 3 8 and Japanese Patent Application Laid-Open No. 7-3 1 22 disclose the use of a bisphenol hydrazone structure. The epoxy acrylate compound reacts with an acid anhydride and an acid dianhydride simultaneously and has a high molecular weight, and a photopolymerizable unsaturated compound represented by the general formula (7) formed by introducing a carboxyl group. [Chemical 9]

COOH

-0-X-0-C0 Y CO Γ i Ί 0 X—0-CO- ZO-CO- IL ”m LI J COOH (where X is a group represented by formula (8), and Y is an acid anhydride For residues other than the anhydride group, Z is a residue other than the anhydride group of the acid dianhydride, and I and k represent the degree of polymerization, and the m / k molar ratio is 1/99 to 90/10). [Chemical 1 0]

When using this compound, there is no sticking after pre-baking. However, when adjusting this compound, the acid anhydride not only reacts with the hydroxyl group of the epoxy acrylate, but also relates to the condensation reaction, so it is not easy to control the molecular weight and acid value of the compound. As a result, when the compound is dissolved in a solvent, even if the concentration of the same solid component is increased due to the solution viscosity of the photoresist solution, the workability in dissolving, filtering, or coating the solid component is not good. In addition, the coating characteristics deteriorated so that the film thickness in the substrate surface became uneven, resulting in a problem of uneven development characteristics 591339. In addition, Japanese Patent Application Laid-Open No. 9-3 2 5 4 9 4 discloses a composition in which only an epoxy acrylate compound having a bisphenol hydrazone structure is reacted with an acid dianhydride, and an interactive copolymer containing a carboxyl group is a main component. However, there are a lot of unreacted epoxy acrylate compounds left in the composition, and there is a fear that the water resistance, solvent resistance, and alkali solubility are reduced. In order to reduce the unreacted epoxy acrylic compound, it is better to increase the use ratio of the acid dianhydride. At this time, when the molecular weight is increased, the viscosity of the solution becomes higher, and the workability is significantly reduced. In view of the above circumstances, the present invention is to provide a photopolymerizable unsaturated resin without the above disadvantages and easy to control the molecular weight, a method for efficiently producing the same, and a method including the photopolymerizable unsaturated resin and pre-baking. The coating film will not stick, the heat resistance of the cured film after light irradiation (small shrinkage of the thick film during heat treatment), transparency, adhesion, hardness, and chemical resistance (small shrinkage of the thick film after immersion in an alkaline solution) are excellent. It can be developed with a weakly alkaline aqueous solution and a radiation-sensitive resin composition with an appropriate solution viscosity and easy viscosity adjustment. The inventors have intensively studied the results to achieve the above purpose, and found that After the epoxy (meth) acrylate of the bisphenol hydrazone structure reacts with tetracarboxylic dianhydride to form an oligomer, by using a two-stage reaction in which the terminal hydroxyl group is blocked with dicarboxylic anhydride, the above-mentioned can be obtained without Disadvantages, a novel photopolymerizable unsaturated resin with easy control of molecular weight and carboxyl group, and then a compound containing the photopolymerizable unsaturated resin and epoxy group The photopolymerization initiator composition as the radiation-sensitive resin composition of the present invention accomplished the purpose can be obtained based on the findings -10-591339. In other words, the present invention provides a photopolymerizable unsaturated resin, which is a photopolymerizable unsaturated resin having a number average molecular weight of 1,500 or more represented by the general formula (1), and which is composed of a dicarboxylic anhydride. And tetracarboxylic dianhydride in a molar ratio of 1: 99 ~ 6 5: 3 5

COOH Plant I Ί H〇〇C— Y—C0— 0—X —〇—CO— Z—C0-0 — X — 0—CO ~ Y ~ COOH (1) I ″ n

COOH (where 'x is a group represented by the general formula (2), [Chem 1 2]

(Wherein 1 ^ each represents an independent hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a halogen group, and 1 to 2 each represents an independent hydrogen atom or a methyl group), and η represents 1 to 2 0 In the integer, γ represents a residue other than the anhydride group of a dicarboxylic anhydride. 'Z represents a residue other than the anhydride group of a tetracarboxylic dianhydride.) Furthermore, the present invention provides a method for producing a photopolymerizable unsaturated resin having a number average molecular weight of 1,500 or more represented by the general formula (1), which comprises combining an epoxy compound represented by the general formula (3) with (Meth) acrylic acid is reacted to obtain a (meth) acrylic acid ester derivative represented by the general formula (4), and then reacted with a tetracarboxylic dianhydride represented by the general formula (5) 591339, and then The two residual acid anhydrides' represented by the formula (6) are added with a molar ratio of dicarboxylic anhydride and tetracarboxylic dianhydride}: 99 to 65..35 to carry out the reaction. [Chem. 1 3]

[Chemical 1 4]

〇 II I 〇-ch2chch2- oc-c = ch2 ⑷

/ \ ./ \ / r, 〇v · zv 〇. (5) \ / \ /

〇C CO (where ′ z represents a residue other than the anhydride group of tetracarboxylic dianhydride) [Chemical formula 1 6] C0 Y [> (6)

'CO 591339 (where γ represents a residue other than the anhydride group of a dicarboxylic anhydride) [Chem. 1 7]

COOH .χ-O-CO- 丫 -COOH (1) [HOOC-V-C °-° * -X-O-CO- Z — C0-

I

COOH (where χ represents a group represented by the general formula (2), [Chem. 1 8]

(Wherein R1, R2, γ, and Z are the same as above, and η is an integer of 1 to 20). In addition, the present invention provides an alkali-soluble radiation-sensitive resin composition containing (A) the aforementioned photopolymerizable unsaturated resin, (B) a compound having an epoxy group, and (C) a photopolymerization initiator. . In a preferred embodiment, the alkali-soluble radiation-sensitive resin composition of the present invention further contains (D) at least one of a photopolymerizable monomer and an oligomer, and is more than 100 parts by weight of (A ) The component is 50 parts by weight or less. The photopolymerizable unsaturated resin of the present invention is a novel resin having a number-average molecular weight of 1,500 or more represented by the general formula (1) (hereinafter referred to as the resin of the present invention). -13-591339 [Chem. 1 9]

