TW200403269A - Resin composition containing fluorene - Google Patents

Abstract

The purpose is to provide a heat-curable or radiation-curable functional epoxy resin. The curable article thereof having high hardness, high level heat resistance and electric property. The shrinkage of the resin during the curing is low and the pattering property thereof is excellent. Provided are a specific epoxy resin having fluorene skeleton, an epoxy resin acrylic resin, and an alkali-soluble radiation-curable unsaturated resin having fluorene.

Description

200403269 (1) Description of the invention: (1) The technical field to which the invention belongs The present invention relates to a novel buckwheat-containing epoxy resin, thorium-containing epoxy acrylate resin, and thallium-containing alkali. Solvent-type radiation polymerizable unsaturated resin, a method for producing the resin, and a thermosetting or radiation-curable resin composition containing the resin. In addition, the present invention relates to a molded article having excellent heat resistance and electrical characteristic hardness obtained by using the resin composition. The present invention also relates to a radiation-sensitive linear resin composition containing the above-mentioned soluble radiation-ray polymerizable unsaturated resin, which is a protective film such as a modulation color filter, a liquid crystal display element, an integrated circuit element, a solid-state imaging element, or an interlayer insulation. Useful composition for films. (2) Prior art Generally, epoxy resin is hardened by various hardeners to form hardened materials with excellent mechanical properties, water resistance, chemical resistance, heat resistance, and electrical properties. Therefore, it can be used in a wide range of adhesives, coatings, laminated boards, molding materials, and injection molding materials. In the past, the most commonly used epoxy resins in the industry were liquid and solid bisphenol A type epoxy resins. Epoxy-based polymer materials have used epoxy acrylate resins since ancient times. This resin is used in a range of, for example, a photosensitive material (for example, Non-Patent Document 1). However, these resins are insufficient in heat resistance, electrical characteristics, and hardness, for example, in a range in which a high level of heat resistance is required. [Non-Patent Document 1] "Photosensitive Resin" by Yafu Yamaoka and Hiroshi Morita, published by Kyoritsu, March, 1988, 82-84 pages. (3) Summary of the Invention 200302269 Problems to be Solved by the Invention The object of the present invention is to solve the above-mentioned conventional problems. The object of the present invention is to provide a hardened material with high hardness, high level of heat resistance and electrical characteristics, and shrinkage during hardening. Functional epoxy resin with low rate, excellent patternability, thermosetting or radiation curing properties. Another object of the present invention is to provide a method for producing the resin and a composition containing the resin. Another object of the present invention is to provide a molded body obtained by curing the resin composition. Solve the problem of the abundance of the particles The fluorene-containing epoxy resin of the present invention is represented by the following general formula (1):

(Wherein L represents each independently a hydrogen atom or a methyl group, η represents each independently an integer of 0 to 10, and m represents each independently an integer of 2 to 5). A preferred embodiment is that m = 2 in the general formula (1). The method for preparing a manganese-containing epoxy resin of the present invention includes a step of reacting epichlorohydrin in a polyfunctional hydroxyl-containing fluorene compound represented by the following general formula (2), [Chem. 9]

(Wherein R! Each independently represents a hydrogen atom or a methyl group, η each independently represents an integer of 0 to 10, and m each independently represents an integer of 2 to 5). 200403269 In a preferred embodiment, m = 2 in the general formula (2). The epoxy resin composition of the present invention contains the above-mentioned epoxy-containing epoxy resin. The present invention includes a molded article obtained by curing the buckwheat-containing epoxy resin composition as described above. The manganese-containing epoxy acrylate resin of the present invention is characterized by the following general formula (3):

(Wherein h and R2 each independently represent a hydrogen atom or a methyl group, η each independently represents an integer of 0 to 10, and m is each independently an integer of 2 to 5). In a preferred embodiment, m = 2 in the general formula (3). The first production method of the epoxy-containing acrylate resin containing Chiang Kai-shek of the present invention includes the step of reacting (meth) acrylic acid in a manganese-containing epoxy resin represented by the following general formula (1),

【Chemical 1 1】

(Wherein R 1 each independently represents a hydrogen atom or a methyl group, η each independently represents an integer of 0 to 10, and m each independently represents an integer of 2 to 5). In a preferred embodiment, m = 2 in the general formula (3). The second production method of the fluorene-containing epoxy acrylate resin of the present invention is characterized in that 200403269 is contained in a polyfunctional hydroxyl group-containing fluorene compound represented by the following general formula (2) to act on propylene oxide (meth) acrylate Steps, [化 12]

(Wherein Ri represents each independently a hydrogen atom or a methyl group, η represents each independently an integer of 0 to 10, and m represents each independently an integer of 2 to 5). In a preferred embodiment, in the general formula (3) of the above-mentioned polyfunctional hydroxyl-containing fluorene compound, m = 2. The thermosetting composition of the present invention is characterized by the above-mentioned manganese-containing epoxy acrylate resin. The radiation-sensitive linear resin composition of the present invention is characterized by containing the above-mentioned manganese-containing epoxy acrylate resin. The present invention includes a molded article obtained by curing the above-mentioned thermosetting composition or radiation-sensitive resin composition. The alkali-soluble radiation-polymerizable unsaturated resin containing fluorene of the present invention is characterized in that a polybasic carboxylic acid or an anhydride thereof is obtained by reacting a fluorene-containing epoxy acrylate resin represented by the general formula (3) (1) H2C = C- CO- H2C- CH- CH2h 0- CH-R: OH '\ R,

CH2- CH-0 4 CH2- CH-CH2- O- C- c = ch2 Rj I OH j 200403269 (where R! And R 2 each independently represent a hydrogen atom or a methyl group, and η each independently represent. An integer of 10 to 10, m is an integer of 2 to 5 each independently). In a preferred embodiment, m = 2 in the general formula (3). The method for preparing a manganese-base-soluble radiation-polymerizable unsaturated resin according to the present invention is characterized by including a polybasic carboxylic acid or its anhydride in a fluorene-containing epoxy acrylate resin represented by the following general formula (3): Reaction step, [化 14]

(Wherein L and R2 each independently represent a hydrogen atom or a methyl group, η each independently represents an integer of 0 to 10, and m is each independently an integer of 2 to 5). In a preferred embodiment, m = 2 in the general formula (3). The radiation-sensitive resin composition of the present invention contains the above-mentioned alkali-soluble radiation-polymerizable unsaturated resin containing buckwheat. (4) Embodiments Embodiments of the invention · A · Jiang-containing epoxy resin The fluorene-containing epoxy resin of the present invention is represented by the following general formula (1): [化 1 5]

200403269 (where R i each independently represents a hydrogen atom or a methyl group, η each independently represents an integer of 0 to 10, and m is each independently an integer of 2 to 5). The dill-containing epoxy resin is described in this specification as "pyrene-containing epoxy resin (1)", "epoxy resin (1)", and the like. It is preferable that m 値 is 2 in the general formula (1). Particularly, a resin containing two epoxy groups based on an ortho bond in a benzene ring is preferred. The epoxy resin (1) is obtained by, for example, reacting epichlorohydrin in a polyfunctional radical-containing swallow compound represented by the following general formula (2): [Chem. 16]

