JP2005325331A - New fluorene-containing resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting or radiation curable functional epoxy resin that is suitable to use as a protective coating material for various electronic parts, as a material for forming an interlayer insulation film, as a binder composition for color resist, etc., and whose cured products have a high hardness, a high level of heat resistance and electric property and a low rate of shrinkage in a curing process and that is excellent in a patterning property. <P>SOLUTION: A specially designed epoxy resin having a fluorene skeleton, an epoxy resin acrylate and a fluorene-containing alkali soluble-type radiation curable unsaturated resin are provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel fluorene-containing epoxy resin having heat and radiation curability, a fluorene-containing epoxy acrylate resin, a fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin, a method for producing the resin, and thermosetting including the resin Or a radiation curable resin composition. Furthermore, this invention relates to the molded object which is excellent in heat resistance and an electrical property obtained using this resin composition, and has high hardness. The present invention further relates to a radiation-sensitive resin composition comprising the above alkali-soluble radiation-polymerizable unsaturated resin, which is an interlayer insulating film or a protective film (for example, a color filter, a liquid crystal display) in a liquid crystal display or an electronic component. The present invention relates to a composition useful for preparing an interlayer insulating film and a protective film used for an element, an integrated circuit element, a solid-state imaging element and the like.

  Generally, an epoxy resin is cured with various curing agents to form a cured product having excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, and the like. Therefore, it is used in a wide range of fields such as adhesives, paints, laminates, molding materials and casting materials. Conventionally, there are liquid and solid bisphenol A type epoxy resins as epoxy resins most used industrially. Conventionally, epoxy acrylate resins have been widely used as epoxy-based functional polymer materials. This resin is used, for example, in the field of photosensitive materials (Non-Patent Document 1), but these resins have insufficient heat resistance, electrical properties, and hardness, and require a high level of heat resistance. It is insufficient in the field. In order to solve these problems, epoxy resins and epoxy acrylate resins having a fluorene skeleton have been introduced (Patent Documents 1 and 2). In these patent documents, epoxy resins and epoxy acrylate resins having a bisphenolfluorene type skeleton are introduced, and these resins have improved heat resistance and electrical characteristics.

  However, in recent applications in the electric / electronic field, higher levels of heat resistance and electrical characteristics are required. In addition, a high-purity epoxy resin having a bisphenolfluorene-type skeleton has a high melting point, poor compatibility with various curing agents, solvents and the like, and lacks handling properties. By synthesizing an epoxy resin having a high molecular weight type bisphenolfluorene type skeleton, the melting point can be lowered and compatibility with various curing agents and solvents can be improved. However, a high molecular weight type bisphenolfluorene type can be obtained. An epoxy resin having a skeleton has a very high melt viscosity. For this reason, in the production of an epoxy resin having a bisphenolfluorene type skeleton, it is necessary to use a large amount of solvent or keep the process temperature high, which is disadvantageous in terms of cost. In addition, due to the properties of poor compatibility and high melt viscosity, when an epoxy resin composition is used, the amount of fluorene compound that can be added to the composition is limited, and the characteristics of the fluorene compound can be fully utilized. It may be difficult or there may be restrictions on the conditions of the modification reaction using these epoxy resins.

Akio Yamaoka and Hiroshi Morita "Photosensitive resin", Kyoritsu Shuppan, first published in March 1988, pp. 82-84 JP 63-218725 A JP 7-48424 A

  The object of the present invention is to solve the above-mentioned conventional problems. The object of the present invention is that the cured product has high hardness, heat resistance and electrical properties at a high level, and shrinkage upon curing. The object is to provide a thermosetting or radiation curable functional epoxy resin having a low rate and excellent patternability. Another object of the present invention is to provide a method for producing the resin and a composition containing the resin. Still another object of the present invention is to provide a molded article obtained by curing such a resin composition. Furthermore, compared to conventional fluorene compounds, the present invention provides low-cost fluorene compounds that are highly compatible with solvents and the like and have good handling properties, and broaden the application range of these fluorene compounds.

  The fluorene-containing epoxy resin of the present invention is represented by the following general formula (1):

(Wherein, n is an integer from 0 to 10).

  The production method of the fluorene-containing epoxy resin of the present invention is represented by the following general formula (2):

And a method comprising the step of allowing epichlorohydrin to act on the fluorene compound represented by formula (1).

The epoxy resin composition of the present invention relates to a composition containing a fluorene-containing epoxy resin.

The present invention relates to a molded article obtained by curing the epoxy resin composition described above.

  The fluorene-containing epoxy acrylate resin of the present invention has the following general formula (3):

(Wherein R ₁ and R ₂ are each independently a hydrogen atom or a methyl group, and n is each independently an integer of 0 to 10).

  The 1st manufacturing method of the fluorene containing epoxy acrylate resin of this invention is following General formula (1):

It is related with the method including the process of making (meth) acrylic acid act on the fluorene containing epoxy resin shown by (In formula, n is an integer of 0-10).

  The second production method of the fluorene-containing epoxy acrylate resin of the present invention is represented by the following general formula (2):

It relates to a method comprising the step of allowing glycidyl (meth) acrylate to act on the fluorene compound represented by formula (1).

  The present invention relates to a thermosetting composition containing the fluorene-containing epoxy acrylate resin described above.

  The present invention relates to a radiation-sensitive resin composition containing any one of the above fluorene-containing epoxy acrylate resins.

  The present invention relates to a molded product obtained by curing the thermosetting composition or the radiation-sensitive resin composition.

  The fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin (A) of the present invention has the following general formula (3):

(Wherein R ₁ and R ₂ are each independently a hydrogen atom or a methyl group, and n is each independently an integer of 0 to 10), a polybasic carboxylic acid or The present invention relates to a resin obtained by reacting the anhydride.

  The production method of the fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin (A) of the present invention is represented by the following general formula (3):

(Wherein R ₁ and R ₂ are each independently a hydrogen atom or a methyl group, and n is each independently an integer of 0 to 10), a polybasic carboxylic acid or It relates to a method comprising the step of reacting the anhydride.

  The fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin (B) of the present invention has the following general formula (3):

(Wherein R ₁ and R ₂ are each independently a hydrogen atom or a methyl group, and n is each independently an integer of 0 to 10), and a mixture of a polyhydric alcohol and a fluorene-containing epoxy acrylate resin And a resin obtained by reacting a polybasic carboxylic acid or an anhydride thereof.

As a preferred embodiment, the following general formula (3):

(Wherein, R ₁ and R ₂ are each independently a hydrogen atom or a methyl group, and n is each independently an integer of 0 to 10) and a hydroxyl group of a fluorene-containing epoxy acrylate resin and a hydroxyl group of a polyhydric alcohol The fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin described above, wherein the molar ratio is 99/1 to 50/50.

In a preferred embodiment, the polyhydric alcohol is one or more polyhydric alcohols selected from trimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol and dipentaerythritol. The fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin described above.

  The production method of the fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin (B) of the present invention is represented by the following general formula (3):

(Wherein R ₁ and R ₂ are each independently a hydrogen atom or a methyl group, and n is each independently an integer of 0 to 10), and a mixture of a polyhydric alcohol and a fluorene-containing epoxy acrylate resin And a method comprising reacting a polybasic carboxylic acid or an anhydride thereof.

  The present invention relates to a radiation-sensitive resin composition containing the fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin (A) or (B) described above.

  The present invention relates to an interlayer insulating film of a liquid crystal display formed by the radiation sensitive resin composition described above.

  The present invention relates to a protective film for a liquid crystal display formed by the radiation sensitive resin composition described above.

    According to the present invention, a novel fluorene-containing epoxy resin, a fluorene-containing epoxy acrylate resin, a fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin, and a simple production method thereof are thus provided. These resins can be polymerized and cured by heat or radiation. A cured molded article or thin film obtained using a resin composition containing these has high hardness, high transparency, high level of heat resistance and electrical characteristics, and low degree of curing shrinkage. Furthermore, when the alkali-soluble radiation-polymerizable unsaturated resin of the present invention is used, a thin film having a desired pattern and having the above-mentioned excellent properties can be accurately formed on a substrate. In particular, when the alkali-soluble radiation-polymerizable unsaturated resin of the present invention to which a polyhydric alcohol is added, the heat discoloration is further improved. Therefore, the resin or resin composition of the present invention is used for a protective film forming material for liquid crystal displays, electronic components, etc. (color filters, liquid crystal display elements, integrated circuit elements, solid-state imaging elements, etc.); interlayer insulating film forming materials, color resists Binder composition; Solder resist used in the production of a printed wiring board; Coating agent;

A. Fluorene-containing epoxy resin The fluorene-containing epoxy resin of the present invention is represented by the following general formula (1):

Here, n is an integer from 0 to 10.

  This fluorene-containing epoxy resin may be described as “fluorene-containing epoxy resin (1)”, “epoxy resin (1)”, or the like in this specification.

  The epoxy resin (1) is obtained, for example, by allowing epichlorohydrin to act on a fluorene compound represented by the following general formula (2):

  This fluorene compound may be described as “fluorene compound (2)” in the present specification.

  This fluorene compound (2) can be prepared by methods known in the art. For example, it can be prepared by the method described in JP2003-221352A.

  The reaction between the fluorene compound (2) and epichlorohydrin is usually performed in a temperature range of 50 to 120 ° C. for 3 to 10 hours. N in the general formula (1) is determined by the molar ratio of the fluorene compound (2) and epichlorohydrin.