COOH Plant 1 Ί HOOC- 丫 -CO-〇X-O-CO- Z-CO-O — X-O-CO-V-COOH (1) I ″ n

COOH (wherein 乂, 、, 2 and 11 are the same as above), the (meth) acrylic acid ester derivative is reacted with a tetracarboxylic dianhydride (residue Z), and the dicarboxylic anhydride (residual The group is Y) It is obtained by adding a dicarboxylic anhydride and a tetracarboxylic dianhydride in a molar ratio of 99: 65 ′ · 35. The resin of the present invention is characterized by having a structure in which hydroxyl groups at both ends are terminated by a dicarboxylic anhydride, and substantially does not have the dicarboxylic anhydride residue in the polymerization chain. In this regard, Japanese Patent Application Laid-Open No. 5-3 3 9 3 56 describes that the photopolymerizable unsaturated compound represented by the general formula (7) has a dicarboxylic anhydride residue in the polymerization chain, but is different from the resin of the present invention. And, even if it is not limited to the terminal hydroxyl group by di; carboxylic acid anhydride, it is different from the present invention. The production method of the general formula (7) is different from the method of the present invention in that an epoxy acrylate compound having an bisphenol hydrazone structure, an acid anhydride, and an acid dianhydride are reacted at the same time. The photopolymerizable unsaturated resin represented by the general formula (1) can be produced extremely efficiently by the method shown below. First, an epoxy compound represented by the general formula (3) is prepared. In the epoxy compound (3), each of L series represents an independent hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group or a halogen group, and an alkyl group having 1 to 5 carbon atoms is preferably a methyl group or an ethyl group. Methyl is more preferred. R, a biscresol hydrazone type epoxy compound which is also a methyl group is preferred. As the halogen group, B r, C 1, and F are preferably used. 591339 [Chemical 2 〇]

The epoxy compound represented by the general formula (3) can be easily produced, for example, by reacting bisphenol fluorene or biscresol fluorene with epichlorohydrin such as epichlorohydrin. A commercially available bisphenol fluorene type epoxy compound can be used. Next, the epoxy compound of the general formula (3) is reacted with (meth) acrylic acid to obtain a (meth) acrylate derivative represented by the general formula (4). The compound represented by the general formula (3) can be used alone or in combination of two or more kinds. It is also possible to use a combination of acrylic acid and methacrylic acid. 【化 2 1】.