(Where, R, each independently represents a hydrogen atom or a methyl group, η, each independently represents an integer of 0 to 10, and m, each independently represents an integer of 2 to 5). This polyfunctional hydroxyl group-containing amidine compound is described in the present specification as a "multifunctional hydroxyl group-containing dill compound (2)". It is preferable that m 値 is 2 in the general formula (2). Particularly, a resin containing two hydroxyl groups based on an ortho bond in a benzene ring is preferred. The polyfunctional hydroxyl-containing fluorene compound can be prepared by a method known in this range. For example, a compound with m = 2 and n = 0 is prepared by a method described in Japanese Patent Application Laid-Open No. 200 1-206862. The reaction of the polyfunctional hydroxyl-containing fluorene compound (2) with epichlorohydrin is usually performed at a temperature range of 50 to 120 ° C for 3 to 10 hours. The epoxy resin composition of this invention contains the said epoxy resin (1). This epoxy resin (1) can be used alone or in combination of two or more. 200403269 The epoxy resin composition may contain (i) Z-oxygen resin in addition to the above-mentioned epoxy resin (1), (ii) reactive diluent, (丨 丨)) hardener, (丨v) Hardening accelerator, (v) additives, (vi) solvents, etc. Epoxy resins other than the epoxy resins in (i) above include bisphenol-based epoxy resins such as bisphenol A, bisphenol S, and bisphenol F; and polyfunctional phenol-based epoxy resins such as phenol resin and cresol novolac resin. Naphthalene-based epoxy resins such as naphthol-type epoxy resins; biphenyl-type epoxy resins; and alizarin-based epoxy resins other than the above-mentioned epoxy resins (1). The reactive diluent of the above (11) is a low-viscosity epoxy compound added for viscosity adjustment, and it is particularly preferably a low-viscosity epoxide compound having more than two functions. The reactive diluent particles are as follows: dipropylene oxide, butanediol dipropylene oxide, dipropylene oxide aniline, neopentyl alcohol propylene oxide, cyclohexanedimethanol_diglycidyl ether , Alkylene dipropylene oxide, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol tricyclopropyl ether, 4-ethylene Cyclohexene monooxide, vinylcyclohexyl dioxide, methylethenylcyclohexyl dioxide, and the like. These reactive diluents can be used singly or in combination of two or more. The above (in) hardener is not particularly limited, for example, amine compounds, imidazole compounds, carboxylic acids, phenols, quaternary ammonium salts, methylol-containing compounds, and tri flic acid salts , Boron trifluoride ether complexes, boron trifluoride, diazonium salts that generate acids by light or heat, salt, scorch salts, benzo azo iron salts, money salts Potential cationic polymerization catalysts for scale salts. The hardening accelerator of the above (IV) is, for example, 1,8-diazide ring (5.4.0) undecene-7 and its benzene salt, phenol novolac resin salt, carbonate, formate, etc.- 12- 200403269 amines (including tertiary amines) and their derivatives; 2-methylimidazole, 2-phenylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2 -Imidazoles such as phenyl-4-methylimidazole; organic phosphines such as ethylphosphine, propylenephosphine, phenylphosphine, triphenylphosphine, trialkylphosphine (the first, second, and third phosphines) Class) and so on. The additives (v) described above include, for example, reinforcing materials or concrete filling materials, colorants, pigments, flame retardants, hardening compounds (cured monomers, oligomers, or resins). As the above-mentioned reinforcing agent or filler, powdery or fibrous reinforcing agent or filler can be used. Powdery reinforcing agents or fillers are made of, for example, the following materials: metal oxides such as alumina and magnesium oxide; metal carbonates such as calcium carbonate and magnesium carbonate; diatom powder, alkaline magnesium silicate, Sand compounds such as fired clay, fine powdered sand, dissolved _ Yixing chemical sand, crystalline sand, etc .; metal hydroxides such as aluminum hydroxide; other kaolin, mica, quartz powder, graphite, molybdenum disulfide, etc. . Fibrous reinforcement or filler particles are as follows: glass fiber, ceramic fiber, carbon fiber, alumina fiber, silicon carbide fiber, borane fiber, polyester fiber, polyamide fiber, and the like. Examples of the colorant, pigment, or flame retardant include titanium dioxide, iron black, molybdenum red, dark blue, blue, cadmium yellow, cadmium red, antimony trioxide, red phosphorus, bromine compounds, and triphenyl phosphate. The above-mentioned curable compound is used for the purpose of improving the resin properties of the final coating film, adhesive layer, and molded article. For example, alkoxide resin, melamine resin, fluororesin, vinyl chloride resin, acrylic resin, polysiloxane resin, polyester resin, and the like. These hardening compounds are contained within a range that does not impair the original properties of the resin composition of the present invention. These additives may be used singly or in combination of two or more kinds. As the solvent of the above (vi), for example, the following solvents can be used: alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, -13-200403269 ethylene glycol monobutyl ether , Glycol dimethyl ether, Diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, Diethylene glycol dimethyl ether, Diethylene glycol diethyl ether, Diethylene glycol monobutyl ether, etc. ; Methyl Cellosolve Acetate, Ethyl Cellosolve Acetate, Butyl Cellosolve Acetate, Propylene Glycol Methyl Ether Acetate, Alkane Glycols such as 3-methoxybutyl-1 · acetate Monoalkyl ether acetates; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, methyl isobutyl ketone, methyl aromatic ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentane Ketones such as ketones; and ethyl 2-hydroxypropionate, methyl 2-mercapto-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, and glycolic acid Ethyl ester, methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, ethyl acetate, butyl acetate, methyl lactate, milk The ethyl esters of these solvents may be used alone or in combination of two or more. The composition of the present invention can be formed into a shaped body depending on the purpose. The formed body may be a product formed into a desired shape from a hardened material of the composition itself, or a coating film formed of a hardened material of the composition formed on a substrate. For example, the above-mentioned composition is melted by heating as needed, and flows into a predetermined mold and is heated or irradiated to obtain a shaped body having a desired shape. Alternatively, a solvent-containing liquid composition is coated on the substrate and dried, and then a hardened film is formed on the substrate by heating or irradiation with radiation. The molding method and hardening conditions are not particularly limited. For example, when molding using a predetermined mold, a molding method by heating and pressing or a low-temperature molding method called cold pressing is used. A method of heating and pressing, for example, a method called manual lay-up or spray lay-up, a method in which the composition of the present invention is filled with a mold under normal pressure, and then heated and hardened; a conversion pressing device is used, and injection molding is used. A method of applying 200403269 heating and compression; and a continuous forming method such as a continuous layer forming method, a continuous drawing forming method called Pultrus ^ n, a single yarn blowing forming method, and the like. Further, in these molding methods, an intermediate molding material may be prepared by mixing the above-mentioned resin composition with a reinforcing agent or impregnating the reinforcing agent, and molding and curing the intermediate molding material. Examples of the reinforcing agent include woven and non-woven fabrics made of resin and glass. The intermediate molding material obtained by using it is, for example, a sheet-shaped intermediate molding material called SMC (Slab-Molding Compound); a liquid or solid intermediate molding material called BMC (Berg quantitative molding compound) or a premix ; Glass cross tube or pad and so on impregnated with the pre-stained body of the present invention. The gadolinium-containing epoxy resin of the present invention is excellent in heat resistance and is easily hardened by heat or radiation. This epoxy resin-containing resin composition is excellent in molding processing 'as described above, and can be easily formed into a predetermined shape by a mold or a thin film can be formed on a substrate. These formed bodies (including films) obtained by heat or radiation hardening have excellent heat resistance and environmental resistance, high mechanical properties such as bending properties, high toughness, impact resistance, and good processability. In addition to the excellent heat resistance and other properties mentioned above, the molded article obtained from the epoxy resin composition has excellent insulation properties, small curing shrinkage, and excellent dimensional stability. Therefore, the composition can be used as an electrical and electronic material sealant. In addition, this composition is excellent in heat resistance, adhesiveness, and hardenability, and is therefore suitable for bottling materials and coating materials for various electronic parts such as capacitors. When the sealing material or bottling agent used as an electronic insulating material is used, the same method as the conventional sealing resin using an epoxy resin can be used. In addition, since the cured product is excellent in transparency, it can also be used as a thermosetting resin composition for an optical display. -15- 200403269 B · Ethylene-containing epoxy acrylate resin The manganese-containing epoxy acrylate resin of the present invention is represented by the following general formula (3): [化 7]

(Wherein 'R! And R2 each independently represent a hydrogen atom or a methyl group, η each independently represents an integer of 0 to 10, and m each independently represents an integer of 2 to 5). The Xue-containing epoxy-based acrylate resin is described in this specification as "manganese-containing epoxy-based acrylate resin (3)", "epoxy-based acrylate resin (3)", and the like. In the general formula (3), It is preferable to use m 値 as 2. Particularly, two resins containing propylene oxo moieties based on an ortho bond in a benzene ring are preferred. The epoxy acrylate resin (3) is, for example, as described below. In the above epoxy resin (1) represented by the formula, (meth) acrylic acid is reacted:

(Wherein R, each independently represents a hydrogen atom or a methyl group, and η each independently represents an integer of 0 to 10 'm is an integer of 2 to 5 each independently represented). Or obtained by reacting propylene oxide (meth) acrylate in a fluorene compound (2) containing a polyfunctional hydroxyl group represented by the following general formula: [Chem. 1 9] -16- 200403269

(Wherein 1 ^ and R2 each independently represent a hydrogen atom or a methyl group, η each independently represents an integer of 0 to 10, and 0 is each independently an integer of 2 to 5). The reaction of the above-mentioned epoxy resin (1) with (meth) acrylic acid, and the reaction of the polyfunctional hydroxyl-containing compound (2) with glycidyl (meth) acrylate, are based on the need to use a suitable solvent in It is performed in a temperature range of 50 to 120 ° C for 5 to 30 hours. The solvents used above are, for example, methylcellosolve acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl-1 -acetate, and other alkylene monoalkane ether acetates; methyl ethyl Ketones such as ketones and methylaryl ketones. Among them, ethylene glycol monomethyl ether acetate and 3-methoxybutyl-1-acetate. The said epoxy acrylate resin (3) has thermosetting property and radiation hardening property. Here, the radiation line is a general term for visible light rays, ultraviolet rays, electron rays, X rays, α rays, / 3 rays, r rays, and the like. Therefore, the resin composition of the epoxy-containing acrylate resin (3) is a function of a thermosetting or radiation-sensitive resin composition. The epoxy-based acrylate resin (3) may be contained alone or in a mixture of two or more kinds in any composition. When the epoxy-containing acrylate resin (3) is a radiation-sensitive resin composition, the composition contains (I) a photopolymerization initiator in addition to the epoxy-based acrylate resin (3), When it is a thermosetting resin composition, (II) a radical initiator may be contained. In addition, these compositions contain (III) in addition to the epoxy acrylate resin described above, and may contain a photo- or thermosetting acrylate compound, (IV) additives, (V) solvents, and the like. The (i) photopolymerization initiator contained in the radiation-sensitive linear resin group 200403269 of the epoxy-group-containing acrylic resin (3) of the present invention has the above-mentioned epoxy-acrylate resin (3) and It is necessary that the photocurable acrylate compound contained above is a compound that starts a photopolymerization effect and / or a compound having a sensitizing effect. The photopolymerization initiator is, for example, the following compounds: acetophenone, 2,2-diethoxyacetophenone, P-dimethylacetophenone, p-dimethylaminopropylacetophenone, dichloride Acetophenones such as acetophenone, trichloroacetophenone, p-th-butylacetophenone; benzophenone, 2-benzophenone chloride, p, p, _bisdimethylamine Benzophenones such as benzyl benzophenone; benzyl ethers such as benzyl, phenylene, phenylmethyl ether, phenyl isopropyl ether, phenyl isobutyl ether; benzyl dimethyl condensation Sulfur compounds such as ketones, thioxanthone, 2-thioxanthone chloride, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone; 2-ethyl Anthraquinones, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3-diphenylanthraquinone, and other anthraquinones; azobisisobutyronitrile, phenylhydrazone peroxide, Organic peroxides such as oxides; and thiol compounds such as 2-sulfobenzimidazole, 2-fluorenylbenzoxazole, and 2-fluorenylbenzothiazole. These compounds can be used singly or in combination of two or more kinds. Moreover, it does not function as a photopolymerization initiator per se, but by using the above-mentioned compounds in combination, a compound that increases the ability of the photopolymerization initiator can be added. When this compound is used in combination with benzophenone, for example, tertiary amines such as triethanolamine are effective. As the (II) radical initiator contained in the thermosetting resin composition, a ketone peroxide-based compound, a difluorenyl peroxide-based compound, a hydrogen peroxide-based compound, and a dialkyl peroxide-based compound can be used. Free radical initiators for compounds, ketal peroxide compounds, alkyl perester compounds, percarbonate compounds, and azobis compounds. In particular, it is suitable to use a difluorenyl peroxide -18-200403269 system or an azobis-based radical initiator. For example, benzamyl peroxide, α, α-azobis (isobutyronitrile) and the like are generally used. The epoxy acrylate resin (3) of the above-mentioned (III) has an external light or thermosetting acrylate compound depending on the necessary physical properties of the composition, and is used as a viscosity modifier or photocrosslinking agent. The specified range contains. The acrylate compound is, for example, a compound having 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like having monovalent hydroxyl groups. Acrylates; and ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate , Tetramethyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol Multi-components of tris (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol (meth) acrylate, etc. ( (Meth) acrylate. These compounds can be used singly or in combination of two or more kinds. The above-mentioned additives (IV) depend on the purpose of use of the composition, and include a thermal polymerization inhibiting agent, an adhesion promoter, a defoaming agent, a surfactant, a plasticizer, and the like. Such medium heat polymerization inhibitors are, for example, hydroquinone, hydroquinone monomethyl ether, pyrrole, 3-butylcatechol, thienol, and the like. The adhesion assistant is added for the purpose of improving the adhesion to the substrate when the liquid composition containing the epoxy-based acrylate resin (3) is applied to the substrate. The adhesion assistant is a silane compound (functional silane coupling agent) having a reactive substituent such as a carboxyl group, a methacryl group, an isocyanate group, an epoxy group, and the like. A specific example of the functional sarane coupling agent is trimethoxy. Methylsilyl-19- 200403269 benzoic acid, methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, 7-isocyanatepropyltriethoxy Silane, glycidoxypropyltrimethoxysilane, yS- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. Examples of the defoaming agent include polysiloxane compounds, fluorine compounds, and acrylic compounds. The surfactant contains the purpose of making it easy to apply the liquid composition and improving the flatness of the obtained coating film. Surfactants include, for example, polysilicone silicon, fluorine-based, and acrylic compounds. Specific examples include B Μ -1 〇〇〇 [made by BM Black Rice (transliteration) company]; Mekafak (Transliteration), F142D, Mekafak F172, Mekafak 173 and Mekafak F1 83 [ Dainippon Ink Chemical Industry Co., Ltd.]; Frontton FC-135, Frontton FC-170C, Frontton FC-4 3 0, and Frontton FC-431 [Sumitomo History Riem (transliteration) (share) system]; Severon S-112, Severon S-113, Severon S-131, Severon S-141 and Severon S -1 4 5 [Asahi Glass Co., Ltd.]; S Η-2 8 PA, S Η -1 9 0, S Η -1 9 3, 3 redundant -603 2, 318428, 00-57 and 0 (: -190 [East Lisi compound (made by Li Si)], etc. Plasticizers such as dibutyl phthalate, dioctyl phosphonate, trimethylamidine, etc. As the solvent of (V), for example, the following solvents are used: alcohols such as methanol and ethanol ; Ethers such as tetrahydrofuran; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, two Ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether Alcohol ethers; methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol methyl ether acetate, 3-methoxybutyl-1-acetate Alkanediol monoalkane ether acetates; Aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, methyl isobutyl ketone, -20- 200403269 methylene acetone, cyclohexanone, 4- Ketones such as 4-methyl-2-pentanone; and ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, and ethyl 2-mercapto-2-methylpropionate Esters, ethyl ethoxyacetate, ethyl glycolate, 2-hydroxy ^ methyl butyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy Esters of methyl propionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, etc. These solvents can be used alone or in combination of two or more. The radiation used when the radiation-sensitive linear resin composition of the present invention is hardened is in the order of the length of the wavelength, such as visible light, ultraviolet rays, electron rays, χ rays, alpha rays, / 3 rays, r rays, etc. among these. Economics and efficiency In terms of practical use, ultraviolet rays are the best radiation. The ultraviolet rays used in the present invention are ultraviolet light emitted by lamps such as low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, arc lamps, metal halide lamps, and xenon lamps. The above-mentioned radiation having a shorter wavelength than ultraviolet rays has high chemical reactivity and is theoretically superior to ultraviolet rays, but ultraviolet rays are more practical in terms of economic efficiency. The composition of the present invention can be a shaped body depending on its purpose. The formed article may be a desired shape formed of a hardened product of the composition itself, or a coating film formed of a hardened product of the composition formed on a substrate. @ For example, a solvent-containing liquid composition is coated on a substrate and dried, and then a radiation film or heat is applied to form a hardened film on the substrate. Or, the above-mentioned radiation-hardenable or thermosetting composition is heated and melted as required, and flows into a predetermined mold 'to obtain a shaped body having a desired shape by irradiation with radiation. The formed body (including the coating film) formed from the composition of the present invention has high hardness, extremely excellent heat resistance, and high refractive index. The buckwheat-containing epoxy acrylate resin (3) has excellent heat resistance, and is known to be easily hardened by heat or radiation. The thermosetting or radiation-sensitive linear composition containing an epoxy-acrylic resin can be used for various applications. Specific examples include various coating agents, and particularly, coating agents requiring high hardness and heat resistance. Or use it as a photoresist ink material for color filters; materials for protective films of electronic parts (such as materials for forming protective films for liquid crystal display elements, integrated circuit elements, solid photographic elements, etc. including color filters); / Or a material for forming a planarizing film; a soldering photoresist used for manufacturing a printed wiring board; or a suitable photosensitive composition for forming a columnar distance adjuster instead of a bead distance adjuster in a liquid crystal display element. In addition, the composition of the present invention is used as a material for various optical parts (lenses, LEDs, plastic films, substrates, optical discs, etc.); a coating agent for forming and protecting the optical part; Etc.); coating agents for manufacturing polarizing plates; raw materials for photosensitive resin compositions for holographic recording. C. Radon-containing alkali-soluble radiation polymerizable unsaturated resin The rhenium-containing alkali-soluble radiation polymerizable unsaturated resin of the present invention is a rhenium-containing epoxy acrylate resin represented by the following general formula (3) : [Chem. 20] Γ ·? / V] 1 \ 0 H2C = C- C- 0- H2C- CH- CH2l · 0-CH- CH24 0 L k2 \ m 0 | CHrai-〇4cH2--CH-CH2- 0 ~ CC «CH2 / 'L 〇HL · One (where R1 and R2 each independently represent a hydrogen atom or a methyl group, n is an integer each independently representing 0 to 10, each is an integer independently representing 2 to 5 ). The polybasic carboxylic acid is a carboxylic acid having several carboxyl groups such as a dicarboxylic acid and a tetracarboxylic acid. The polybasic carboxylic acid or an anhydride thereof is, for example, the following compounds: maleic acid, -22-200403269 itaconic acid Dicarboxylic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, methyl elongation methyltetrahydrophthalic acid, chloro acid, methyltetrahydrophthalic acid, glutaric acid, etc. Acids and their anhydrides; the four residual acids of trimellitic acid or its anhydride, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, and the like Acid dianhydride and so on. Examples of the above-mentioned manganese-based alkali-soluble radiation-polymerizable unsaturated resin are resins represented by the following general formula (4): [Chem. 2 1]