  The epoxy resin composition of the present invention contains the epoxy resin (1). This epoxy resin (1) can be used alone or in a mixture of two or more. The epoxy resin composition may further comprise (i) an epoxy resin other than the epoxy resin (1), (ii) a reactive diluent, (iii) a curing agent, (iv) a curing accelerator, ) Additives, (vi) solvents and the like.

  Examples of the epoxy resin other than the epoxy resin (1) of (i) above include bisphenol epoxy resins such as bisphenol A, bisphenol S and bisphenol F; polyfunctional phenol epoxy resins such as phenol resin and cresol novolac resin; naphthol type Examples thereof include naphthalene type epoxy resins such as epoxy resins; biphenyl type epoxy resins; fluorene type epoxy resins other than the above epoxy resin (1).

  The reactive diluent (ii) is a low-viscosity epoxy compound added for viscosity adjustment, and a bifunctional or higher-functional low-viscosity epoxy compound is particularly preferable. Examples of the reactive diluent include the following compounds: diglycidyl ether, butanediol diglycidyl ether, diglycidyl aniline, neopentyl glycol glycidyl ether, cyclohexane dimethanol diglycidyl ether, alkylene diglycidyl ether, polyglycol. Diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, 4-vinylcyclohexene monooxide, vinylcyclohexene dioxide, methylated vinylcyclohexene dioxide, phenylglycidyl ether, 4-tert-butyl Phenyl glycidyl ether, o-phenyl phenyl glycidyl ether, etc. These reactive diluents can be used alone or in combination of two or more.

The curing agent (iii) is not particularly limited, but amine compounds, imidazole compounds, carboxylic acids, phenols, quaternary ammonium salts, methylol group-containing compounds, triflic acid (Trif1ic
acid) salts, boron trifluoride etherate compounds, boron trifluoride, diazonium salts that generate acid by light or heat, sulfonium salts, iodonium salts, benzothiazolium salts, ammonium salts, phosphonium salts And cationic cationic polymerization catalyst.

  Examples of the curing accelerator (iv) include 1,8-diazacyclo (5.4.0) undecene-7 and amines thereof (including tertiary amines) such as phenol salts, phenol novolac salts, carbonate salts, and formate salts. ) And derivatives thereof; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole; ethylphosphine, propylenephosphine, And organophosphines (first, second, and third phosphines) such as phenylphosphine, triphenylphosphine, and trialkylphosphine.

  Examples of the additive (v) include reinforcing materials or fillers, colorants, pigments, flame retardants, and curable compounds (curable monomers, oligomers, or resins). As the reinforcing agent or filler, a powdery or fibrous reinforcing agent or filler is used. Examples of the powdery reinforcing agent or filler include materials comprising the following materials: metal oxides such as aluminum oxide and magnesium oxide; metal carbonates such as calcium carbonate and magnesium carbonate; diatomaceous earth powder, basic Silicon compounds such as magnesium silicate, calcined clay, finely divided silica, fused silica and crystalline silica; metal hydroxides such as aluminum hydroxide; other kaolin, mica, quartz powder, graphite, molybdenum disulfide and the like. Examples of the fibrous reinforcing agent or filler include the following materials: glass fiber, ceramic fiber, carbon fiber, alumina fiber, silicon carbide fiber, boron fiber, polyester fiber, polyamide fiber, and the like. Examples of the colorant, pigment, or flame retardant include titanium dioxide, iron black, molybdenum red, bitumen, ultramarine, cadmium yellow, cadmium red, antimony trioxide, red phosphorus, a bromine compound, and triphenyl phosphate. The curable compound is used for the purpose of improving the properties of the resin in the final coating film, adhesive layer, molded article and the like. Examples thereof include alkyd resins, melamine resins, fluororesins, vinyl chloride resins, acrylic resins, silicone resins, and polyester resins. These curable compounds are contained in amounts that do not impair the original properties of the resin composition of the present invention. These additives can be used alone or in combination of two or more.

  Examples of the solvent (vi) include the following solvents: alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol Glycol ethers such as dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether; methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol methyl ether acetate, 3-methoxybutyl-1 -Acet Alkylene glycol monoalkyl ether acetates such as toluene; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone; Ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, 3- Esters such as methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate and ethyl lactate. These solvents may be used alone or in a combination of two or more.

  The composition of the present invention is formed into a molded product according to the purpose. The molded body may be a product having a desired shape made of a cured product of the composition itself, or a coating film made of a cured product of the composition formed on a substrate. For example, the composition is heated and melted as necessary, poured into a predetermined mold and heated or cured by irradiation with radiation to obtain a molded article having a desired shape. Alternatively, a cured composition can be formed on the substrate by applying and drying a liquid composition containing a solvent on the substrate and then heating or irradiating with radiation.

  The molding method and the curing conditions are not particularly limited. For example, when molding using a predetermined mold, a molding method by heating and pressurization or a low-temperature molding method called cold press is used. As a method by heating and pressing, for example, a method of filling the composition of the present invention in a mold at normal pressure by a method called hand lay-up or spray lay-up and then heat-curing; by injection molding using a transfer press device Examples thereof include a method of heat compression; and a continuous molding method such as a continuous lamination molding method, a continuous drawing method called pultrusion, and a filament winding molding method. In these molding methods, an intermediate molding material can be obtained by mixing the resin composition with a reinforcing agent or impregnating the reinforcing agent, and then molding and curing the intermediate molding material. Examples of the reinforcing agent include woven fabric and nonwoven fabric made of resin, glass and the like. As an intermediate molding material obtained by using this, for example, a sheet-like intermediate molding material called SMC (Sheet Molding Compound); a liquid or solid intermediate molding material called BMC (Berck Molding Compound) or premix A prepreg obtained by impregnating the composition of the present invention into a glass cloth, a mat or the like.

  The fluorene-containing epoxy resin of the present invention has excellent heat resistance and is easily cured by heat or radiation irradiation. Since the resin composition containing this epoxy resin is excellent in moldability, it is easy to form into a predetermined shape by a mold or form a thin film on a substrate as described above. Molded bodies (including thin films) obtained by curing these with heat or radiation have excellent heat resistance and environmental resistance, high mechanical strength such as bending properties, high toughness, thermal shock resistance, and good Has moldability.

  In addition to the above properties such as heat resistance, the molded product obtained from this epoxy resin composition is excellent in insulation, has small curing shrinkage and excellent dimensional stability. Useful for electronic material sealants. Furthermore, since this composition is excellent in heat resistance, adhesiveness, curability, etc., it is suitably used for potting materials, coating materials, etc. for various electronic parts such as capacitors. When used as a sealing material for an electronic insulating material or as a potting agent, it can be used in the same manner as a sealing resin using an epoxy resin that has been conventionally used. Furthermore, since cured | curing material is excellent in transparency, it is useful also as a thermosetting resin composition for optical devices.

B. Fluorene-containing epoxy acrylate resin The fluorene-containing epoxy acrylate resin of the present invention is represented by the following general formula (3):

Here, R ₁ and R ₂ are each independently a hydrogen atom or a methyl group, and n is each independently an integer of 0 to 10.

  This fluorene-containing epoxy acrylate resin may be described as “fluorene-containing epoxy acrylate resin (3)”, “epoxy acrylate resin (3)”, or the like in this specification.

  The said epoxy acrylate resin (3) is obtained by making (meth) acrylic acid act on the above-mentioned epoxy resin (1) represented by the following general formula, for example:

  Here, n is an integer from 0 to 10.

  Alternatively, it is obtained by allowing glycidyl (meth) acrylate to act on the fluorene compound (2) represented by the following general formula:

  The reaction between the epoxy resin (1) and (meth) acrylic acid and the reaction between the fluorene compound (2) and glycidyl (meth) acrylate are both carried out using an appropriate solvent as required, and are in the range of 50 to 120. It is carried out in the temperature range of 5 ° C. for 5 to 30 hours. Examples of the solvent that can be used include alkylene monoalkyl ether acetates such as methyl cellosolve acetate, propylene glycol monomethyl ether acetate, and 3-methoxybutyl-1-acetate; ketones such as methyl ethyl ketone and methyl amyl ketone. Of these, propylene glycol monomethyl ether acetate and 3-methoxybutyl-1-acetate are preferred.

  The epoxy acrylate resin (3) has thermosetting properties and radiation curable properties. Here, the radiation is a generic term for visible light, ultraviolet rays, electron beams, X-rays, α rays, β rays, γ rays, and the like. Therefore, the resin composition containing this epoxy acrylate resin (3) functions as a thermosetting or radiation-sensitive resin composition. In any composition, the epoxy acrylate resin (3) may be contained singly or as a mixture of two or more.

  When the resin composition containing the epoxy acrylate resin (3) is a radiation-sensitive resin composition, the composition contains (I) a photopolymerization initiator in addition to the epoxy acrylate resin (3). In the case of a thermosetting resin composition, (II) a radical initiator may be contained. Further, any of these compositions may contain a light or thermosetting acrylate compound other than the above (III) epoxy acrylate resin (3), (IV) additive, (V) solvent and the like.