Then, the obtained (meth) acrylate derivative 'represented by the general formula (4) and the tetracarboxylic dianhydride represented by the general formula (5) are reacted in an appropriate solvent. 【化 M】 OC C0 / \ ./ \, ° \ '/ z \ / ° OC OC C0 591339 (where z is the same as above) After the reaction is finished, the reaction product is made into the general formula (6) The indicated dicarboxylic anhydride is reacted in a suitable solvent. [Chemical formula 2 3] C0 / \ 〇 (6) '〇 / (where γ is the same as above) In this reaction, it is necessary to add a dicarboxylic acid used in the reaction at a molar ratio of 1: 9 9 to 6 5: 3 5 The anhydride is reacted with tetracarboxylic dianhydride. It is preferably 5 · 95 to 60:40, and more preferably 5:99 to 50:50. In other words, when the proportion of the dicarboxylic anhydride is less than 1 mole% of all the anhydrides, the molecular weight tends to increase and the resin viscosity tends to increase. Due to the high viscosity of the resin and the poor workability when the photoresist solution is prepared, the molecular weight becomes larger, and the resin in the unexposed part during the coating film cannot be dissolved in the developing solution, resulting in the problem that the intended pattern cannot be obtained during development. . In addition, when the proportion of the dicarboxylic anhydride is more than 65 mol% of the total anhydride, the molecular weight of the obtained resin becomes small, and there is a problem of residual adhesion of the coating film after pre-baking, or a problem of heat resistance or solvent resistance. The solvent used when the (meth) acrylic acid ester derivative reacts with a dicarboxylic anhydride or a tetracarboxylic anhydride, as long as it can dissolve the components used in the reaction and the reaction product and does not adversely affect the reaction Without special restrictions. For example, it is preferable to use a cellosolve solvent such as ethyl cellosolve acetate, butyl cellosolve acetate, or the like. The reaction is preferably performed at a quantitative reaction temperature between tetracarboxylic dianhydride and dicarboxylic anhydride and the hydroxyl group in the (meth) acrylic acid ester derivative of formula (4). For example, in the reaction of a (methyl-16-yl) acrylate derivative with a tetracarboxylic dianhydride, it is usually performed at 100 to not :, preferably 1 to 15 to 125 ° C. When the reaction temperature is higher than 130 ° C, due to the polymerization of some (meth) acrylate derivatives, it is due to the sharp increase in molecular weight. If the reaction temperature is lower than 100 ° C, the reaction may not proceed smoothly and there may be unreacted Tetracarboxylic dianhydride remains. The reaction product of the (meth) acrylic acid ester derivative and tetracarboxylic dianhydride is preferably reacted with dicarboxylic anhydride at 80 to 110 ° C, more preferably 80 to 90 ° C. If the reaction temperature is higher than 10 ° C, some (meth) acrylate derivatives may cause polymerization, which is the reason for the sharp increase in molecular weight. If the reaction temperature is lower than 8 ° C, the reaction may not proceed smoothly, and there may be unreacted dicarboxylic anhydride. In the production of the resin of the present invention, the total amount of the tetracarboxylic dianhydride and the anhydride group of the dicarboxylic anhydride is 0.6 to 1 equivalent and 0.75 to 1 equivalent of the hydroxyl group of the (meth) acrylate derivative. ~ 1 equivalent is preferred. If the total amount of acid anhydride groups is less than 0.6 equivalents, in order to achieve a high sensitivity to sufficiently increase the molecular weight, the necessary polymerizable double bond group cannot be fully introduced. Conversely, if the acid anhydride group is greater than 1 equivalent, Similarly, not only the molecular weight is not easily increased, but unreacted tetracarboxylic dianhydride or dicarboxylic anhydride may remain, which is the cause of deterioration of the developability. The tetracarboxylic dianhydride represented by the general formula (5) is, for example, Aromatic polycarboxylic anhydrides such as pyromellitic anhydride, isopentaerythritol tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, etc. Furthermore, the general formula (6) Dicarboxylic anhydrides such as maleic anhydride, succinic anhydride Itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylextended methyltetrahydrophthalic acid, chlorobridged anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, etc. 17-591339 The present invention The molecular weight and acid value of the photopolymerizable unsaturated resin can be controlled by controlling the reaction conditions when a (meth) acrylic acid ester derivative is reacted with a tetracarboxylic dianhydride, and the η in general formula (1) can be adjusted. The alkali-soluble radiation-sensitive resin of the present invention can be cured by blending a photopolymerization initiator and hardened to obtain a hardened product having high transparency and excellent heat resistance. Secondly, the alkali-soluble radiation-sensitive radiation of the present invention The (A) photopolymerizable unsaturated resin of the present invention can be prepared by compounding (B) a compound having epoxy group 0 and (C) a photopolymerization initiator. (A) Component The photopolymerizable unsaturated resin can be used alone or in combination of two or more kinds. For example, a bisphenol fluorene type resin and a biscresol fluorene type resin can be used as the (A) component of the photopolymerizable unsaturated resin. For compounds having (B) component epoxy groups A compound having at least one epoxy group can be used. For example: phenol novolac lacquer type epoxy resin, cresol novolac lacquer type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, Epoxy resin such as bisphenol S epoxy resin, biphenyl epoxy resin, alicyclic epoxy resin and resin, or phenyl glycidyl ether, p-butylphenol glycidyl ether, and tri epoxy resin Propyl isocyanate, diglycidyl isocyanate, allyl glycidyl ether, glycidyl methacrylate, etc. In terms of the component (B) component, the component (B) may be used alone or in combination Two or more types are used. The photopolymerization initiator of the component (C) is the component (D) as described above and a photopolymerizable monomer or oligomer to be contained as the component (D) (described below) A compound of a photopolymerization initiator and / or a compound having a sensitizing effect. (C) Components such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone-18-591339, p-dimethylaminoacetophenone, dichloroacetophenone Ketones, trichloroacetophenones, acetophenones such as 3--butylacetophenone, or benzophenones, 2-chlorobenzophenones, p, p'-bisdimethylamine Benzophenones such as methyl benzophenone, or benzyl, phenylene, benzyl ether, phenyl isopropyl ether, phenyl isobutyl ether, etc., or benzyl dimethyl Sulfur compounds such as ketals, thioxanthone, 2-thioxanthyl chloride, 2,4-diethylthioxanthine, 2-methylthioxanthine, 2-isopropylthioxanthine, or 2-ethylanthraquinone , Anthraquinones such as octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3-diphenylanthraquinone, azobisisobutylfluorene, phenylfluorenyl peroxide, cumene oxidation Organic peroxides such as compounds, or thiol compounds such as 2-fluorenylbenzimidazole, 2-fluorenylbenzoxazole, and 2-fluorenylbenzothiazole. These compounds may be used singly or in combination of two or more kinds. In addition, the substance itself does not function as a photopolymerization initiator. By using the above compounds in combination, a compound that increases the ability of the photopolymerization initiator can be added. This compound is, for example, a tertiary amine such as triethanolamine which is effective when used in combination with benzophenone. The radiation-sensitive resin composition of the present invention preferably contains 5 to 50 parts by weight (B) and 0.1 to 30 parts by weight (C) with respect to 100 parts by weight of the (A) φ component, and more preferably contains 10 to 30 parts by weight of the component (B) and 1 to 20 parts by weight of the component (C). With respect to 100 parts by weight of the component (A), when the content of the component (B) is less than 5 parts by weight, the characteristics of the composition of the present invention after hardening, especially the alkali resistance is insufficient, and if it is more than 100 parts by weight It is easy to cause cracks and decrease in adhesion during hardening. In addition, if the content of the component (C) is less than 0.1 parts by weight with respect to 100 parts by weight of the component (A), the photopolymerization rate will be slowed and the sensitivity will tend to decrease. In addition, if it is more than 30 parts by weight, since -19- j π · Γ5 · cannot reach the substrate, the adhesion between the substrate and the resin tends to be poor. The resin composition of the present invention may contain a photopolymerizable monomer or oligomer as a component (D) as needed, and may be used in combination with the purpose of use. The photopolymerizable monomer or oligomer is, for example, the monomer or oligomer described below. For example, monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, or ethylene glycol di ( Meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethyl glycol di (methyl) ) Acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, isopentaerythritol di (meth) acrylate, isopentaerythritol tri (methyl) Base) acrylate, isopentaerythritol tetra (meth) acrylate, diisopentaerythritol tetra (meth) acrylate, diisopentaerythritol hexa (meth) acrylate. (Meth) propylene triesters such as glycerol (meth) acrylate. These monomers or oligomers may be used singly or in combination of two or more kinds. The monomer or oligomer of the component (D) is used as a viscosity adjusting agent or a photo-crosslinking agent, and it can be used in combination within a range that does not impair the properties of the resin composition of the present invention as required. Usually, at least one of the above monomers and oligomers is blended with 50 parts by weight or less with respect to 100 parts by weight of the photopolymerizable unsaturated resin of the component (A). When the monomer or oligomer is used in an amount of more than 50 parts by weight, the adhesion after pre-baking may be problematic. In the radiation-sensitive composition of the present invention, it can be blended with, for example, an epoxy-based hardening accelerator, a thermal polymerization inhibitor, an antioxidant, an adhesion promoter, and a surfactant, as long as it is not detrimental to the purpose of the invention , Defoamer, etc.-20-additives. Examples of the epoxy hardening accelerator include amine compounds, imidazole compounds, carboxylic acids, phenols, quaternary ammonium salts, and methylol-containing compounds. By adding a small amount of an epoxy-based hardening accelerator to heat the coating film, the obtained photoresist film has improved heat resistance, solvent resistance, acid resistance, plating resistance, adhesion, electrical characteristics, and hardness. Thermal polymerization inhibitors include, for example, hydroquinone, hydroquinone monomethyl ether, pyrogallol, 3-catechol, phenol thienol, and the like. In addition, the adhesion of the obtained composition can be improved by adding an adhesion promoter. The adhesion assistant is preferably a silane compound (functional silane coupling agent) having a reactive substituent such as a carboxyl group, a methacryl group, an isocyanate group, and an epoxy group. Specific examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-epoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. The defoaming agent is, for example, a silicon-based, fluorine-based, or acrylic-based compound.