(Wherein 1 ^ and R2 each independently represent a hydrogen atom or a methyl group, Y represents a residue of a dicarboxylic anhydride, η each independently represents an integer of 0 to 10, and nl each independently represents 2 to 5 Integer). The resin represented by the general formula (4) is obtained by reacting a dicarboxylic anhydride represented by the following general formula (5) as a polybasic carboxylic acid anhydride in the epoxy-based acrylic resin (3). [化 22] \ / ° ⑸

CO (where Y is a residue of a dicarboxylic anhydride) The above-mentioned alkali-soluble light-ray polymerizable unsaturated resin containing Jiang is described in this specification as "alkali-soluble alkali-soluble radiation-polymerizable unsaturated containing buckwheat." "Shuyuezhi", "Alkali-soluble radiation polymerizable unsaturated resin", "Radiation-23-200403269 polymerizable unsaturated resin", etc. In the general formula (3), m 値 is preferably 2. In particular, resins containing two ortho-positioned compounds in the benzene ring containing an acrylofluorenyl group are preferred. The light-sensitive resin composition of the buckwheat-soluble soluble radiation-polymerizable unsaturated resin contains the mango-based alkali-soluble radiation-polymerizable unsaturated resin and, if necessary, ( a) Photopolymerization initiator, (b) Polymerizable monomers or oligomers other than the alkali-soluble radiation-polymerizable unsaturated resin containing manganese, (c) Compounds having epoxy groups, (㈨ Additives) (E) Solvent The above (a) photopolymerization initiator refers to a compound having a photopolymerization initiating effect and / or a sensitizing effect. Examples of the compound include the following compounds: acetophenone, 2,2-monomethyl Acetophenones, acetophenone dichloride, acetophenone trichloride, acetophenones such as P-three-butylacetophenone; benzophenone, benzophenone chloride Ketones, p, p'-bisdimethylaminobenzophenones and other benzophenones; benzyl, phenylene, anisole, phenylisopropyl ether, phenylisobutyl ether, etc. Phenyl ethers; benzyldimethylketal, thioxanthone, 2-thioxanthone chloride, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropyl Thioxanthone Substances; 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3-diphenylanthraquinone, and other anthraquinones; azoisobutyronitrile, benzamidine Organic peroxides such as oxides and cumene peroxides; and thiol compounds such as 2-fluorenylbenzimidazole, 2-fluorenylbenzoxazole, and 2-fluorenylbenzothiazole. These compounds may be It can be used alone or in combination of two or more types. In addition, although it does not function as a photopolymerization initiator in itself, it can be added with a compound having the ability to increase the photopolymerization initiator by using it in combination with the above compounds. The compound is, for example, a combination When benzophenone is used, for example, tertiary amines such as triethanolamine having an effect of 24 to 200403269. Polymerizable monomers or oligomers other than the alkali-soluble radiation-polymerizable unsaturated resin containing fluorene of the above (b) The polymer is a monomer or oligomer that can be polymerized by radiation, and can be combined with physical properties depending on the purpose of use of the composition. The monomer or oligomer that is polymerized by radiation is, for example, the following monomer or oligomer Product: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) propylene Monomers having hydroxyl groups such as esters, 3-hydroxypropyl (meth) acrylates; and ethylene glycol di (meth) acrylates, diethylene glycol di (meth) acrylates, and triethylene glycol di (Meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane Tris (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (a) (Meth) acrylates such as acrylic acid esters, glycerol (meth) acrylates, etc. These monomers or oligomers may be used alone or in combination of two or more. These monomers or oligomers It has a function as a viscosity adjusting agent or a photocrosslinking agent, and is contained within a range that does not impair the properties of the resin composition of the present invention. Usually, at least one of the above monomers and oligomers is contained in the composition in an amount of 50 parts by weight or less for 1,000 parts by weight of the alkali-soluble radiation-polymerizable unsaturated resin. When the content of the monomer or oligomer is more than 50 parts by weight, stickiness may occur after pre-baking. (C) The compound having an epoxy group is a polymer or a monomer having at least one epoxy group. Polymers having at least one epoxy group such as phenol novolac lacquer type epoxy resin, cresol novolac lacquer type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type Epoxy Resin, Link-25- 200403269 This type of epoxy resin, alicyclic epoxy resin and other aliphatic epoxy resin. Monomers having at least two epoxy groups such as phenylglycidyl ether, p-butylphenol glycidyl ether, triglycidyl isocyanate, diglycidyl isocyanate, allyl oxapropyl ether, Glycidyl methacrylate and the like. These compounds may be used alone or in combination of two or more. These compounds having an epoxy group are contained within a range that does not impair the properties of the resin composition of the present invention. Generally, 100 parts by weight of the fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin contains 50 parts by weight or less of a compound having an epoxy group. If it is more than 50 parts by weight, the composition containing the component is likely to cause cuts when the composition is hardened, and the adhesiveness is reduced. The above-mentioned additives (d) include a thermal polymerization inhibitor, an adhesion promoter, an epoxy-based hardening accelerator, a surfactant, and an antifoaming agent, etc., and these are contained in the composition in an amount that does not impair the object of the present invention. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrrole, 3-butylcatechol, and thiazol. The said adhesion promoter is contained when it improves the adhesiveness of the composition obtained. The adhesion promoter is preferably a radical compound having a reactive substituent such as a carboxyl group, a methacryl group, an isocyanate group, or an epoxy group (functional silane coupling is complete!}). Specific examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, r-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, r -Isocyanatopropyltriethoxysilane, r-glycidoxypropyltrimethoxysilane, / 3- (3, 'epoxycyclohexyl) ethyltrimethoxysilane, and the like. Examples of the epoxy-based hardening accelerator include amine compounds, imidazole compounds, carboxylic acids, phenols, quaternary ammonium salts, or methylol-containing compounds 200403269. By containing a small amount of an epoxy-based hardening accelerator, various properties such as heat resistance, solvent resistance, acid resistance, plating resistance, adhesion, electrical characteristics, and hardness of the obtained cured film are improved by heating. The surfactant is contained, for example, when the liquid composition is easily coated on a substrate, and thereby the flatness of the obtained film can be improved. Surfactants include, for example, BM-1000 [made by BM Black Rice (Transliteration)]; Mekafak (Transliteration), F142D, Mekafak F172, Mekafak 173, and Mekafak F183 [Danik Ink Chemical Industry Co., Ltd.]; Frontalon FC-135, Floronton FC-170C, Floronton FC-4 3 0, and Floronton FC-431 [Sumitomo Shriem (Transliteration) (share)]; Sefron S-1 12, Sefron S-1 13, Sefron S-131, Sefron S-141 and Sefron S-145 [Asahi Glass (stock) system]; SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57 and DC-190 [Toray Silicon Compound (stock) system] and so on. The antifoaming agent is, for example, a compound of polysiloxane type, fluorine type, acrylic type or the like. The above-mentioned (e) solvent contained in the radiation-sensitive resin composition of the present invention is used for uniformly dissolving each component in the composition, for example, when it is easily coated on a substrate. The solvent does not react with each component in the composition, and any organic solvent that can dissolve or