  The photopolymerization initiator (I) that can be contained in the radiation-sensitive resin composition containing the epoxy acrylate resin (3) of the present invention includes the epoxy acrylate resin (3) and the photocuring agent that is optionally contained. A compound having an effect of initiating photopolymerization of a functional acrylate compound and / or a compound having a sensitizing effect. Examples of such a photopolymerization initiator include the following compounds: acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert. -Acetophenones such as butyl acetophenone; benzophenones such as benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone; benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether; Benzyldimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropyl Sulfur compounds such as luthioxanthone; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone; azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, etc. Organic peroxides; and thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole.

  These compounds may be used individually by 1 type, and can also be used in combination of 2 or more type. In addition, a compound that does not act as a photopolymerization initiator per se, but that can increase the ability of the photopolymerization initiator by using it in combination with the above-mentioned compound can also be added. Examples of such compounds include tertiary amines such as triethanolamine which are effective when used in combination with benzophenone.

  Examples of the radical initiator (II) that can be contained in the thermosetting resin composition include ketone peroxide compounds, diacyl peroxide compounds, hydroperoxide compounds, dialkyl peroxide compounds, and peroxyketal compounds. , Radical initiators composed of alkyl perester compounds, percarbonate compounds, azobis compounds, and the like are used. In particular, diacyl peroxide type or azobis type radical initiators are suitable, and for example, benzoyl peroxide, α, α'-azobis (isobutyronitrile), etc. are widely used.

  The light or thermosetting acrylate compound other than the epoxy acrylate resin (3) of (III) is used as a viscosity modifier or a photocrosslinking agent depending on the physical properties required for the composition. In the composition within the range of. Examples of such acrylate compounds include the following compounds: monovalent acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate; and ethylene Glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) Acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, polyvalent (meth) acrylates such as glycerol (meth) acrylate.

  These compounds can be used alone or in combination of two or more.

  As the additive (IV), a thermal polymerization inhibitor, an adhesion assistant, an antifoaming agent, a surfactant, a plasticizer and the like are used depending on the purpose of use of the composition.

  Among these, examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine and the like.

  The adhesion assistant is added for the purpose of improving the adhesion to the substrate when a liquid composition containing the epoxy acrylate resin (3) is applied to the substrate. As the adhesion assistant, a silane compound (functional silane coupling agent) having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanato group, or an epoxy group is preferably used. Specific examples of such functional silane coupling agents include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ -Glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like.

  Examples of antifoaming agents include silicone compounds, fluorine compounds, acrylic compounds, and the like.

  The surfactant is contained for the purpose of facilitating application of the liquid composition and improving the flatness of the resulting coating film. Examples of the surfactant include silicone-based, fluorine-based, and acrylic compounds. Specifically, for example, BM-1000 (manufactured by BM Hemy); Megafuck F142D, Megafuck F172, Megafuck F173, and Megafuck F183 [manufactured by Dainippon Ink & Chemicals, Inc.]; Fluorard FC-135, Fluorard FC-170C, Florard FC-430 and Florard FC-431 [manufactured by Sumitomo 3M Limited]; Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141 and Surflon S-145 [Asahi Glass Co., Ltd. SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57 and DC-190 [manufactured by Toray Silicone Co., Ltd.].

  Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and tricresyl.

  Examples of the solvent (V) include the following solvents: alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol Glycol ethers such as dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether; methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol methyl ether acetate, 3-methoxybutyl-1 -Acetate Any alkylene glycol monoalkyl ether acetates; aromatic hydrocarbons such as toluene, xylene; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone; and 2 -Ethyl hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, 3-methoxypropion Esters such as methyl acrylate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate and ethyl lactate. These solvents may be used alone or in a combination of two or more.

  Examples of the radiation used for curing the radiation-sensitive resin composition of the present invention include visible light, ultraviolet light, electron beam, X-ray, α-ray, β-ray, and γ-ray in order from the longest wavelength. Of these, ultraviolet rays are the most preferable radiation from the viewpoint of economy and efficiency. As the ultraviolet light used in the present invention, ultraviolet light oscillated from a lamp such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, an arc lamp, a metal halide lamp, or a xenon lamp can be preferably used. The radiation having a shorter wavelength than ultraviolet rays is theoretically superior to ultraviolet rays because of its high chemical reactivity, but ultraviolet rays are practical from the viewpoint of economy.

  The composition of the present invention is formed into a molded product according to the purpose. The molded body may be a product having a desired shape made of a cured product of the composition itself, or a coating film made of a cured product of the composition formed on a substrate.

  For example, a cured film can be formed on a substrate by applying and drying a liquid composition containing a solvent on the substrate and then irradiating or heating with radiation (for example, light). Alternatively, the radiation-curable or thermosetting composition is heated and melted as necessary, poured into a predetermined mold, heated, or irradiated with radiation to obtain a molded article having a desired shape.

  A molded body (including a coating film) formed from the composition of the present invention has high hardness, extremely excellent heat resistance, and further has a high refractive index.

  The fluorene-containing epoxy acrylate resin (3) of the present invention is excellent in heat resistance and is easily cured by heat or radiation irradiation. The thermosetting or radiation-sensitive composition containing this epoxy acrylate resin is used for various applications. Specifically, for example, it is useful as various coating agents, particularly coating agents that require high hardness and heat resistance. Or resist ink materials for color filters; materials for protective films such as liquid crystal displays and electronic components (for example, forming materials for protective films used for color filters, liquid crystal display elements, integrated circuit elements, solid-state imaging elements, etc.); interlayer insulation And / or a material for forming a flattened film; a solder resist used in the production of a printed wiring board; or a photosensitive composition suitable for forming a columnar spacer as an alternative to a bead spacer in a liquid crystal display. Furthermore, the composition of the present invention comprises materials for various optical parts (lenses, LEDs, plastic films, substrates, optical disks, etc.); a coating agent for forming a protective film for the optical parts; an adhesive for optical parts (adhesive for optical fibers) Etc.); a coating agent for producing a polarizing plate; a photosensitive resin composition raw material for hologram recording, and the like.

C. Fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin The fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin (A) of the present invention is a fluorene-containing epoxy acrylate resin represented by the following general formula (3):

(Wherein R ₁ and R ₂ are each independently a hydrogen atom or a methyl group, n is an integer of 0 to 10) and obtained by reacting a polybasic carboxylic acid or an anhydride thereof.

  The fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin (B) of the present invention is a fluorene-containing epoxy acrylate resin represented by the following general formula (3):

(Wherein R ₁ and R ₂ are each independently a hydrogen atom or a methyl group, n is an integer of 0 to 10) and a polybasic alcohol are reacted with a polybasic carboxylic acid or its anhydride Is obtained.

  The polybasic carboxylic acid used for the preparation of the fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin (A) or (B) is a carboxylic acid having a plurality of carboxyl groups such as dicarboxylic acid and tetracarboxylic acid. Such polybasic carboxylic acids or anhydrides include the following compounds: maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid , Methyl endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, glutaric acid and other dicarboxylic acids and their anhydrides; trimellitic acid or its anhydride, pyromellitic acid, benzophenonetetracarboxylic acid, 4- (1, 2-Dicarboxyethyl) -1,2,3,4-tetrahydride Naphthalene-1,2-dicarboxylic acid, biphenyl tetracarboxylic acid, tetracarboxylic acid, and their dianhydrides such as biphenyl ether tetracarboxylic acid and the like.

  The polyhydric alcohol used for the preparation of the fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin (B) refers to a compound containing two or more hydroxyl groups in the molecule, and examples thereof include the following compounds. , But not limited to: ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, dimethylolbutanoic acid, dimethylolpropanoic acid, Tartaric acid, glycerin, diglycerin, trimethylolethane, trimethylolpropane, isocyanuric acid tris (2-hydroxyethyl), ditrimethylolpropane, ditrimethylolethane, pentaerythritol, erythritol, xylitol, sorbi Lumpur, inositol, dipentaerythritol, poly glycerin. Among these, when a trifunctional or higher functional compound such as trimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol is used, the adhesion between the thin film obtained from the composition containing the resin and the substrate Is preferable, and the transparency of the film is excellent. These polyhydric alcohols may be used alone or in combination of two or more.

  The fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin (B) can be obtained by reacting the fluorene-containing epoxy acrylate resin, a polyhydric alcohol, and a polybasic carboxylic acid or an anhydride thereof. In this reaction, the addition order of the fluorene-containing epoxy acrylate resin, the polyhydric alcohol, and the polybasic carboxylic acid is not particularly limited. For example, there are methods in which these are mixed and reacted at the same time, fluorene-containing epoxy acrylate resin and polyhydric alcohol are mixed, then polybasic carboxylic acid or its anhydride is added, mixed and reacted. Further, a polybasic carboxylic acid may be further added to these reaction products for reaction.

  By appropriately selecting the type and number of the polybasic carboxylic acid or its anhydride, various fluorene-containing alkali-soluble radiation-polymerizable unsaturated resins (A) having a bisxylenolfluorene skeleton and different structures Or (B) can be manufactured. Specifically, for example, the following (Ai) to (A-iii) and (Bi) to (B-iii) shown in the following first to sixth fluorene-containing alkali-soluble radiation-polymerizable imperfections Saturated resins are prepared, but these are exemplary.