In addition, by adding a surfactant, the obtained composition can be easily coated, and the flatness of the obtained film can be improved. Examples of surfactants: BM-1 0 0 0 (made by BM Black Rice), Mekafak F142D, same F172, same F173 and same F183 (made by Dainippon Ink Chemical Industry Co., Ltd.), Fluron Raton FC -1 3 5, same as FC-170C, fluoron raton FC- 430 and same FC-431 (manufactured by Sumitomo Slieem Co., Ltd.), Seflon S-112, same as S-113, same as S-131 , Same as S-141 and same S-145 (made by Asahi Glass Co., Ltd.), SH-28PA-21-591339, SH-190, SH-193, SZ-6032, SF-8428, DC-57 and DC-190 (Manufactured by Toray Polysilane Co., Ltd.). The radiation-sensitive resin composition of the present invention can be uniformly dissolved in a general organic solvent by dissolving (A) component, (B) component, (C) component, and (D) component or other additives as needed, in a general organic solvent. Mix and modulate. The organic solvent is not particularly limited as long as it does not react with each component in the composition and dissolves each other. For example, alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl methyl ether, and ethylene glycol monoethyl ether; methyl Cellosolvic acid acetates, ethylcellosolve acetates, and other glycol alkyl ether acetates; diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, Diethylene glycols such as ethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether; propylene glycol methyl ether acetate, propylene glycol ether ether acetate and other propylene glycol alkyl ether acetates; Aromatic hydrocarbons such as toluene, xylene, methyl ethyl ketone, methyl pentanone, cyclohexanone, ketones such as 4-methyl-4-methyl-2-pentanone; and 2-hydroxypropionic acid Ethyl ester, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, methyl 2-hydroxy-2-methylbutyrate, 3 -Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, methyl lactate, ethyl lactate And other esters. Among these, alcohol ethers, alkanediol alkyl ether acetates, diethylene glycol dialkyl ethers, ketones, and esters are preferred, and the more preferred is ethyl 3-ethoxypropionate , Ethyl lactate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and methylpentanone. These solvents may be used alone or in combination of two or more. -22-591339 The composition of the present invention thus prepared is usually used after being filtered, for example, with a microporous filter having a pore diameter of 1 · 〇 ~ 〇 · 2μπ]. The method of applying the solution of the radiation-sensitive resin composition of the present invention on a substrate may be any of a method using a stain method, a spray method, and a roll coater, a slit coater, a rod coater, and a spin coater. One way. In this way, the resin composition solution is applied to a thickness of 1 to 30 μm, and then the solvent is removed to form a film. The radiation used in the radiation-sensitive resin composition of the present invention is arranged in order of wavelength length, and visible light, ultraviolet rays, electron rays, X-rays, alpha rays, beta rays, gamma rays, and the like can be used. Among these, ultraviolet rays are practically the best radiation in terms of economy and efficiency. As the ultraviolet rays used in the present invention, ultraviolet rays emitted from low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, or arc lamps, xenon lamps, and the like can be used. The above-mentioned radiation having a shorter wavelength than ultraviolet rays has high chemical reactivity, is theoretically superior to ultraviolet rays, and is more practical in terms of economic efficiency. After the photosensitive layer formed of the resin composition provided on the substrate is selectively exposed using the radiation described above, the non-irradiated portion of the radiation is removed by developing processing with a developing solution to pattern the film. Examples of the development method include a liquid holding method, a dipping method, and a shaking dipping method. The developing solution is, for example, an alkali developing solution and an organic solvent capable of dissolving the composition of the present invention. Examples of the base used for preparing the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium methylsilicate, ammonium, ethylamine, n-propylamine, diethylamine, diethylamine ethanol, and di-n Propylamine, triethylamine, methyldiethylamine, dimethyl-23-591339 methylethanolamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, pyrargin, 1 , 8-diazide ring (5,4,0) -7-Eleven, 1,5-diazide bicyclic (4,3,0) -5-nonan, preferably sodium carbonate, Tetramethylammonium hydroxide. If necessary, a water-soluble organic solvent such as methanol, ethanol, propanol, ethylene glycol or the like, a surfactant and the like can be used as a developing solution in an appropriate amount in the alkaline aqueous solution. The development of the resin composition of the present invention is usually performed at a temperature of 10 ~ 50 ° C, preferably 20 ^ ~ 40 ° C, using a commercially available developer or cleaner. After alkali development, in order to improve alkali resistance, it is preferable to perform an epoxy hardening treatment by heating. In the resin composition of the present invention, by performing heat treatment, not only the durability to strongly alkaline water can be significantly improved, but also various properties such as adhesion to glass, copper and other metals, heat resistance, and surface hardness can be improved. The heating temperature and heating time of the heating and hardening conditions are, for example, 80 to 200 ° C and 10 to 120 minutes. Next, a method for producing a film by photopolymerization of a radiation-sensitive resin composition of the present invention will be described by way of example. First, a photoresist liquid made of the resin composition is coated on a substrate by any method. In the examples, a spin coater is used. Of course, coating methods such as dip coating or rod coating, such as roll coating and slit coating, can also be used. After the photoresist is applied, pre-baking is performed to evaporate the solvent. Then, an ultra-high-pressure mercury lamp or the like is used for tight exposure, and the unexposed portion is developed with an aqueous solution of about 1% by weight of sodium carbonate and washed with water. Then, the film is completely dried by post-baking at a temperature of about 20CTC, and the desired heat resistance, transparency, and excellent adhesion, hardness, solvent resistance, and alkali resistance can be obtained. Laminated. The radiation-sensitive resin composition of the present invention is extremely useful as an insulating film, an insulating coating, an adhesive, a printing ink, or a coating agent, and is particularly useful as a color filter material for a liquid crystal display device or a solid-state imaging device. In addition, the hardened material has excellent hardness, welding heat resistance, transparency, acid resistance, alkali resistance, solvent resistance, insulation resistance, electrolytic corrosion resistance, and plating resistance, and the smoothness of the film when used as a coating agent. For example, when it is used as a material for a color filter, it can be used as a protective film for a color filter by adding a leveling agent to the resin composition of the present invention. At this time, ITO (indium tin oxide) can be sputtered on the protective film at a high temperature of 250 ° C, and sufficient resistance to strong acid and alkali treatment can be obtained when the I TO pattern is formed. It is considered that the resin composition of the present invention is extremely excellent in this respect even when the conventional protective film cannot sputter IT0 even at a temperature of 200 ° C. In addition, by mixing pigments or carbon black in the above-mentioned compounds, each can be used as a color photoresist ink or a photoresist ink for a black substrate. In this case, a conventional organic pigment or an inorganic pigment can be used as the pigment. The cured film obtained by curing the composition of the present invention has excellent heat resistance, transparency, adhesion to a substrate, acid resistance, alkali resistance, surface hardness, and the like. In addition, since the cured film is an organic coating film, it has a low electromotive force. Therefore, the composition of the present invention can be used for many applications other than the color filter described above. For example: materials for protective films of electronic parts (such as materials for forming protective films for liquid crystal display elements, integrated circuit elements, solid-state imaging elements, etc. containing color filter gas); interlayer insulation and / or planarization films Forming materials; -25-591339 soldering photoresist used in printed wiring boards; or alkali-soluble photosensitive composition suitable for forming column spacers instead of bead spacers in liquid crystal display elements . Moreover, the composition