disperse them is not particularly limited. For example, the following compounds: alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, and diethylene glycol monoethyl ether Alcohol ethers such as methyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, etc .; methyl cellosolve acetate, ethyl solvent Cellulose acetates, butyl cellosolve acetates, propylene glycol methyl ether acetate, 3-methoxybutyl-1-acetate, and other alkyl glycol monoalkyl ether acetates 200403269; toluene, xylene And other aromatic hydrocarbons; methyl ethyl ketone, methyl isobutyl ketone, methyl aromatic ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, and other ketones; Ethyl Acetate, 2-Methyl 2-Methylpropionate, 2-Methyl Ethyl Methyl Propionate, Ethyl Ethyl Acetate, Ethyl Glycolate, 2-Methyl_2_Methyl Methyl butyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3. methyl ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, acetic acid Esters of butyl ester, methyl lactate, ethyl lactate, etc. Among these, alcohols, alcohols, glycols, acid acetates, diethylene glycols, ethers, ketones, and esters are preferred, especially ethyl 3-ethoxypropionate and ethyl lactate. Esters, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and methylpentanone are more preferred. These solvents can be used alone or in combination of two or more. The test-soluble radiation-polymerizable unsaturated resin containing the test substance of the present invention is soluble in test-tests and can be hardened by radiation irradiation. The radiation-sensitive resin composition containing the radiation polymerizable unsaturated resin can be formed into a desired shape, and can be used for various purposes by being hardened by radiation. In particular, it is used for the purpose of forming a thin film on a substrate with this composition, and irradiating it with radiation to form a thin film with a desired pattern by development. For example, when a thin film is formed on a substrate for radiation curing and development as described above, the components of the above composition containing a solvent are usually first mixed to obtain a liquid composition. It is preferred that it be filtered through a microporous filter such as a pore size of 1.0 to 0.2 μm to form a homogeneous liquid. Then, the liquid composition was applied on a substrate to obtain a coating film. The coating method includes a dipping method, a spray method, a roll coating method, a gap coating method, a rod coating method, a spin coating method, and the like. In particular, a spin coating method is generally used. In this way, after coating the liquid resin composition at a thickness of ˜ ~ 3 〇 # m -28- 200403269, the solvent is removed to form a thin film. Usually, in order to sufficiently remove the solvent, a pre-baking treatment is performed. The thin film of the substrate is loaded with a mask having a desired pattern, and then irradiated with radiation. The radiation used is in the order of the length of the wavelength, such as visible light, ultraviolet rays, electron rays, x-rays, ^ rays, Θ rays,? , Line, etc. 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 lamps such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, an arc lamp, a metal halide lamp, and a xenon lamp are used. The above-mentioned radiation 'having a shorter wavelength than ultraviolet rays has high chemical reactivity and is theoretically superior to ultraviolet rays, but ultraviolet rays are more practical in terms of economy. By the above irradiation, the exposed portion is hardened by the polymerization reaction, and the unexposed portion is developed with a developing solution. Thereby, the unirradiated portion of the radiation is removed, and a film having a desired pattern is obtained. The developing method is, for example, a liquid holding method, a dipping method, a shaking dipping method, or the like. The above-mentioned developing solution is, for example, an alkaline aqueous solution, a mixed solution of the alkaline aqueous solution and a water-soluble organic solvent and / or a surfactant, and an organic solvent in which the composition of the present invention is dissolved, preferably an alkaline aqueous solution and a surfactant Mixed liquid. The alkali used for the alkaline aqueous solution used for developing the radiation-sensitive linear resin composition of the present invention is prepared by using, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium methylsilicate, ammonium, ethylamine, n- Propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, Piperidine, 1,8-diazidebicyclo (5.4.0) -7-undecene, 1,5-diazidebicyclo (4.3.0) -5-nonene, preferably sodium carbonate , Tetramethylammonium hydroxide and so on. 200403269 describes water-soluble organic solvents such as methanol, ethanol, acetone, and the like. To this test aqueous solution, water-soluble organic solvents such as methanol, ethanol, propanol, and ethylene glycol, surfactants, etc. are added in an appropriate amount as needed. The development of the resin composition of the present invention is usually performed at a temperature of 10 to 5 ° C., preferably 20 to 40 ° C., using a commercially available developing machine or an ultrasonic washing machine. When the alkali resistance is improved, it is better to heat and apply an epoxy hardening treatment (post-baking treatment). The heat treatment in the resin composition of the present invention can not only significantly improve the durability against strong alkaline water, but also improve the resistance to alkaline water. Various properties such as the adhesion, heat resistance, and surface hardness of metals such as ketones or glass. The heating temperature and heating time for the heat hardening conditions, for example, 80 to 250 ° C, 10 to 120 minutes. Preferred heating The temperature is 100 ~ 200 ° C. In this way, a hardened film having a desired pattern can be prepared. The hardened film obtained by hardening the composition of the present invention has heat resistance, transparency, adhesion to a substrate, acid resistance, Excellent alkali resistance, chemical resistance, solvent resistance, surface hardness, etc. In addition, the cured film is an organic coating film and has a low dielectric constant. Therefore, the composition of the present invention can be used, for example, as a suitable electronic component. Material for protective film Materials for forming protective films such as color filters, liquid crystal display elements, integrated circuit elements, solid-state imaging elements, etc.); materials for forming interlayer insulating films and / or flattening films; adhesives for color resistors; manufacturing and printing Welding photoresist used in wiring boards; or alkali-soluble type photosensitive composition that forms bead pitch adjusters instead of bead pitch adjusters for liquid crystal display elements. In addition, the composition of the present invention is used as various optical parts ( Materials for lenses, LEDs, plastic films, substrates, optical discs, etc .; coatings for the protection of optical parts; adhesives for optical parts (adhesives for optical fibers, etc.); coatings for polarizing plate manufacturing; holograms Photosensitive -30-200403269 raw material for recording resin composition, etc. [Examples] The present invention will be specifically described below based on examples. Example 1 (Synthesis of Epoxy Resin) 150 g of the following formula (2.a) The polyfunctional hydroxyl-containing fluorene compound (n = 0, m: z2 in the above general formula (2)) was dissolved in 700 g of epichlorohydrin, and 1.8 g of benzyltriene was added. Ethylammonium chloride Then, it was stirred for 5 hours. Then, 165 g of a sodium hydroxide aqueous solution was added dropwise under reduced pressure (150 mmHg) and 70 ° C. for 3 hours. During this time, the generated water was azeotroped by epichlorohydrin After removing the system, the distilled epichlorohydrin was returned to the system. After dripping, the reaction was continued for 30 minutes. Then, the salt generated by filtration was taken out, washed with water and distilled to remove the epichlorohydrin. 220 grams of epoxy resin (1. a) was obtained. The epoxy equivalent of the resin was 200 g / eq. [化 2 3]