(Ai) First fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin: obtained by mixing and reacting a fluorene-containing epoxy acrylate resin and one polybasic carboxylic acid or its anhydride. resin;
(A-ii) Second fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin: a mixture of a fluorene-containing epoxy acrylate resin and two or more polybasic carboxylic acids or anhydrides thereof (for example, dicarboxylic acid A resin obtained by mixing and reacting with a mixture of an anhydride and a tetracarboxylic dianhydride). ;and,
(A-iii) Third fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin: a reaction between a fluorene-containing epoxy acrylate resin and tetracarboxylic acid or a dianhydride thereof, and the resulting reaction product and dicarboxylic acid or Resin obtained by reacting with its anhydride.

(Bi) Fourth fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin: a fluorene-containing epoxy acrylate resin, a polyhydric alcohol, and one kind of polybasic carboxylic acid or anhydride thereof are mixed, Resin obtained by reaction;
(B-ii) Fifth fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin: a mixture of a fluorene-containing epoxy acrylate resin, a polyhydric alcohol, and two or more polybasic carboxylic acids or anhydrides thereof (For example, a resin obtained by mixing and reacting with a mixture of dicarboxylic acid anhydride and tetracarboxylic dianhydride). ;and,
(B-iii) Sixth fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin: a reaction product obtained by reacting a fluorene-containing epoxy acrylate resin, a polyhydric alcohol, and a tetracarboxylic acid or a dianhydride thereof. Resin obtained by reacting a product with dicarboxylic acid or its anhydride.

  The thus obtained fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin (A) or (B) having a different structure is used depending on the intended use.

  The “polybasic carboxylic acid or anhydride thereof” means “at least one of a specific polybasic carboxylic acid and an anhydride corresponding thereto”. For example, the polybasic carboxylic acid is phthalic acid. An acid refers to at least one of phthalic acid and phthalic anhydride.

  Further, “a mixture of polybasic carboxylic acids or anhydrides thereof” and “a mixture of two or more types” mean that at least two types of polybasic carboxylic acids or anhydrides thereof are simultaneously present. Therefore, in the methods (A-ii) and (B-ii), at least two types of polybasic carboxylic acids or their anhydrides are involved in the reaction.

  In any of the above methods, the fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin can be obtained by changing the fluorene-containing epoxy acrylate resin, polyhydric alcohol, polybasic carboxylic acid or anhydride thereof in the above-described method (order). For example, it is produced by dissolving (suspending) in a cellosolve solvent such as ethyl cellosolve acetate or butyl cellosolve acetate and reacting by heating.

  In the production of the fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin, the molar ratio of the hydroxyl group of the fluorene-containing epoxy acrylate resin to the hydroxyl group of the polyhydric alcohol is 99 / It is preferable to adjust so that it may become 1 to 50/50, and it is more preferable that it is 95/5 to 60/40. When the molar ratio of the hydroxyl group of the polyhydric alcohol exceeds 50%, the molecular weight of the resulting resin increases rapidly and there is a risk of gelation. Moreover, if it is less than 1%, it tends to be difficult to improve heat resistance and heat discoloration.

  The polybasic carboxylic acid or an anhydride thereof is 0.3 to 1 equivalent in terms of an acid anhydride group, preferably 0. 0, based on a total of 1 equivalent (mol) of the fluorene-containing epoxy acrylate resin and the hydroxyl group of the polyhydric alcohol. It is subjected to the reaction at a ratio of 4 to 1 equivalent. If the polybasic carboxylic acid or its anhydride is less than 0.3 equivalent in terms of acid anhydride group, the molecular weight of the resulting alkali-soluble resin will not increase. Therefore, when exposure and development are performed using such a radiation-sensitive resin composition containing an alkali-soluble resin, the resulting film may have insufficient heat resistance or the film may remain on the substrate. is there. When the polybasic carboxylic acid or its anhydride exceeds 1 equivalent in terms of acid anhydride group, unreacted acid or acid anhydride remains, and the molecular weight of the resulting alkali-soluble resin becomes low, and the resin In some cases, the developability of the radiation-sensitive resin composition containing is poor.

  In addition, acid anhydride group conversion shows the quantity when all the carboxyl groups and acid anhydride groups contained in the polybasic carboxylic acid to be used or its anhydride are converted into acid anhydride.

  In the production of the second and third fluorene-containing alkali-soluble radiation-polymerizable unsaturated resins, two or more polybasic carboxylic acids or anhydrides thereof are used. Generally, dicarboxylic anhydride and tetracarboxylic dianhydride are used. The ratio between the dicarboxylic acid anhydride and the tetracarboxylic dianhydride is preferably 1/99 to 90/10, and more preferably 5/95 to 80/20, as a molar ratio. If the ratio of the dicarboxylic acid anhydride is less than 1 mol% of the total acid anhydride, the resin viscosity becomes high and workability may be lowered. Furthermore, since the molecular weight of the obtained resin becomes too large, when the thin film is formed on the substrate using the radiation-sensitive resin composition containing the resin and the exposure is performed, the exposed portion is in contact with the developer. It tends to be difficult to dissolve and difficult to obtain the desired pattern. When the proportion of the dicarboxylic acid anhydride exceeds 90 mol% of the total acid anhydride, the molecular weight of the resin obtained becomes too small. Therefore, when a coating film is formed on the substrate using the composition containing the resin, pre-beg Problems such as sticking remaining in the subsequent coating film are likely to occur.

  In any of the above cases, the reaction temperature is preferably 50 to 130 ° C, more preferably 70 to 120 ° C during the reaction of the fluorene-containing epoxy acrylate resin, the polyhydric alcohol, and the polybasic carboxylic acid or its anhydride. is there. When the reaction temperature exceeds 130 ° C., some condensation of carboxyl groups and hydroxyl groups occurs, and the molecular weight increases rapidly. On the other hand, if it is less than 50 ° C., the reaction does not proceed smoothly, and unreacted polybasic carboxylic acid or its anhydride remains.

  The fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin of the present invention thus obtained is suitably used as the main component of the radiation-sensitive resin composition.

  In the present specification, the fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin is referred to as “fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin”, “alkali-soluble radiation-soluble unsaturated resin”, “ May be described as "radiation polymerizable unsaturated resin".

  The radiation-sensitive resin composition containing the fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin of the present invention includes the fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin, and, if necessary, (a) light A polymerization initiator, (b) a polymerizable monomer or oligomer other than the fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin, (c) a compound having an epoxy group, (d) an additive, (e) a solvent, etc. contains.

  The photopolymerization initiator (a) refers to a compound having a photopolymerization initiating action and / or a compound having a sensitizing effect. Examples of such compounds include the following compounds: acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone. Benzophenones such as benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone; benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzyldimethyl ketal Thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthione Sulfur compounds such as xanthene; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone; organics such as azobisisobutyronitrile, benzoyl peroxide, cumene peroxide Peroxides; and thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole.

  These compounds may be used individually by 1 type, and may be used in combination of 2 or more type. Furthermore, a compound which does not act as a photopolymerization initiator itself but can increase the ability of the photopolymerization initiator by using it in combination with the above compound can also be added. Examples of such compounds include tertiary amines such as triethanolamine which are effective when used in combination with benzophenone.

  The polymerizable monomer or oligomer other than the fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin in the above (b) is a monomer or oligomer that can be polymerized by radiation, and the physical properties according to the intended use of the composition It can be contained according to. Examples of such monomers or oligomers that can be polymerized by radiation include the following monomers or oligomers: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and the like. Monomers having a hydroxyl group of; and ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, Trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, (meth) acrylic acid esters such as glycerol (meth) acrylate. These monomers or oligomers may be used alone or in combination of two or more.

  These monomers or oligomers can be contained as long as they act as a viscosity modifier or a photocrosslinking agent and do 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 based on 100 parts by weight of the alkali-soluble radiation-polymerizable unsaturated resin. When the content of the monomer or oligomer exceeds 50 parts by weight, a problem arises in sticking property after pre-baking.

  As the compound (c) having an epoxy group, a polymer or monomer having at least one epoxy group is used. Examples of the polymer having at least one epoxy group include a phenol novolac epoxy resin, a cresol novolac epoxy resin, a bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol S epoxy resin, a biphenyl epoxy resin, and an alicyclic ring. There is an epoxy resin such as an epoxy resin. Examples of the monomer having at least one epoxy group include phenyl glycidyl ether, p-butylphenol glycidyl ether, triglycidyl isocyanurate, diglycidyl isocyanurate, allyl glycidyl ether, and glycidyl methacrylate. These compounds may be used alone or in combination of two or more.

  The compound which has these epoxy groups may be contained in the range which does not impair the property of the resin composition of this invention. Usually, the compound having an epoxy group is contained in a proportion of 50 parts by weight or less per 100 parts by weight of the fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin. When the amount exceeds 50 parts by weight, cracking occurs when the composition containing the component is cured, and the adhesion tends to be lowered.

  Examples of the additive (d) include thermal polymerization inhibitors, adhesion assistants, epoxy group curing accelerators, surfactants, antifoaming agents, etc., and these are in amounts that do not impair the purpose of the present invention. Contained in the composition.

  Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine and the like.

  The adhesion aid is contained in order to improve the adhesion of the resulting composition. As the adhesion assistant, a silane compound (functional silane coupling agent) having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanato group, and an epoxy group is preferable. Specific examples of this functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycol. Sidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like can be mentioned.

  Examples of the epoxy group curing accelerator include amine compounds, imidazole compounds, carboxylic acids, phenols, quaternary ammonium salts, and methylol group-containing compounds. By containing a small amount of an epoxy group curing accelerator, various properties such as heat resistance, solvent resistance, acid resistance, plating resistance, adhesion, electrical properties and hardness of the cured film obtained by heating are improved.