of the present invention is suitable for use as a material for various optical parts (lenses, LEDs, plastic films, substrates, optical discs, etc.); a coating agent for forming a protective film of the optical part; an adhesive for optical parts (adhesion for optical fibers) Agents, etc.); coating agents for manufacturing polarizing plates; photosensitive resin compositions for hologram recording, and the like. ㈣Embodiments Examples The present invention will be described more specifically with examples in the following, but the present invention is not limited by these examples. (Example 1 · Production of Resin 1) In a 500 ml four-necked flask, 235 g of a bisphenol fluorene type epoxy resin (epoxy compound represented by formula (3); R1 = H; epoxy equivalent 23 5), 110 Mg of tetramethyl chloride, 100 mg of 2,6-th-3-butyl-4-methylphenol, and 72.0 g of acrylic acid 'were blown into the air at a speed of 25 ml / min at 90 to 100 ° C. Garue dissolves. Then, the solution was slowly heated in a cloudy state and heated to completely dissolve at 12 ° C. Then the solution was made transparent and viscous and continued to be stirred. Among them, 'measure the acid value and continue to heat to less than 1.0 mg KOH / g. It takes 12 hours until the acid value reaches the target. Next, it is cooled to room temperature to obtain a colorless, transparent, solid, bisphenol fluorene type epoxy acrylate represented by the general formula (4) (Ri = H, r2 = h). ο Then add 600 g of propylene glycol monomethyl ether acetate to 307.0 g of the above-mentioned bisphenol fluorene type epoxy acrylate to dissolve it, and then mix with 5 g of 2 6-591339 benzophenone tetraresidic anhydride and 1 g of tetraethyl bromide, slowly heating up, and reacting for 4 hours at 11 ο ~ 1 15 ° C. After confirming the disappearance of the acid anhydride group, make 3,8. Og of 1,2,3,6-tetrahydrophthalic anhydride Mix and react at 9 ° C for 6 hours to obtain Resin 1 (where Y / Z molar ratio = 50.0 / 50.0) represented by the general formula (1). The disappearance of the acid anhydride is confirmed by IR spectrum. Example 2: Production of Resin 2) 3 07 · 0 g of the bisphenol fluorene type epoxy acrylate produced in Example 1 was used, and 600 g of propylene glycol monomethyl was added. After the ether acetate was made into a solution, 104.7 g of benzophenone tetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed, the temperature was gradually raised, and the reaction was carried out at 110 to 115 ° C for 4 hours. Confirm After the acid anhydride group disappeared, 5.2 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C for 6 hours to obtain a resin 2 ( Among them, the molar ratio of Y / Z = 2 3.5 / 76.5). The disappearance of the acid anhydride was confirmed by an IR spectrum in the same manner as in Example 1. (Example 3: Production of Resin 3) 37.0 · g was used in Example 1 The produced bisphenol fluorene type epoxy acrylate was added with 600 g of propylene glycol monomethyl ether acetate as a solution, and 67.6 g of benzophenone tetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed, and slowly The temperature was raised, and the reaction was carried out at 110 to 115 ° C for 4 hours. After confirming the disappearance of the acid anhydride group, 48.6 g of 1'2'3,6-tetrahydrophthalic anhydride was mixed and the temperature was at 90 ° C. The reaction was continued for 6 hours to obtain a resin 3 (wherein, the molar ratio of Y / Z = 60/40) was obtained. The disappearance of the acid anhydride was confirmed by an IR spectrum. (Example 4: Resin 4 (Manufactured) Manufactured in Example 1 using 3 07 · 0g Phenol fluorene type epoxy acrylate, after adding 600 g of propylene glycol monomethyl ether acetate to make a solution, 96.6 g of bis 27-591339 benzophenone tetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed, slowly The temperature was raised, and the reaction was carried out at 110 to 115 ° C for 4 hours. After confirming the disappearance of the acid anhydride group, 45.6 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed, and the mixture was heated at 9 01 : Reacted for 6 hours to obtain resin 4 (wherein, the Y / Z molar ratio = 50.0 / 50.0)-was obtained. The disappearance of the acid anhydride was confirmed by the IR spectrum in the same manner as in Example 1. -(Example 5: Production of Resin 5) In a 500 ml four-necked flask, 244 g of a biscresol fluorene type epoxy resin (epoxy compound represented by formula (3); κΗ3; epoxy equivalent is 244), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-th-3-butyl-4-methylbenzene, and 72.0 g of acrylic acid. Air was blown into the mixed solution at a rate of 25 ml / min, and heated and dissolved at 90 to 100 ° C to prepare a white turbid solution. Then, the solution was heated in a white turbid state and completely dissolved by heating to 120 ° C. A cloudy solution will increase the temperature, and then become transparent and sticky. After turbidity, the acid value was measured every certain time, and heating was continued to less than 1.0 mg KOH / g. It takes 12 hours for the acid value to reach the target. Next, it was cooled to room temperature to obtain a colorless, transparent, solid, biscresol fluorene type epoxy acrylate (R1 = CH3, R2 = H; i φ ο). Then, at 3 1 6 · 0 g of the biscresol fluorene epoxy propionate thus obtained was added to 600 g of propylene glycol monomethyl ether acetate to dissolve, and then 0.5 0.5 g of benzophenone (tetraresidic anhydride and 1 g of brominated acid) were mixed. The temperature was gradually increased, and the reaction was carried out for 4 hours at 110 to 115 ° C. After confirming the disappearance of the acid anhydride group, 3 δ. 〇g 1,2,3,6-tetrahydrophthalic anhydride was mixed, and The reaction was performed at 9 ° C for 6 hours to obtain resin 1 represented by the general formula (1) (wherein, the Y / Z mole ratio = 50.0 / 50.0). The disappearance of the acid anhydride was confirmed by IR spectrum.-2 8- 591339 (Comparative Example 1: Production of Resin 6) Using 3 07. Og of bisphenol fluorene type epoxy acrylate produced in Example 1 and adding 600 g of propylene glycol monomethyl ether acetate as a solution, 102.3 g of two Benzophenonetetracarboxylic dianhydride was mixed with 1 g of tetraethylammonium bromide, and the temperature was gradually increased, and the reaction was performed at 110 to 115 ° C for 4 hours. After confirming that the acid anhydride group disappeared, 0.5 g of 1 , 2,3,6-tetrahydrophthalic anhydride Mix and react at 90 ° C for 6 hours to obtain resin 6 represented by the general formula (1). However, in this resin 6, the molar ratio of Y / Z = 0.8 / 99.2 is outside the scope of the present invention. The disappearance of the acid anhydride was confirmed by IR spectrum in the same manner as in Example 1. (Comparative Example 2: Production of Resin 7) 37.0 g of the bisphenol fluorene type epoxy acrylate produced in Example 1 was used, and 600 g of propylene glycol was added. After monomethyl ether acetate was prepared as a solution, 48.3 g of benzophenone tetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed, and the temperature was gradually increased, and the reaction was performed at 110 to 11 for 4 hours. It was confirmed that the acid anhydride group disappeared. Then, 68.4 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C for 6 hours to obtain a resin 7 represented by the general formula (1). The disappearance of the acid anhydride is similar to that of Examples 1 was confirmed by IR spectrum in the same way. However, in this resin 7, the Y / Z mole ratio = 7 5/2 5 is out of the scope of the present invention. (Comparative Example 3: Production of resin 8) Use 3 07. Og is a bisphenol fluorene type epoxy acrylate prepared in Example 1. After adding 600 g of propylene glycol monomethyl ether acetate as a solution, 80.5 g of benzophenone tetracarboxylic dianhydride, 3 8.0 g of 1,2,3,6-tetrahydrophthalic anhydride and ig tetraethylammonium bromide are mixed, the temperature is gradually increased, and the reaction is performed at 1 1 to 1 15 ° C for 6 hours to obtain the general formula (7) The resin 8 shown (wherein the Y / Z molar ratio = 50.0 / 50. -29-591339). The disappearance of the acid anhydride was confirmed by IR spectrum in the same manner as in Example 1. This resin 8 does not have the structure of the resin of the present invention. (Comparative Example 4: Production of Resin 9) Using 30.7 g of the bisphenol fluorene type epoxy acrylate produced in Example 1 and adding 300 g of propylene glycol monomethyl ether acetate as a solution, 1 1 4 g of 1,2,3,6-tetrahydrophthalic anhydride and 1 g of tetraethylammonium bromide were mixed, the temperature was gradually raised, and the reaction was performed at 90 to 100 ° C for 4 hours to obtain resin 9. The disappearance of the acid anhydride was confirmed by IR spectrum. Table 1 shows the equivalent ratios and properties of the resins 1 to 5 obtained in Examples 1 to 5 and the resins 6 to 9 obtained in Comparative Examples 1 to 4 at the time of manufacture. -30- 591339 Table resin No. Y / Z molar ratio equivalent resin acid value (mg K0H / g) theoretical resin acid value (mg K0H / g) number average molecular weight solution viscosity (mPa · s, 25 °) Example 1 Resin 1 50/50 2 / 0.5 / 1.0 100 99.8 3,700 1,060 Example 2 Resin 2 23.5 / 76.5 2 / 0.2 / 1.3 99.6 99.5 7,000 3,240 Example 3 Resin 3 60/40 2 / 0.64 / 0.86 100 100.2 1,800 640 Implementation Example 4 Resin 4 50/50 2 / 0.6 / 1.2 113.7 113.3 6,520 2,000 Example 5 Resin 5 50/50 2 / 0.5 / 1.0 97.8 96.8 4,100 1,230 Comparative Example 1 Resin 6 0.8 / 99.2 2 / 0.006 / 1.494 99.3 99.2 8,670 11,700 Comparative example 2 resin 7 75/25 2 / 0.9 / 0.6 100.6 100.2 less than 1,000 330 comparative example 3 resin 8 50/50 2 / 0.5 / 1.0 88.8 99.8 6,700 4,500 comparative example 4 resin 9 100/0 2 / 1.5 / 0 100.2 100 less than 1,000 160 In addition, the equivalent ratio and each evaluation item in Table 1 are as follows. 