OH OH

-31- 200403269 The obtained epoxy resin was refined by fractionating GPC, and the structure analysis of the obtained purified epoxy resin was performed. The results are described below. 1 Η ~ N M R is shown in Figure 1. [1] Melting point: 5 8 · 7 ° C (by DSC) [2] W-NMR (solvent: DMS 0-d6, internal standard: TMS) peak δ, ppma, a '2.4-2.9 8H b, b' 3.0-3.2 4H c, c '3.6-4.4 8H d, e, f 6.4-6.9 6H g, h, i 7.2-7.9 8H [3] MS m / n = 606 (m +) Example 1 (using epoxy-containing Preparation and evaluation of a molded article of a thermosetting resin composition of a resin) 100 parts by weight of an epoxy resin (1. a) obtained in Example 1 and 760 parts by weight of a methyl hexahydrophthalic anhydride type hardener (Nippon Physico Chemical) 1 part by weight of 2-ethyl "4-methylimidazole (2E4MZ) as a catalyst was mixed into a mixture of Rika Sidon (translated) MH-700 made by the company, and the resulting mixture was charged into 100%. In a stainless steel mold with a thickness of 1 mm × 100 mm and a thickness of 1 mm, it was heated in an oven at 1 ο ° C for 1 hour, and then heated at 180 ° C for 4 hours to heat-harden. Using the obtained formed body (test piece), The following items were evaluated. [1] Heat resistance: Tg was measured by DSC (manufactured by Seiko Electronics Co., Ltd. DSC210) 200403269 [2] Dielectric constant and dielectric tangent: TR-1 100 Electric body loss Measured by a dynamic measuring device (Ando Electric Co., Ltd.). [3] Elasticity: Using a dynamic viscoelasticity measuring device DMS 6100 (manufactured by Seiko Denshi Kogyo Co., Ltd.) in a temperature range of 50 to 25 0 ° C, two The side bend type measurement has a response when the sine wave is 1 Hz, and the storage elastic modulus E is obtained. The composition of the composition used in this example is shown in Table 1, and the evaluation result of the obtained test piece is shown in Table 2. The following Example 3 and Comparative Example 1 are shown in Tables 1 and 2. Example 3 Except changing 100 parts by weight of epoxy resin (1.a) to 40 parts by weight of epoxy resin (1.a) and 60 parts by weight of double A test piece was prepared and evaluated in the same manner as in Example 2 except that a mixture of a phenol A type epoxy resin (AER-260 manufactured by Asahi Kasei Epoxy Co., Ltd.) was used, and a methylhexahydrophthalic anhydride type hardener was changed to 77 parts by weight. Comparative Example 1 100 parts by weight of a bisphenol A type epoxy resin (manufactured by Asahi Kasei Epoxy Co., Ltd .: AER-260) and 79 parts by weight of a phenol novolac resin type hardener (manufactured by Dainippon Ink Chemical Industry Co., Ltd.) TD-21 31), 1 part by weight of triphenylphosphine (TPP) as a catalyst is mixed, The obtained mixture was poured into a mold made of stainless steel, heated in an oven at 100 ° C for 1 hour, and then heated at 180 ° C for 4 hours, and then heat-cured. The obtained formed body (test piece) and the test piece of Example 2 were used. Perform the same assessment. -33- 200403269 Table 1 Composition (parts by weight) Epoxy resin (la) AER-260 Ricciton MH-700 Phenol novolak resin type hardener 2E4MZ TPP Example 2 100 — 76 — 1 _ Example 3 40 60 77-1 1 _ Comparative Example 1 — 100 — 79 — 1. Table 2

Tgfc) Dielectric constant Dielectric tangent storage elasticity E, (25 ° C) Example 2 201 2.90 0.0133 3,200Mpa Example 3 165 3.00 0.0201 3,200Mpa Comparative Example 1 107 3.45 0.0267 2,900Mpa Example 4

(Film and evaluation using a thermosetting resin composition containing an epoxy resin) 30 parts by weight of the epoxy resin (1 · a) obtained in Example 1 was dissolved in 70 parts by weight of glycerol monomethyl ether acetate (PG M EA), 3 parts by weight of a catalyst Sayaton (transliteration) SI-60 (made by Sanxin Chemical Industry Co., Ltd.) was mixed. Then, the obtained mixture was coated on a glass substrate using a spinner, and baked on a hot plate of 90 seconds for 120 seconds to obtain a coating film having a film thickness of about 2 // m. It was then post-baked in an oven at 240 C for 1 hour to heat harden. The obtained thermosetting film was evaluated for the following items. (1) Refractive index: Regarding the obtained thermosetting film, the refractive index of 6 3 2.8 n m was measured with an optical interference film quality measurement base. -34- 200403269 (2) Light transmittance: For the heat-cured film obtained above, the spectral transmittance of the visible light range was measured with Hitachi spectrophotometer U-2000. (3) Abrasion resistance (scratch resistance): The surface of the heat-cured film on the substrate is gently pressed with a # 1 00 steel wire, and the steel wire is rubbed back and forth 30 times, and the coating film is judged according to the following criteria The degree of abrasion on the surface to evaluate the abrasion resistance. 〇: No scratches △: There are scratches, but gloss can be maintained. X: There are countless scratches, which impair the gloss. (4) Adhesiveness: Based on JIS 1 5 5 2 and evaluated by grid peel test. (5) Pencil hardness: Measure the pencil hardness based on the] IS-K-5 400. (6) Film shrinkage rate = find the change rate of film thickness before and after baking [(film thickness before post-baking-after @ 考 后 的 膜厚) / (film thickness before post-baking)] X 100 copies The composition of the composition used in the examples is shown in Table 3, and the evaluation of the obtained thin month molybdenum is shown in Table 4. The following Example 5 and Comparative Example 2 are shown in Table 3 and $ ^. Example 5 Except changing 30 parts by weight of epoxy resin (1.a) to 12 parts by weight of epoxy resin (1a and 18 parts by weight of bisphenol A-type epoxy resin (Dai Nihon Ink Chemical Industry Co., Ltd.) A Picuron (transliteration) 8 60) mixture was prepared under the same {| conditions as in Example 4 to make a hardened film and evaluated. 200403269 Comparative Example 2 Except that epoxy resin (1. a) was changed to bisphenol A Type epoxy resin (Yepikolong 8 60 manufactured by Dainippon Ink Chemical Industry Co., Ltd.), and a cured film was prepared under the same conditions as in Example 4 and evaluated. Table 3 Composition (parts by weight) Epoxy resin ( la) Yepicron 860 PGMEA Thayerton SI-60 Example 4 30 — 70 3 Example 5 12 18 70 3 Comparative Example 2 — 30 70 3 Table 4 Refractive index light transmittance friction resistance adhesive pencil hardness film Shrinkage (400nm) (%) Example 4 1.621 96.9 〇100 / 100 4H 1.5 Example 5 1.601 96.1 Δ 100/100 3H 2.3 Comparative Example 2 1.578 93.0 X 100/100 2B 3.5