  The surfactant is included, for example, to facilitate application of a liquid composition on a substrate, and the flatness of the resulting film is also improved. Surfactants include, for example, BM-1000 (manufactured by BM Hemy), MegaFuck F142D, MegaFuck F172, MegaFuck F173 and MegaFuck F183 (Dainippon Ink Chemical Co., Ltd.), Florard FC-135, Fluorard FC-170C, Fluorard FC-430 and Fluorard FC-431 (manufactured by Sumitomo 3M), Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141 and Surflon S-145 (Asahi Glass Co., Ltd.) )), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57 and DC-190 (manufactured by Toray Silicone Co., Ltd.).

  Examples of the antifoaming agent include silicone, fluorine, and acrylic compounds.

  The solvent (e) that can be contained in the radiation-sensitive resin composition of the present invention is used to uniformly dissolve each component in the composition, for example, to facilitate coating on a substrate. Such a solvent is not particularly limited as long as it is an organic solvent that does not react with each component in the composition and can dissolve or disperse them. Examples include the following compounds: 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 ethyl ether, and ethylene glycol monoethyl ether; methyl Ethylene glycol alkyl ether acetates such as cellosolve acetate and ethyl cellosolve acetate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether; Propylene glycol alkyl ether acetates such as lenglycol methyl ether acetate and propylene glycol ethyl ether acetate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone Ketones such as; and ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-2-methylbutane Acid methyl, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyrate , Methyl lactate, esters such as ethyl lactate.

  Of these, glycol ethers, alkylene glycol alkyl ether acetates, diethylene glycol dialkyl ethers, ketones and esters are preferred, and in particular ethyl 3-ethoxypropionate, ethyl lactate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether Acetate and methyl amyl ketone are preferred. These solvents may be used alone or in a combination of two or more.

  The fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin of the present invention is soluble in alkali and can be cured by irradiation. The radiation-sensitive resin composition containing this radiation-polymerizable unsaturated resin is molded into a desired shape, cured by radiation, and used for various purposes. In particular, it is used for the purpose of forming a thin film having a predetermined pattern by forming a thin film on a substrate with the composition, irradiating with radiation, and developing.

  For example, as described above, in the case where a thin film is formed on a substrate and radiation curing and development are performed, usually, each component of the composition containing a solvent is first mixed to obtain a liquid composition. For example, it is more preferable to filter this with a Millipore filter having a pore diameter of about 1.0 to 0.2 μm to obtain a uniform liquid. Next, this liquid composition is applied onto a substrate to obtain a coating film. Examples of the coating method include a dipping method, a spray method, a roller coating method, a slit coating method, a bar coating method, and a spin coating method. In particular, a spin coating method is widely used. By applying the liquid resin composition to a thickness of about 1 to 30 μm by these methods and then removing the solvent, a thin film is formed. Usually, a pre-bake treatment is performed to sufficiently remove the solvent.

  After placing a mask having a desired pattern on the thin film of the substrate, irradiation with radiation is performed. Examples of the radiation used include visible light, ultraviolet light, electron beam, X-ray, α-ray, β-ray, and γ-ray in order from the longest wavelength. Of these, ultraviolet rays are the most preferable radiation from the viewpoint of economy and efficiency. Ultraviolet light oscillated from a lamp such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, an arc lamp, or a xenon lamp can be preferably used as the ultraviolet light used in the present invention. Radiation having a shorter wavelength than ultraviolet rays has high chemical reactivity and is theoretically superior to ultraviolet rays, but ultraviolet rays are practical from the viewpoint of economy.

  By the irradiation, the exposed part is cured by a polymerization reaction. Unexposed portions are developed with a developer. Thereby, the non-irradiated part of the radiation is removed, and a thin film having a desired pattern is obtained. Examples of the developing method include a liquid piling method, a dipping method, and a rocking dipping method.

  Examples of the developer include 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 can be dissolved. It is a liquid mixture with an active agent.

  Examples of the base used for preparing an alkaline aqueous solution suitable for developing the radiation-sensitive resin composition of the present invention include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo (5.4.0) -7-undecene, 1,5-diazabicyclo (4.3.0) -5-nonane, preferably sodium carbonate, tetramethylammonium hydroxide, etc. It is needed. Examples of the water-soluble organic solvent include methanol, ethanol, acetone and the like.

  An appropriate amount of a water-soluble organic solvent such as methanol, ethanol, propanol, or ethylene glycol, or a surfactant is added to the alkaline aqueous solution as necessary.

  The development of the resin composition of the present invention can be usually performed at a temperature of 10 to 50 ° C., preferably 20 to 40 ° C., using a commercially available developing machine or ultrasonic cleaner.

  After alkali development, in order to improve alkali resistance, it is desirable to apply an epoxy curing treatment by heating (post-bake treatment). In the resin composition of the present invention, by performing heat treatment, not only the durability against strong alkaline water is remarkably improved, but also various properties such as adhesion to metals such as copper or glass, heat resistance, surface hardness, etc. improves. About the heating temperature and heating time in this heat-hardening conditions, 80-250 degreeC and 10-120 minutes are mentioned, for example. A preferable heating temperature is 100 to 200 ° C. In this way, a cured thin film having a desired pattern can be obtained.

  The cured film obtained by curing the composition of the present invention is excellent in heat resistance, transparency, adhesion to a substrate, acid resistance, alkali resistance, chemical resistance, solvent resistance, surface hardness, and the like. Furthermore, since this cured film is an organic coating film, it has a low dielectric constant. Therefore, the composition of the present invention is, for example, a material for a protective film such as a liquid crystal display or an electronic component (for example, a material for forming a protective film used for a color filter, a liquid crystal display element, an integrated circuit element, a solid-state imaging element, etc.); Insulating film and / or planarizing film forming material (for example, interlayer insulating film and / or planarizing film forming material used for color filters, liquid crystal display elements, integrated circuit elements, solid-state imaging elements, etc.); Color resist binder : Solder resist used for production of printed wiring board; Or, it is preferably used as an alkali-soluble type photosensitive composition suitable for forming a columnar spacer as an alternative to a bead spacer in a liquid crystal display. Furthermore, the composition of the present invention comprises materials for various optical parts (lenses, LEDs, plastic films, substrates, optical disks, etc.); a coating agent for forming a protective film for the optical parts; an adhesive for optical parts (adhesive for optical fibers) Etc.); a coating agent for producing a polarizing plate; a photosensitive resin composition for hologram recording, and the like.

  Hereinafter, based on an Example, this invention is demonstrated concretely.

Example 1
(Synthesis of epoxy resin)
407 g of the fluorene compound represented by the following formula (2) was dissolved in 1390 g of epichlorohydrin, 2.2 g of benzyltriethylammonium chloride was further added, and the mixture was stirred at 100 ° C. for 5 hours. Next, under reduced pressure (150 mmHg), 210 g of 40% aqueous sodium hydroxide solution was added dropwise at 70 ° C. over 3 hours. Meanwhile, the produced water was removed from the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After completion of the dropping, the reaction was continued for another 30 minutes. Then, after removing the salt produced | generated by filtration and washing with water, epichlorohydrin was distilled off until solid content became 50%, and 1000g of methanol was added. The precipitated crystals were separated by filtration and dried to obtain 460 g of a white powdery epoxy resin (1.a) where n≈0 in the following formula (1). The epoxy equivalent of this resin was 265 g / eq.

The obtained epoxy resin was purified by preparative GPC, and the resulting purified epoxy resin was subjected to structural analysis. The results are shown below. FIG. 1 shows a ¹ H-NMR chart, FIG. 2 shows a ¹³ C-NMR chart, and FIG. 3 shows a FD-MS (field desorption ionization mass spectrometry) chart.

  [1] Melting point: 194 ° C. (according to DSC)

[2] ¹ H-NMR (solvent: CHCl ₃ -d ₁ , internal standard: TMS)
Peak δ, ppm
d, e, d ', e' 2.16 12H
a1, a1 '2.67-2.68 2H
a2, a2 '2.84-2.86 2H
b, b '3.29-3.34 2H
c1, c1 '3.68-3.72 4H
c2, c2 '3.96-3.99 4H
f, f ', h, l 6.78 4H
g, g ', i, j, m, n 7.24-7.40 6H
k, o 7.73-7.75 4H

[3] ¹³ C-NMR (solvent: CHCl ₃ -d ₁ , internal standard: TMS)
Peak δ, ppm
d, e, d ', e' 16.671
a, a '44.781
b, b '50.813
l 64.728

c, c '73.172
k, g, k ', g' 120.250
o, u 126.502
m, s 127.503
h, h '127.769
n, p, t, v 128.748
j, j '130.394
i, i '140.204
q, w 141.623
r, x 151.767
f, f '154.513

[3] FD-MS m / n = 518 (m ⁺ )

Comparative Synthesis Example 1
350 g of fluorene compound represented by the following formula (4) was dissolved in 1390 g of epichlorohydrin, 2.2 g of benzyltriethylammonium chloride was further added, and the mixture was stirred at 100 ° C. for 5 hours. Next, under reduced pressure (150 mmHg), 210 g of 40% aqueous sodium hydroxide solution was added dropwise at 70 ° C. over 3 hours. Meanwhile, the produced water was removed from the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After completion of the dropping, the reaction was continued for another 30 minutes. Then, after removing the salt produced | generated by filtration and washing with water, epichlorohydrin was distilled off until solid content became 50%, and 1000g of methanol was added. The precipitated crystals were separated by filtration and dried to obtain 420 g of a white powdery epoxy resin (5.a) where n≈0 in the following formula (5). The epoxy equivalent of this resin was 233 g / eq.