1) The equivalent ratio indicates bisphenol (or biscresol) 芴 -type epoxy acrylate / monobenzone. Equivalent ratio of tetra-residual acid monoanhydride / 1,2 '3,6-tetrahydroanhydride. 2) The resin acid value is measured in a 100 ml Erlenmeyer flask! The sample g was dissolved by adding 30 ml of acetone, and then titrated with an aqueous solution of 0.1 M N aOH using bromine thyme osmium blue liquid as an indicator. 3) The number average molecular weight is a conversion 値 measured by gel permeation chromatography. 4) The viscosity of the solution is determined by using a B-type viscometer to dissolve the resin at 50% by weight in propylene glycol monomethyl ether acetate, and measure it at 2rc. As can be seen from the results in Table 1, the resin of the present invention has a theoretical value of about 5 to about the same as the real value of the acid value of the resin. Therefore, the condensation reaction is not caused in the reaction-3 1-591339. (L) Resin not constructed. In addition, there is no increase in molecular weight after a period of time ', so it can be proved that it can be produced industrially stably. In addition, since the Mohr of Y / Z is smaller than 1/99, the resin 6 has a larger molecular weight and a higher viscosity. Moreover, since the molar ratio of γ / Z is 65/35, the resin 7 has a smaller molecular weight and a lower viscosity. Resin 8 shows its physical properties (reduced acid value and increased viscosity). Even if the mixing ratio of acid anhydride / acid dianhydride is the same, the molecular weight will increase due to the condensation reaction and the solution viscosity will increase. This tendency is considered to be caused by a longer and longer reaction time. In addition, the molecular weight of resin 9 becomes smaller, and the viscosity of the solution also decreases. (Examples 6 to 12 and Comparative Examples 5 to 8) Photoresist unsaturated resins (Resins 1 to 9) obtained in Examples 1 to 5 and Comparative Examples 1 to 4 were used to prepare a photoresist having a composition shown in Table 2 Solution. Moreover, Example 1 3 is a 1: 1 composition of resin 1 (bisphenol fluorene type resin) and resin 5 (biscresol fluorene type resin). -32_ 591339 Table 2 Example tmm 6 7 8 9 10 11 12 13 5 6 7 8 Photopolymerizable unsaturated resin resin 1 resin 1 resin 2 resin 2 resin 3 resin 4 resin 5 resin 1 resin 5 resin 6 resin 7 resin 8 Resin 9 20.0 20.0 20.0 20.0 20.0 20.0 20.0 10.0 10.0 20.0 20.0 20.0 20.0 Diisopentaerythritol hexaacrylate — 8.6 — 8.6 8.6 8.6 8.6 8. 6 8.6 8.6 8.6 8.6 Tetramethylbiphenyl epoxy resin 3 4.4 3 4.4 4.4 4.4 4.4 4.4 4.4 4.4 4.4 4.4 4.4 Michler's ketone 0.1 0.2 0.1 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Eurekachia 907 0.6 1.2 0.6 1.2 1.2 1.2 1.2 1.2 1. 2 1.2 1.2 1.2 1.2 Propylene glycol monomethyl ether acetate Esters 76.3 65.6 76.3 65.6 65.6 65.6 65.6 65.6 65.6 65.6 65.6 65.6 Total 100 100 100 100 100 100 100 100 100 100 100 100 The numbers refer to parts by weight and the 'tetramethylbiphenyl-type epoxy resin used is an oiled osmium shell Company name, "Yepicton YX_4000", epoxy equivalent 193. In addition, the Yilu Cachia 907 is manufactured by Chiba Specialty Chemicals. The obtained photoresist solution was applied on a glass substrate using a spinner, and pre-baked on a 90-degree hot plate for 120 seconds to form a coating film having a film thickness of about 2 μm. A photomask having a predetermined pattern was placed on the coating film, and a UV light having a wavelength of 405 nm and a light intensity of 9.5 mW / cm2 was irradiated onto the coating film with an energy line of 100 mJ / cm2 using a high-pressure mercury lamp of 250W. Exposure processing. After the irradiation, an unexposed portion of the coating film was removed by performing a development treatment at 25 ° C for 30 seconds using a sodium bicarbonate aqueous solution at a weight%. Then, it wash | cleaned by ultrapure water. The glass substrate having the film subjected to the exposure treatment and the development treatment was left in a 200 ° C oven for 30 minutes (post-baking treatment), and the film was heated and hardened to obtain a heat-cured film. The evaluation of each resin concerning the formation of the above coating film, exposure, development processing, and heating process, that is, the obtained heat-cured film was performed as follows. -33-591339 (η coating film dryness: The dryness of the coating film after pre-baking is evaluated on the basis of π s-Κ-5 4 〇 0. The evaluation criteria are as follows. 〇: No sticking at all △: Slightly There is a sticking situation X: There is a significant sticking situation. (2) The developability of the alkali solution is that the pre-baked coating film without exposure treatment is immersed in a 1% by weight sodium carbonate aqueous solution for 30 seconds. "Development" Enlarges the substrate after development by 50 times, and visually evaluates the remaining resin. The evaluation criteria are as follows. ○: Those with good developability (those with no photoresist residue on the glass at all) △: Development Those with poor performance (those with slight photoresist residues on the glass) X: People with poor imaging properties (those with many photoresist residues on the glass) (3) Exposure sensitivity during exposure and development The grading plate (negative reticle with optical density of 12 steps) is used as a photomask to perform adhesion, exposure, and development on the coating film. Then, the number of steps of the remaining grading plate is calculated. The number in Table 3 is the number of steps The evaluation method is that the higher the number of segments remaining at high sensitivity, the higher the hardness. (Heat cured film) of the reference system measured at a hardness test method of the nS-K- 5400. Using a pencil hardness tester, the highest hardness without damage to the coating film when the 9.8N load was suspended on the heat-cured film was used as the hardness. -34-591339 The pencil used for comparison is "Mitsubishi High Quality". (5) Adhesion The adhesion between the coating film (heat cured film) and the glass substrate was measured by a peel test. The coated film was cross-cut and made at least 100 chessboards, and then peeled off with an adhesive tape (registered trademark), and the peeling state of the chessboards was evaluated under an optical microscope at 50 times magnification. The evaluation criteria are as follows. 〇: No peeling at all X: Those who have confirmed peeling (6) Heat resistance Put the heat-cured film in a 25 (TC oven for 3 hours, perform hardening and baking, and determine the film thickness change rate before and after hardening (( Film thickness before hardening and baking-film thickness after hardening and baking) / (film thickness before hardening and baking)) X 1 00. The evaluation criteria are as follows. ○: Excellent heat resistance (5% of film thickness change) Below: △: Slightly better heat resistance (5% to 10% change in film thickness) X: Poor heat resistance (more than 10% change in film thickness) (7) Chemical resistance (i) Acid solution: less than 5 weight % HC 1 aqueous solution for 24 hours at room temperature (ii) alkaline solution ii-1: immersed in 5% by weight NaOH solution for 24 hours at room temperature i 1-2 ·· 4% by weight KOH solution at 50 ° C 10 minutes immersion II-3: Immersion in 1% by weight NaOH aqueous solution at 80 ° C for 5 minutes (iii) Solvent-35- 591339 1 i 1-1: N-methylpyrrolidone at 40 ° C for 10 minutes iii-2: immersed in N-methyl P bilobazone for 5 minutes at 80 ° C to determine the change in film thickness before and after immersion ((film thickness before immersion-film thickness after immersion) / (immersion Previous film thickness)) X 1 00. The evaluation criteria are as follows: ○: Excellent chemical resistance (5% of film thickness change rate of all solutions) △: Slightly better heat resistance (film thickness change rate of all solutions 5) % ~ 1 0%) X: Poor heat resistance (the rate of change in film thickness of all solutions is more than 10%) The above results are shown in Table 3.-36- 591339 Table 3