Example 6 (Synthesis of epoxy acrylate resin) In a 300 ml four-necked flask, 230 grams (epoxy equivalent 200 g / eq) of the epoxy resin (1.a) obtained in Example 1, 600 mg of triethylbenzyl chloride, 56 mg of 2,6-diisobutylphenol, and 83 g of acrylic acid were blown into the air at a rate of 10 mL / min and dissolved by heating at 90 to 10 CTC. Then, slowly raise it to 120 ° C. Continue stirring until the solution is clear and thick. During the measurement of the acid value, heating and stirring were continued until 1.0 mg of KOH / g. It takes 15 hours until -36- 200403269 acid value reaches the target. A light yellow transparent, solid, polyfunctional epoxy acrylate resin (3. a) was prepared. [Chemical 25]

(3.a) Example 7 (Preparation and evaluation of cured film of photocurable resin composition using epoxy acrylate resin) 100 parts by weight of epoxy acrylate resin obtained in Example 6 (3. a), and 3 parts by weight of Ilukachia 907 was dissolved in PGMEA as a solvent to make a 30% strength solution. The epoxy-based acrylate resin-containing solution was coated on a glass substrate using a spinner, and pre-baked on a hot plate at 90 ° C for 120 seconds to obtain a coating film having a thickness of about 2 // m. Then, a high-pressure mercury lamp was irradiated with light of 300 m] / cm2 to harden the coating film. The surface characteristics of the obtained cured coating film were evaluated by the same test method as in Example 4. The composition of the composition used in this example is shown in Table 5, and the evaluation result of the obtained cured film is shown in Table 6. The following Example 8 and Comparative Example 3 are shown in Table 5 and Table 6. Example 8 Except that 100 parts by weight of the epoxy acrylate resin (3. a) of Example 7 was changed to 60 parts by weight of the epoxy acrylate Except for a mixture of the resin (3.a) and 40 parts by weight of dipentaerythritol hexaacrylate (DPHA), a film was prepared under the same conditions of -37-200403269 as in Example 7 and evaluated. Comparative Example 3 A film was formed and evaluated under the same conditions as in Example 7, except that the epoxy acrylate resin (3. "" was changed to a bisphenol a epoxy acrylate resin in Example 7). 5 Epoxy acrylate (3.a) DPHA Bisphenol A epoxy acrylate resin Lukachia 907 Example 7 100 — One 3 Example 8 60 40 _ 3 Comparative Example 3 One 100 3 Table 6 Scratch resistance Refractive index pencil hardness Adhesion Light transmittance (400nm) Film shrinkage Example 7 〇1.583 5H 100/100 97.0 8.6 Example 8 〇1.570 4H 100/100 96.9 10.0 Comparative Example 3 X 1.558 HB 100/100 95.0 32.4 Example 9 (Examination of Synthesis of Soluble Radiation Polymerizable Unsaturated Resin) 46 grams of propylene glycol monomethyl ether acetate was added to 56 grams of epoxy acrylate resin (3.a) prepared in Example 7. (PGMEA) After dissolving, 31 g of tetrahydrophthalic anhydride (TPA) and 0.1 g of tetraethylammonium bromide were mixed. The temperature was gradually increased, and the reaction was performed at 110 to 115 ° C for 6 hours. Preparation of alkali-soluble radiation polymerizable unsaturated resin (4.a) lipid PGMEA solution (light yellow transparent liquid The acid anhydride confirmed by the IR spectrum disappeared. -38-200403269 of [26]

Example 10 (Synthesis of alkali-soluble radiation-polymerizable unsaturated resin) To 56 grams of epoxy acrylate resin (3.a) prepared in Example 6 was added 51 grams of propylene glycol monomethyl ether ethyl. After dissolving the acid ester (pgmE), 9.8 g of biphenyltetracarboxylic acid (B PDA) and 0.1 g of tetraethylammonium were mixed to slowly increase the temperature, and the reaction was performed at 1 1 0 to 1 15 ° C 1 2 hours. Then, 4.7 g of tetrahydrophthalic anhydride (THPA) was added to the above reactant, and the reaction was performed at 90 ° C to 95 ° C for 4 hours. In this way, a PGMEA solution of an alkali-soluble radiation-polymerizable unsaturated resin was prepared. The disappearance of the acid anhydride was confirmed by IR spectrum. Example 11 1 (Preparation and evaluation of a thin film using a composition containing an alkali-soluble radiation-polymerizable unsaturated resin) The alkali-soluble radiation-polymerizable property obtained in Example 9 with a solid content of 30 parts by weight An unsaturated resin (4.a), 15 parts by weight of dipentaerythritol hexaacrylate (DPHA), and 3 parts of Eucalyptus 907 were dissolved in PGMEA as a solvent to prepare a solution having a concentration of 30% by weight. This solution was applied on a glass substrate using a spinner 'and pre-baked on a hot plate at 90 ° C for 12Q seconds to form a coating film having a thickness of about m -39-200403269. A mask with a predetermined pattern is placed on the coating film surface of the glass substrate having the coating film, and a 250W high-pressure mercury lamp is used under a nitrogen atmosphere, and ultraviolet rays with a wavelength of 4.05 nm and a light intensity of 9.5 mW / cm2 are irradiated with an energy of 1,000 mJ / cm2 . Then, a 1% by weight sodium carbonate aqueous solution was used at 25 ° C for 30 seconds to remove the unexposed portion of the coating film. Secondly, it was washed with ultrapure water. The obtained substrate with a thin film was placed in an oven at 200 ° C and subjected to a post-baking treatment for 30 minutes to heat harden the thin film (hereinafter, this hardened film is referred to as a heat hardened film). The evaluation of the heat-cured film prepared in this example, that is, the evaluation of the obtained cured film was performed using the items shown below. < 1> Dryness of the coating film The dryness of the pre-baked coating film was evaluated based on JIS-K-5400. The comparison of the evaluation is as follows. 〇: No sticky feeling at all △: Slightly sticky feel X: Significant sticky feel < 2 > The developability to an alkaline aqueous solution makes the above-mentioned glass substrate with a coating film immersed in the film without exposure treatment Imaging was performed in a 1% by weight sodium carbonate aqueous solution for 30 seconds. The glass substrate after development was visually evaluated to increase the residual resin by 50 times. The comparison of evaluation is as follows. 〇: Good developability (no resin residue on glass at all) △: Poor developability (some resin residue on glass) x: Poor developability (a lot of resin remains on glass) < 3 & gt Exposure Sensitivity -40- 200403269 The step-by-step tabulation machine (negative mask with optical density of 12 steps) as a photomask is brought into close contact with the coating film for exposure and development. Then, observe the number of remaining tabulating machine segments (the more the number of remaining segments in the δ-level estimation system sensitivity). < 4 > The highest hardness of the heat-hardened film obtained based on the hardness of the coating film. The hardness is based on the test method of JZ s Κ-5 4 0 0, using a pencil hardness tester, and the coating film has no scratches at a load of 9.8 N. Means. The pencil used is "Mitsubishi High Quality". < 5 > Adhesion to the substrate A cross cut of at least 100 squares was placed on the obtained heat-cured film, and then a peeling test was performed using a glass tape (registered trademark), and the magnification was evaluated with an optical microscope and 50 times Detachment of chessboard. The comparison of evaluation is as follows. 〇: No peeling at all X: Some peeling < 6 > Heat resistance The obtained heat-cured film was placed in an oven at 250 ° C for 3 hours and hardened. The change rate of the film thickness before and after hardening [(film thickness before hardening-film thickness after hardening) / (film thickness before hardening)] x 1 〇 is calculated. The comparison of evaluation is as follows. 〇: Very low change rate of film thickness (less than 5% change in film thickness) △: Low change rate of film thickness (5% to 10% change in film thickness) X: High change rate (film change rate) (10% or more) < 7 > Chemical resistance The resulting substrate having a heat-curable film was immersed in the following chemicals under the following conditions. -41-200403269 (i) Acid solution: immersed in 5% by weight HCL aqueous solution for 24 hours (ii) Alkaline solution: ii-1: immersed in 5% by weight NaOH solution at room temperature for 24 hours ii-2 : Immersed in 4% by weight KOH aqueous solution at 50 ° C for 10 minutes ii-3: immersed in 1% by weight NaOH aqueous solution at 80 ° C for 5 minutes (iii) solvent: ni-l: at N-methylpyrrolidone, immersed at 40 ° C for 1 minute Ui-2: Film thickness change rate before and after immersion at N-methylpyrrolidone, 80 ° C for 5 minutes ((film thickness before immersion-film thickness after immersion) ) / (Film thickness before dipping)) X 100. Based on the obtained film thickness change rate, the chemical resistance was evaluated. The evaluation criteria are as follows. 〇: Excellent chemical resistance (less than 5% change in film thickness of all solutions) △: Slightly better chemical resistance (5 to 10% change in film thickness of any solution) X: Inferior chemical resistance (any solution The film thickness change rate is 10% or more.) The results are shown in Table 7. The results of the following Examples 12 to 14 and Comparative Example 4 are also shown in Table 7. Example 12 A thin film was prepared and evaluated under the same conditions as in Example 11 except that dipentaerythritol hexapropionate was changed to trimethylolpropane triacrylate (TMPTA). Example 1 3 Except for using a composition containing 6 parts by weight of a tetramethylbiphenyl type epoxy resin (Yepicton (YX-4 0 0 0) manufactured by Japan Epoxy Resin Co., Ltd.) Example 11 A thin film was prepared under the same conditions and evaluated. Example 1 4 -42- 200403269 Except that the alkali-soluble radiation-polymerizable unsaturated resin (4.a) was changed to the test-soluble radiation-polymerizable unsaturated resin obtained in Example 10. Films were produced under the same conditions and evaluated. Comparative Example 4 In Example 11, except that the alkali-soluble radiation-polymerizable unsaturated resin (4 · a) was changed to a bisphenol A-type photopolymerizable unsaturated resin represented by the following formula, Example 11 A thin film was produced and evaluated under the same conditions. [Chemical 27]