Example 2
(Solvent solubility evaluation of fluorene-containing epoxy resin)
20 parts by weight of the epoxy resin (1.a) obtained in Example 1 and 80 parts by weight of a solvent were mixed to confirm solubility. As solvents, toluene, methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), and diethylene glycol methyl ethyl ether were evaluated. The rank of evaluation is as follows.
◯: Dissolved at room temperature Δ: Dissolved when heated, and crystals do not precipitate even when cooled ×: Dissolved when heated, crystals precipitate when cooled, or do not dissolve even when heated

  Table 1 shows the evaluation results of this example and Comparative Example 1 described later.

Comparative Example 1
In Example 2, evaluation was performed in the same manner as in Example except that the epoxy resin (1.a) was changed to the epoxy resin (5.a) obtained in Comparative Synthesis Example 1.

Example 3
(Preparation and Evaluation of Molded Body Using Thermosetting Resin Composition Containing Epoxy Resin)
In a mixture of 100 parts by weight of the epoxy resin (1.a) obtained in Example 1 and 55 parts by weight of a methylhexahydrophthalic anhydride type curing agent (manufactured by Shin Nippon Rika Co., Ltd., Ricacid MH-700), As a catalyst, 1 part by weight of 2-ethyl-4-methylimidazole (2E4MZ) was mixed, and the obtained mixture was put into a stainless steel mold having a size of 100 mm × 100 mm and a thickness of 1 mm, and then placed in an oven at 100 ° C. for 1 hour, and then at 180 ° C. For 4 hours to heat cure. Using the obtained molded body (test piece), the following items were evaluated.

[1] Heat resistance:
Tg is measured by DSC (DSC210 type manufactured by SII Nano Technology Co., Ltd.).

[2] Dielectric constant and dielectric loss tangent:
Measured with TR-1100 type dielectric loss automatic measuring device (manufactured by Ando Electric Co., Ltd.)

[3] Elastic modulus:
Using a dynamic viscoelasticity measuring device DMS6100 (manufactured by SII Nano Technology Co., Ltd.), in the temperature range of −50 to 250 ° C., the response when a 1 Hz sine wave is given in the double-end bending mode is measured and stored. The elastic modulus E ′ is obtained.

  Table 2 shows the composition of the composition used in this example, and Table 3 shows the evaluation results of the obtained test piece. Table 2 and Table 3 also show Example 4, Example 5, Comparative Example 2, and Comparative Example 3 described later.

Example 4
A mixture of 100 parts by weight of epoxy resin (1.a), 73 parts by weight of epoxy resin (1.a) and 27 parts by weight of 4-tert-butylphenylglycidyl ether (manufactured by Nagase ChemteX Corporation, Denacol EX-146) A test piece was prepared and evaluated in the same manner as in Example 3 except that the methylhexahydrophthalic anhydride type curing agent was changed to 59 parts by weight.

Example 5
100 parts by weight of epoxy resin (1.a), 38 parts by weight of 4-tert-butylphenylglycidyl ether (manufactured by Nagase ChemteX Corporation, Denacol EX-146), phenol novolac resin (manufactured by Dainippon Ink & Chemicals, Inc.) TD-2131) 1 part by weight of triphenylphosphine (TPP) as a curing catalyst was mixed with 57 parts by weight of the mixture, and the resulting mixture was put into a stainless steel mold having a size of 100 mm × 100 mm and a thickness of 1 mm. It was heated in an oven for 1 hour and then at 180 ° C. for 4 hours to be thermally cured. Evaluation similar to the test piece of Example 3 was performed using the obtained molded body (test piece).

Comparative Example 2
100 parts by weight of the epoxy resin (1.a) was changed to 100 parts by weight of the bisphenol fluorene type epoxy resin (5.a) synthesized in Comparative Synthesis Example 1, and 63 parts by weight of a methylhexahydrophthalic anhydride type curing agent. Except that it changed to (2), adjustment of the test piece was attempted in the same manner as in Example 3, but the compatibility with the methylhexahydrophthalic anhydride type curing agent was poor, and the test piece could not be prepared.

Comparative Example 3
In Example 5, 100 parts by weight of the epoxy resin (1.a) was changed to 100 parts by weight of the bisphenolfluorene type epoxy resin (5.a) synthesized in Comparative Synthesis Example 1, and a phenol novolac type curing agent (Dainippon Ink A test piece was prepared in the same manner as in Example 4 except that TD-2131 manufactured by Chemical Industry Co., Ltd. was changed to 63 parts by weight, and the obtained molded body (test piece) was used. Evaluation similar to the test piece was performed.

Example 6
(Synthesis of epoxy acrylate resin)
In a 500 ml four-necked flask, 265 g of the epoxy resin (1.a) obtained in Example 1 (epoxy equivalent 265 g / eq), 1.3 g of triethylbenzylammonium chloride, 140 mg of 2,6-diisobutylphenol, and acrylic acid 72 g was charged and dissolved by heating at 90 to 100 ° C. while blowing air at a rate of 10 mL / min. Next, the temperature was gradually raised to 120 ° C. Although the solution became clear and viscous, stirring was continued as it was. During this time, the acid value was measured, and heating and stirring were continued until the acid value was less than 1.0 mgKOH / g. It took 15 hours for the acid value to reach the target. A pale yellow transparent and solid polyfunctional epoxy acrylate resin (3.a) was obtained.

Comparative Synthesis Example 2
In a 500 ml four-necked flask, 233 g (epoxy equivalent 233 g / eq) of the epoxy resin (5.a) obtained in Comparative Synthesis Example 1, 1.3 g of triethylbenzylammonium chloride, 140 mg of 2,6-diisobutylphenol, and acrylic 72 g of acid was charged and heated and dissolved at 90 to 100 ° C. while blowing air at a rate of 10 mL / min. Next, the temperature was gradually raised to 120 ° C. Although the solution became clear and viscous, stirring was continued as it was. During this time, the acid value was measured, and heating and stirring were continued until the acid value was less than 1.0 mgKOH / g. It took 15 hours for the acid value to reach the target. A pale yellow transparent and solid polyfunctional epoxy acrylate resin (6.a) was obtained.

Example 7
(Preparation and evaluation of cured film using photocurable resin composition containing epoxy acrylate resin)
100 parts by weight of the epoxy acrylate resin (3.a) obtained in Example 6 and 3 parts by weight of Irgacure 907 (manufactured by Ciba Specialty Chemicals Co., Ltd.) were dissolved in PGMEA as a solvent, and the concentration was 30% by weight. It was set as the solution. A solution containing this epoxy acrylate resin was applied on a glass substrate using a spinner and then pre-baked on a hot plate at 90 ° C. for 120 seconds to obtain a coating film having a thickness of about 2 μm. Next, 300 mJ / cm < ² > light was irradiated with the high pressure mercury lamp (400W), and the coating film was hardened. The obtained photocured film was evaluated for the following items.

(1) Refractive index:
About the obtained thermosetting film | membrane, the refractive index in 632.8 nm is measured with an optical interference type film quality measuring device.

(2) Light transmittance:
About the obtained thermosetting film | membrane, the spectral transmission factor in visible region is measured with the Hitachi spectrophotometer U-2000.

(3) Abrasion resistance (abrasion resistance)
While the surface of the thermosetting film on the substrate is lightly pressed with # 1000 steel wool, the steel wool is reciprocated 30 times and rubbed. The degree of scratches on the surface of the coating film is judged according to the following criteria to evaluate the wear resistance.
○: Not scratched △: Scratched but maintained gloss ×: Countless scratches and loss of gloss

(4) Adhesiveness According to JIS-Z-1552, evaluation is made by a cross-cut peel test.

(5) Pencil hardness Pencil hardness is measured according to JIS-K-5400.

(6) Film Shrinkage Ratio Change rate of film thickness before and after post-baking [(film thickness before post-baking−film thickness after post-baking) / (film thickness before post-baking)] × 100.

  Table 4 shows the composition of the composition used in this example, and Table 5 shows the evaluation results of the obtained thin film. Table 8 and Table 5 also show Example 8 and Comparative Example 4 described later.

Example 8
Example except that 100 parts by weight of the epoxy acrylate resin (3.a) in Example 7 was changed to a mixture of 60 parts by weight of the epoxy acrylate resin (3.a) and 40 parts by weight of dipentaerythritol hexaacrylate (DPHA). A thin film was prepared under the same conditions as in No. 7, and evaluated.

Comparative Example 4
A thin film was prepared and evaluated under the same conditions as in Example 7 except that the epoxy acrylate resin (3.a) in Example 8 was changed to a bisphenolfluorene type epoxy acrylate resin (6.a).

Example 9 (Synthesis of alkali-soluble radiation-polymerizable unsaturated resin (A))
After adding and dissolving 115 g of propylene glycol monomethyl ether acetate (PGMEA) in 100 g of the epoxy acrylate resin (3.a) prepared in Example 6, 23.1 g of biphenyltetracarboxylic acid (s-BPDA) and tetraethylammonium bromide 0 .2 g was mixed, and the temperature was gradually raised and reacted at 110 to 115 ° C. for 12 hours. Next, 11.3 g of tetrahydrophthalic anhydride (THPA) was added to the reaction product, and reacted at 90 to 95 ° C. for 4 hours. Thus, a PGMEA solution (7) of an alkali-soluble radiation-polymerizable unsaturated resin was obtained. The disappearance of the acid anhydride was confirmed by IR spectrum.