Evaluation item Coating film dryness, developability, exposure sensitivity, coating film hardness, adhesiveness, heat resistance, chemical resistance Example 6 〇〇4 4 〇〇 Example 7 〇09 5Η 〇 Example 8 〇 〇 4 4 〇 〇 〇 Example 9 〇09 5Η 〇〇 Example 10 〇09 5Η 〇〇 Example 11 〇 08 5Η 〇 Example 12 〇09 5Η 〇 Example 13 009 5Η 〇 〇Comparative Example 6 〇 一一 —— ——Comparative Example 7 〇09 5Η 〇XX Comparative Example 8 〇09 4Η X 〇Δ Comparative Example 9 X 〇4 3Η XXX Moreover, Comparative Example 5 is not Since the exposed part was not dissolved and could not be patterned, the following evaluation was suspended. From the results in Table 3, it can be seen that the resins of Examples 6 to 12 can achieve the desired physical properties. Moreover, the composition of the resin 1 (bisphenol fluorene type resin) and resin 5 (biscresol fluorene type resin) of Example 13 can also achieve good physical properties. However, since Comparative Example 5 had a molar ratio of Y / Z = 0.8 / 99.2 and the molecular weight of the resin was too large, the unexposed portion did not dissolve in the developing solution, and the target pattern could not be obtained. In addition, in Comparative Example 6, Y / Z = 7 5/2 5, contrary to Comparative Example 5, the molecular weight of the resin is too small, the film thickness changes after hardening and baking, and the film thickness changes after solvent baking after post-baking are significant. , Poor heat resistance and solvent resistance. From the above results, it can be seen that the radiation-sensitive resin composition of the present invention can provide excellent protective films such as heat resistance, transparency, adhesion, hardness, solvent resistance, and alkali resistance. [Effects of the Invention] The photopolymerizable unsaturated resin of the present invention is extremely useful as a photopolymerizable component of an alkali-soluble sexy radioactive resin composition suitable for various applications. The radiation-sensitive resin composition of the present invention contains the photopolymerizable unsaturated resin to form a coating film excellent in heat resistance and transparency as compared with a conventional resin. In addition, the pre-baked coating film is non-adhesive and can be closely exposed, which has the advantage of improving the resolution. However, since the cured film obtained by heating is excellent in acid resistance, alkali resistance, solvent resistance, and surface hardness, it is extremely useful not only for permanent protective photomask applications such as solvent photoresist, but also for printed wiring board-related applications. Etching photoresist or interlayer insulation material, radiation-sensitive adhesive, screen printing photosensitive liquid or photoresist ink, etc. Mon 3 8-