(Where η is about 5) Table 7

Coating film dryness, developability, exposure sensitivity, coating film hardness, adhesion, heat resistance, solvent resistance, Example 11 009, 5 〇 〇 Example 12 〇 〇 8 4 〇 〇 Example 13 〇 〇 5 〇 〇〇 Example M 〇09 5Η 〇〇Comparative Example 4 〇〇2 2 〇XX From the results of Tables 1 to 7, it can be seen that when using the rhenium-containing resin of the present invention, high hardness, high transparency, and a high level of quality can be obtained. Molded body and hardened film with low heat shrinkage and heat resistance and electrical characteristics. In addition, when the soluble radiation-polymerizable unsaturated resin of the present invention is used, a thin film having the above-mentioned superiority of the desired pattern can be formed on the substrate with good accuracy by exposure and development on the substrate. [Effects of the Invention] The present invention can provide a novel manganese-containing epoxy resin, manganese-containing epoxy acrylate resin, and manganese-containing soluble radiation-polymerizable unsaturated resin, and the like. Simple method. These resins can be polymerized and hardened by heat or radiation. A hardened shape or film obtained by using such a resin composition has high hardness, high transparency, high level of heat resistance and electrical characteristics, and has a small degree of hardening shrinkage. In addition, when the alkali-soluble radiation-polymerizable unsaturated resin of the present invention is used, a thin film having the above-mentioned excellent properties with a desired pattern is formed on a substrate with good accuracy. Therefore, the tree or resin composition of the present invention can be used as a protective film forming material for various electronic parts (including a liquid crystal display element of a color filter, an integrated circuit element, a solid-state imaging element, etc.); a forming material of an interlayer insulating film 4. Adhesive composition for color resistors; soldering etchant used in the manufacture of printed wiring boards; materials for optical components.

-44- 200403269 (V) Brief description of the diagrams Figure 1 is a 1H-NMR chart of the buckwheat-containing epoxy resin of the present invention.

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Claims (1)

200403269 6. Scope of patent application: 1 · A manganese-containing epoxy resin, which is characterized by the following general formula (1) (Wherein Ri represents each independently a hydrogen atom or a methyl group, η represents each independently an integer of 0 to 10, and m represents each independently an integer of 2 to 5). 2. The fluorene-containing epoxy resin according to item 1 of the scope of patent application, wherein m = 2 in the general formula (丄). 3. A method for manufacturing a fluorene-containing epoxy resin as described in the first item of the patent application, which is characterized by including a step of reacting epichlorohydrin in a polyfunctional hydroxy-containing compound represented by the following general formula (2) , ⑵ (Where I represents each independently a hydrogen atom or a methyl group, η represents each independently an integer of 0 to 10, and m represents each independently an integer of 2 to 5). 4. The method of claim 3, wherein m = 2 in the general formula (2). 5. An epoxy resin composition, characterized in that it contains a mango-containing epoxy resin as defined in item 1 or 2 of the scope of patent application. 6. A shaped article, characterized by being obtained by hardening the rhenium-containing epoxy resin composition according to item 5 of the patent application. 7. —An epoxy acrylate resin containing buckwheat, which is characterized by the following general formula (3), -46-200403269 (Wherein h and R2 each independently represent a hydrogen atom or a methyl group, and η each independently represent an integer of 0 to 0 and 0 each independently represent an integer of 2 to 5). 8. The epoxy acrylate resin according to item 7 of the patent application scope, wherein m = 2 in the general formula (3). 9. A method for manufacturing an epoxy acrylate resin according to item 7 of the scope of patent application, characterized in that it comprises a step of causing (meth) acrylic acid to act in the epoxy containing epoxy resin represented by the following general formula (1) , (1) (Wherein R i each independently represents a hydrogen atom or a methyl group, n is each independently an integer of 0 to 10, and m is each independently an integer of 2 to 5). 10. A method as claimed in item 9 of the scope of patent application, wherein m = 2 0 1 1 in the general formula (3) of the epoxy resin. A method for producing an epoxy acrylate resin as described in item 7 of the scope of patent application, which It is characterized in that it comprises a step of reacting glycidyl (meth) acrylate in a buckwheat compound containing a polyfunctional hydroxyl group represented by the following general formula (2), -47- 200403269 (Wherein R] each independently represents a hydrogen atom or a methyl group, η each independently represents an integer of 0 to 10, and m is each independently an integer of 2 to 5). 1 2 · The method according to item 11 of the scope of patent application, wherein m = 2 in the general formula (3) of the polyfunctional hydroxyl-containing funeral compound. 1 3-A thermosetting composition, which is characterized by containing a fluorene-containing epoxy acrylate resin such as item 7 or 8 of the patent application park. 1 4 · A radiation-sensitive linear resin composition, characterized in that it contains an epoxy acrylate resin containing mangoes such as those in the scope of patent application No. 7 or 8. 15. A shaped body, characterized by hardening the composition as described in the scope of claims 13 or 14 of the patent application. 16. A kind of alkali-soluble radiation-polymerizable unsaturated resin containing manganese, which is characterized in that a polybasic carboxylic acid or Those obtained by the acid anhydride reaction, (3) (Wherein 1 and R2 each independently represent a hydrogen atom or a methyl group, η each independently represents an integer of 0 to 10, and m each independently represents an integer of 2 to 5). i 7. The thorium-containing alkali-soluble radiation-polymerizable unsaturated resin according to item 16 of the patent application scope, wherein m = 2 in the general formula (3). 1 8. A method for producing an alkali-soluble radiation-polymerizable unsaturated resin containing manganese, which is characterized in that it contains polybasic carboxyl group in an fluorene-containing epoxy acrylate resin represented by the following general formula (3) Step of acid or its anhydride reaction, -48- 200403269 (Wherein I and R2 each independently represent a hydrogen atom or a methyl group, η each independently represents an integer of 0 to 10, and m is each independently an integer of 2 to 5). 19. The method according to item 18 of the scope of patent application, wherein m = 2 in the general formula (3) of the epoxy acrylate resin. 2 0. A radiation-sensitive linear resin composition, which is characterized by containing a catenary-base-soluble radiation-polymerizable unsaturated resin such as those in the scope of claims 16 or 17.