The following items were evaluated for the PGMEA solution of the obtained alkali-soluble radiation-polymerizable unsaturated resin.

(1) Acid value (mgKOH / g)
About 1 g of PGMEA solution of alkali-soluble radiation-polymerizable unsaturated resin is precisely weighed and dissolved in 30 ml of 1,4-dioxane. Add 2 or 3 drops of 1% phenolphthalein ethanol solution as an indicator and perform neutralization titration with 0.1N sodium hydroxide solution. The acid value is determined by the following formula.
Acid value (mgKOH / g) = (0.1N sodium hydroxide solution titration (ml) × 0.1N sodium hydroxide solution factor × 0.1 × 56.11) / sample amount (g)

(2) Determined by average molecular weight GPC measurement. The average molecular weight is calculated from a calibration curve prepared with polystyrene standards.

(3) Color (APHA)
Measured using a color difference / turbidity measuring device COH-300A manufactured by Nippon Nippon Denshoku Industries Co., Ltd. and a special 1 cm glass cell.

(4) Solid content (%)
About 1 g of PGMEA solution of an alkali-soluble radiation-polymerizable unsaturated resin is precisely weighed in an aluminum petri dish and dried under reduced pressure at 20 mmHg or less for 2 hours in a vacuum dryer set at 140 ° C. Before weighing the sample, the weight of the aluminum petri dish is measured in advance. The solid content is determined by the following formula.
Solid content (%) = (weight of sample including weight of aluminum petri dish after drying (g) −weight of petri dish made of aluminum (g)) / sample collection amount (g) × 100

  The results are shown in Table 6. The results of Examples 10 to 14 and Comparative Synthesis Examples 3 to 5 described later are also shown in Table 6.

Example 10
In Example 9, except that biphenyltetracarboxylic acid (s-BPDA) was changed to 19.0 g, the same reaction as in Example 9 was performed to obtain an alkali-soluble radiation-polymerizable unsaturated resin PGMEA solution (8). Obtained.

Example 11
In Example 9, the same as Example 9 except that biphenyltetracarboxylic acid (s-BPDA) was changed to 16.3 g of pyromellitic anhydride (PMDA) and 12.5 g of tetrahydrophthalic anhydride (THPA). Reaction was performed to obtain a PGMEA solution (9) of an alkali-soluble radiation-polymerizable unsaturated resin.

Example 12 (Synthesis of alkali-soluble radiation-polymerizable unsaturated resin (B))
After 115 g of propylene glycol monomethyl ether acetate (PGMEA) was added to 100 g of the epoxy acrylate resin (3.a) prepared in Example 6 and dissolved, 1.0 g of ditrimethylolpropane and biphenyltetracarboxylic acid (s-BPDA) 24. 3 g and tetraethylammonium bromide 0.2 g were mixed, and this was gradually heated and reacted at 110 to 115 ° C. for 12 hours. Next, 11.8 g of tetrahydrophthalic anhydride (THPA) was added to the reaction product, and reacted at 90 to 95 ° C. for 4 hours. Thus, a PGMEA solution (10) of an alkali-soluble radiation-polymerizable unsaturated resin was obtained. The disappearance of the acid anhydride was confirmed by IR spectrum.

Example 13
In Example 12, the same reaction as in Example 12 was performed except that biphenyltetracarboxylic acid (s-BPDA) was changed to 18.0 g of pyromellitic anhydride (PMDA), and an alkali-soluble radiation-polymerizable unsaturated resin was obtained. Of PGMEA solution (11) was obtained.

Example 14
In Example 12, 17.0 g of biphenyltetracarboxylic acid (s-BPDA) was pyromellitic anhydride (PMDA), 0.66 g of ditrimethylolpropane was 0.66 g of trimethylolethane, and 13.2 g of tetrahydrophthalic anhydride (THPA). A reaction similar to that of Example 12 was performed except that the PGMEA solution (12) of an alkali-soluble radiation-polymerizable unsaturated resin was obtained.

Comparative Synthesis Example 3
After adding and dissolving 115 g of propylene glycol monomethyl ether acetate (PGMEA) in 100 g of the epoxy acrylate resin (6.a) prepared in Comparative Synthesis Example 2, 25.7 g of biphenyltetracarboxylic acid (s-BPDA) and tetraethylammonium bromide 0.2g was mixed, this was heated up gradually, and it was made to react at 110-115 degreeC for 12 hours. Next, 12.5 g of tetrahydrophthalic anhydride (THPA) was added to the reaction product, and reacted at 90 to 95 ° C. for 4 hours.
Thus, a PGMEA solution (913) of an alkali-soluble radiation-polymerizable unsaturated resin was obtained. The disappearance of the acid anhydride was confirmed by IR spectrum.

Comparative Synthesis Example 4
Comparative Synthesis Example 3 was the same as Comparative Synthesis Example 3 except that biphenyltetracarboxylic acid (s-BPDA) was pyromellitic anhydride (PMDA) 18.0 g and tetrahydrophthalic anhydride (THPA) was 14.1 g. A similar reaction was performed to obtain a PGMEA solution (14) of an alkali-soluble radiation-polymerizable unsaturated resin.

Comparative Synthesis Example 5
After adding and dissolving 115 g of propylene glycol monomethyl ether acetate (PGMEA) in 100 g of the epoxy acrylate resin (6.a) prepared in Comparative Synthesis Example 2, 0.66 g of trimethylolethane and 18.8 g of pyromellitic anhydride (PMDA) And 0.2 g of tetraethylammonium bromide were mixed, and the temperature was gradually raised and reacted at 110 to 115 ° C. for 12 hours. Next, 14.8 g of tetrahydrophthalic anhydride (THPA) was added to the reaction product, and reacted at 90 to 95 ° C. for 4 hours. In this way, a PGMEA solution (15) of an alkali-soluble radiation-polymerizable unsaturated resin was obtained. The disappearance of the acid anhydride was confirmed by IR spectrum.

Example 15
(Preparation and evaluation of thin films using compositions containing alkali-soluble radiation-polymerizable unsaturated resins)
30 parts by weight of the alkali-soluble radiation-polymerizable unsaturated resin (7) obtained in Example 9 as a solid content, 15 parts by weight of dipentaerythritol hexaacrylate (DPHA), 3 parts by weight of Irgacure 907, solvent Was dissolved in PGMEA to obtain a solution having a concentration of 30% by weight. This solution was applied onto a glass substrate using a spinner and then pre-baked on a hot plate at 90 ° C. for 120 seconds to form a coating film having a thickness of about 2 μm. A mask having a predetermined pattern is placed on the surface of the glass substrate having the coating film, and an ultraviolet ray having a light intensity of 9.5 mW / cm ^{2 is} emitted at a wavelength of 405 nm using a 250 W high-pressure mercury lamp in a nitrogen atmosphere. Irradiation was performed so that the energy amount was 1000 mJ / cm ² . Subsequently, development processing was performed at 25 ° C. for 30 seconds using a 1% by weight aqueous sodium carbonate solution to remove unexposed portions of the coating film. Then, the rinse process was performed with the ultrapure water. The obtained substrate having the thin film was placed in an oven at 200 ° C., post-baking was performed for 30 minutes, and the thin film was heat-cured (hereinafter, the film thus cured is referred to as a heat-cured film).

  The evaluation at the time of preparation of the heat-cured thin film in this example and the evaluation of the obtained cured film were performed for the following items.

<1> Drying property of coating film The drying property of the coating film after the pre-baking is evaluated according to JIS-K-5400. The rank of evaluation is as follows.
○: No sticking is observed △: Slight sticking is recognized ×: Remarkably sticking is recognized

<2> Developability with respect to alkaline aqueous solution The glass substrate having the coating film is developed by immersing it in a 1% by weight sodium carbonate aqueous solution for 30 seconds without exposure treatment. The glass substrate after development is magnified 50 times and the remaining resin is visually evaluated. The rank of evaluation is as follows.
○: Developability is good (no resin remains on the glass)
Δ: Developability is poor (slight resin remains on the glass)
X: Developability is poor (a lot of resin remains on the glass)

<3> Exposure sensitivity A step tablet (negative mask with 12 steps of optical density) is brought into close contact with the coating film as the mask, and exposure and development are performed. Thereafter, the number of steps of the remaining step tablet is examined (in this evaluation method, the higher the sensitivity, the larger the number of remaining steps).

<4> Coating film hardness The hardness of the obtained heat-cured film was scratched on the coating film when a load of 9.8 N was applied using a pencil hardness tester according to the test method of JIS-K-5400. Display with the highest hardness not attached. The pencil used is "Mitsubishi High Uni".