Claims (1)

591339 issued, _ please apply for a patent case No. 9 1 1 24623 "Photopolymerizable unsaturated resin, its preparation method and alkali-soluble radiation-sensitive resin composition using it" (revised on August 21, 1992) Application Patent scope: 1. A photopolymerizable unsaturated resin, the resin is a photopolymerizable unsaturated resin having a number average molecular weight of 1,500 or more represented by the general formula (1), which is composed of dicarboxylic anhydride and The tetracarboxylic dianhydride is obtained by reacting at a molar ratio of 1: 99 ~ 65: 35, COOH. I 'HOOC— Ϋ— C0—0—X—0—CO— Z—C0-0 —X — 0— CO—Y— C00H (1) | Π C00H (where X is a group represented by the general formula (2), (Wherein 1 ^ each represents an independent hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a halogen group, and R2 each represents an independent hydrogen atom or a methyl group), and η represents an integer from 1 to 20, Represents a residue other than the anhydride group of a dicarboxylic anhydride, and Z represents a residue other than the anhydride group of a tetracarboxylic dianhydride). 2. A method for producing a photopolymerizable unsaturated resin having a number-average molecular weight of 1,500 or more as represented by the general formula (1), which is obtained by combining an epoxy compound represented by the general formula (3) with (form) Group) acrylic acid is reacted to obtain a (methyl 591339) acrylate derivative represented by the general formula (4), and then reacted with a tetracarboxylic dianhydride represented by the general formula (5), and then the general formula (6 ), And the dicarboxylic anhydride is added in a molar ratio of 1: 9 9 to 6 5: 3 5 for reaction, 〇C C0 0 ·. ⑸ \ / \ ^ / 〇C C0 (where Z represents a residue other than the anhydride group of the tetracarboxylic dianhydride) cov / \ q ⑹ \. 〇 (where γ represents a residue other than the anhydride group of dicarboxylic anhydride) p COOH I 0-- X-0-CO-Y- COOH η ⑴ HOOC- Y-C0-0--X-0-C0 -2-CO-. Ί COOH-2_ 591339 (where X is a radical not represented by the general formula (2) (Where Ri, L, Y, and Z are the same as above; η is an integer of 1 to 20). 3. —An alkali-soluble radiation-sensitive resin composition 'comprising (A) 100 parts by weight of a photopolymerizable unsaturated resin such as the first patent application scope, (B) a compound having an epoxy group 5〜50 重量 份。 (C) Photopolymerization initiator 0.1 to 30 parts by weight. 4. The soluble radiation-sensitive resin composition according to item 3 of the scope of the patent application, which further contains (D) at least one of a photopolymerizable monomer and an oligomer, and its content is relative to 100 parts by weight (M The component is 50 parts by weight or less.