<5> Adhesiveness to the substrate The resulting heat-cured film is cross-cut so as to make at least 100 squares, and then a peeling test is performed using cello tape (registered trademark). The state of peeling is evaluated by magnifying it 50 times with an optical microscope. The rank of evaluation is as follows.
○: No peeling at all ×: Even a little peeling is recognized

<6> Heat resistance The obtained heat-cured film is placed in an oven at 250 ° C. for 3 hours and cured and baked. Film thickness change rate before and after cure baking [(film thickness before cure baking−film thickness after cure bake) / (film thickness before cure bake)] × 100. The rank of evaluation is as follows.
A: The rate of change in film thickness is very low (the rate of change in film thickness is less than 3%)
◯: Low film thickness change rate (film thickness change rate of 3% to less than 5%)
Δ: Film thickness change rate is slightly high (film thickness change rate of 5% or more and less than 10%)
X: High film thickness change rate (10% or more film thickness change rate)

<7> Heat-resistant discoloration property The obtained heat-cured film is placed in an oven at 250 ° C. for 3 hours and cured and baked. The light transmittance before and after cure baking is measured at a wavelength of 400 to 700 nm using a spectrophotometer “U-2000 (manufactured by Hitachi, Ltd.)”. The change in transmittance is obtained by the following equation.
Change in transmittance = [(transmittance before heating−transmittance after heating) / transmittance before heating] × 100 (%)
◎: Change in transmittance is less than 3% ○: Change in transmittance is in the range of 3% or more and less than 5% Δ: Change in transmittance is in the range of 5% or more and less than 10% ×: The change in transmittance is 10% or more

<8> Chemical resistance The obtained substrate having a heat-cured film is immersed in the following chemicals under the following conditions.
(i) Acidic solution: immersed in 5 wt% HCl aqueous solution at room temperature for 24 hours
(ii) Alkaline solution
ii-1: Immersion in 5 wt% NaOH aqueous solution at room temperature for 24 hours
ii-2: Immersion in 4 wt% KOH aqueous solution at 50 ° C for 10 minutes
ii-3 Soaked in 1 wt% NaOH aqueous solution at 80 ° C for 5 minutes
(iii) Solvent
iii-1: Immersion in N-methylpyrrolidone at 40 ° C. for 10 minutes
iii-2: Immersion in N-methylpyrrolidone at 80 ° C. for 5 minutes Film thickness change rate (%) before and after immersion ((film thickness before immersion−film thickness after immersion) / (film thickness before immersion)) × 100 is determined. Chemical resistance is evaluated based on the calculated film thickness change rate. The criteria for evaluation are as follows.
A: Excellent in chemical resistance (thickness change rate in all solutions is less than 3%)
○: Excellent chemical resistance (change rate of film thickness in all solutions 3% to less than 5%)
Δ: Chemical resistance is slightly inferior (the film thickness change rate in any solution is 5% or more and less than 10%)
X: Inferior in chemical resistance (thickness change rate of 10% or more in any solution)

  The results are shown in Table 7. The results of Examples 16 to 22 and Comparative Examples 5 to 7 described later are also shown in Table 7.

Example 16
A thin film was prepared and evaluated under the same conditions as in Example 15 except that dipentaerythritol hexaacrylate was changed to trimethylolpropane triacrylate (TMPTA).

Example 17
Furthermore, a thin film was prepared and evaluated under the same conditions as in Example 15 except that a composition containing 6 parts by weight of tetramethylbiphenyl type epoxy resin (Epicoat YX-4000 manufactured by Japan Epoxy Resin Co., Ltd.) was used. .

Example 18
Under the same conditions as in Example 15, except that the alkali-soluble radiation-polymerizable unsaturated resin (7) was changed to the alkali-soluble radiation-polymerizable unsaturated resin (8) obtained in Example 10. A thin film was prepared and evaluated.

Example 19
Under the same conditions as in Example 15, except that the alkali-soluble radiation-polymerizable unsaturated resin (7) was changed to the alkali-soluble radiation-polymerizable unsaturated resin (9) obtained in Example 11. A thin film was prepared and evaluated.

Example 20
Under the same conditions as in Example 15 except that the alkali-soluble radiation-polymerizable unsaturated resin (7) was changed to the alkali-soluble radiation-polymerizable unsaturated resin (10) obtained in Example 12. A thin film was prepared and evaluated.

Example 21
Under the same conditions as in Example 15, except that the alkali-soluble radiation-polymerizable unsaturated resin (7) was changed to the alkali-soluble radiation-polymerizable unsaturated resin (11) obtained in Example 13. A thin film was prepared and evaluated.

Example 22
Under the same conditions as in Example 15, except that the alkali-soluble radiation-polymerizable unsaturated resin (7) was changed to the alkali-soluble radiation-polymerizable unsaturated resin (12) obtained in Example 14. A thin film was prepared and evaluated.

Comparative Example 5
In Example 15, except that the alkali-soluble radiation-polymerizable unsaturated resin (7) was changed to the bisphenolfluorene-type alkali-soluble radiation-polymerizable unsaturated resin (13) synthesized in Comparative Synthesis Example 3. A thin film was prepared and evaluated under the same conditions as in Example 15.

Comparative Example 6
In Example 15, except that the alkali-soluble radiation-polymerizable unsaturated resin (7) was changed to the bisphenolfluorene-type alkali-soluble radiation-polymerizable unsaturated resin (14) synthesized in Comparative Synthesis Example 4 , A thin film was prepared and evaluated under the same conditions as in Example 15.

Comparative Example 7
In Example 15, except that the alkali-soluble radiation-polymerizable unsaturated resin (7) was changed to the bisphenolfluorene-type alkali-soluble radiation-polymerizable unsaturated resin (15) synthesized in Comparative Synthesis Example 5. A thin film was prepared and evaluated under the same conditions as in Example 15.

  As is clear from the results of Tables 1 to 6, when the fluorene-containing resin of the present invention is used, it has high hardness, high transparency, high level of heat resistance and electrical properties, and low degree of curing shrinkage. It turns out that a molded object and a cured thin film are obtained. Furthermore, it is clear that 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 the substrate by exposure and development. In particular, it is clear that the heat discoloration is further improved by using the alkali-soluble radiation-polymerizable unsaturated resin of the present invention to which a polyhydric alcohol is added.

^{1 is} a ¹ H-NMR chart of a fluorene-containing epoxy resin of the present invention. It is a ¹³ C-NMR chart of the fluorene-containing epoxy resin of the present invention. It is a FD-MS chart of the fluorene-containing epoxy resin of the present invention.

Claims (19)

The following general formula (1):

(In the formula, n is an integer of 0 to 10). It is a manufacturing method of the fluorene containing epoxy resin of Claim 1, Comprising: The following general formula (2):

A method comprising a step of allowing epichlorohydrin to act on the fluorene compound represented by the formula: An epoxy resin composition comprising the fluorene-containing epoxy resin according to claim 1. The molded object obtained by hardening the epoxy resin composition of Claim 3. The following general formula (3):

(Wherein R ₁ and R ₂ are each independently a hydrogen atom or a methyl group, and n is each independently an integer of 0 to 10). It is a manufacturing method of the fluorene containing epoxy acrylate resin of Claim 5, Comprising: The following general formula (1):

A method comprising a step of allowing (meth) acrylic acid to act on a fluorene-containing epoxy resin represented by the formula (wherein n is an integer of 0 to 10). It is a manufacturing method of the fluorene containing epoxy acrylate resin of Claim 5, Comprising: The following general formula (2):

A method comprising a step of allowing glycidyl (meth) acrylate to act on the fluorene compound represented by formula (1). A thermosetting composition containing the fluorene-containing epoxy acrylate resin according to claim 5. A radiation-sensitive resin composition containing the fluorene-containing epoxy acrylate resin according to claim 5. The molded object obtained by hardening the composition of Claim 8 or Claim 9. The following general formula (3):

(Wherein R ₁ and R ₂ are each independently a hydrogen atom or a methyl group, and n is each independently an integer of 0 to 10), a polybasic carboxylic acid or A fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin obtained by reacting the anhydride. A method for producing a fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin according to claim 11, wherein the following general formula (3):

(Wherein R ₁ and R ₂ are each independently a hydrogen atom or a methyl group, and n is each independently an integer of 0 to 10), a polybasic carboxylic acid or A process comprising reacting the anhydride. The following general formula (3):

(Wherein R ₁ and R ₂ are each independently a hydrogen atom or a methyl group, and n is each independently an integer of 0 to 10), and a mixture of a polyhydric alcohol and a fluorene-containing epoxy acrylate resin A fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin obtained by reacting a polybasic carboxylic acid or its anhydride. The following general formula (3):

(Wherein, R ₁ and R ₂ are each independently a hydrogen atom or a methyl group, and n is each independently an integer of 0 to 10) and a hydroxyl group of a fluorene-containing epoxy acrylate resin and a hydroxyl group of a polyhydric alcohol The fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin according to claim 13, wherein the molar ratio is 99/1 to 50/50. The polyhydric alcohol is one or two or more polyhydric alcohols selected from trimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol. The fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin described. A method for producing a fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin according to claim 13, wherein the following general formula (3):

(Wherein R1 and R2 are each independently a hydrogen atom or a methyl group, and n is each independently an integer of 0 to 10), a mixture of a fluorene-containing epoxy acrylate resin and a polyhydric alcohol A method comprising a step of reacting a basic carboxylic acid or an anhydride thereof. A radiation-sensitive resin composition containing the fluorene-containing alkali-soluble radiation-polymerizable unsaturated resin according to any one of claims 11 and 13 to 15. The interlayer insulation film of the liquid crystal display formed with the radiation sensitive resin composition of Claim 17. The protective film of the liquid crystal display formed with the radiation sensitive resin composition of Claim 17.

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