TW201202276A - Thermocurable resin composition containing (meth) acrylate resin and cured article using the same - Google Patents

Abstract

An objective of this invention is to provide a thermocurable resin composition having excellent transparency, light resistance, weather resistance, heat resistance, flatness, surface hardness and adhesiveness. A thermocurable resin composition of this invention is essentially consisted of (i) a (meth) acrylate resin containing a polymerizable double bond which is obtained by bringing a (meth) acrylate compound having epoxy groups and represented by the general formula (3) into reaction with a part of a carboxylic group of a copolymer of a (meth)acrylate compound represented by the general formula (1) and a (meth) acrylic acid compound represented by the general formula (2), (ii) a polymerizable compound having at least one polymerizable double bond other than the (meth) acrylate resin containing a polymerizable double bond, and (iii) thermal polymerization initiator, and (iv) silane coupling agnet. (provided that R1 represents hydrogen atom or methyl group; R2 represents a hydrocarbon group having a carbon number of 1 to 20, and may contain ether type oxygen atom and urethane bond therein.) (provided that R1 represents hydrogen atom or methyl group.) (provided that R1 represents hydrogen atom or methyl group; R3 represents a divalent hydrocarbon group having a carbon number of 2 to 10; p represents a number of 0 or 1.)

Description

201202276 VI. Description of the Invention: The present invention relates to a thermosetting resin composition which is characterized by having (meth)acrylic acid vinegar and (mercapto)acrylic acid as a constituent unit. A (meth) acrylate resin having a polymerizable double bond is an essential component, and is excellent in optical properties, hardness, adhesion, light resistance, and the like. [Prior Art] For surface protection materials such as a protective film for a color filter, a hard coat material, and a sealing material for an organic device, transparency, light resistance, weather resistance, heat resistance, and flatness are sought. Sex, surface hardness, adhesion, etc. In addition, in the case where the flat panel display ((5)-dance display is continuously required] in recent years, the characteristics required for the surface protective material are becoming higher, and the required items are more diverse. Examples of the material used for the surface protective material include an epoxy resin, an anthracene resin, and a (fluorenyl) acrylate resin. For example, Patent Document i discloses a thermosetting resin using an epoxy resin having a structure of 0, which has a high heat resistance, but the transmittance from an aromatic short-wavelength region may be lowered. Patent Document 2 discloses a thermosetting resin having a time-based epoxy compound, which has sufficient surface hardness, but may be affected by an ionic component derived from a (4) acid generator as a heat and photoinitiator. A thermosetting resin of a copolymer of (fluorenyl)acrylic acid and a (fluorenyl)acrylic acid vinegar having an epoxy group may be insufficient in adhesion of the obtained protective film. [Prior Art Document] 323095 5 201202276 [Patent Document] Patent Document 1 JP-A-2004-69930 Patent Document 2: Japanese Patent Laid-Open Publication No. Hei No. Hei. [Invention] [Problems to be Solved] In order to solve the above-mentioned problem of the conventional resin composition, the present inventors have tried to study the results of the results, and found that (fluorenyl) acrylic vinegar compound and (mercapto) a part of the rebel group in the copolymer of the acrylic acid compound, reacting the (indenyl) propyl vinegar compound having an epoxy group to obtain a (meth) propylene resin containing a poly-human double bond, (4) The (meth)acrylic acid vinegar resin containing a polymerizable i bond can have surface hardness, adhesion transparency, and light resistance while maintaining the transparency of (meth)acrylic acid acrylate. In addition, the adhesion resistance is excellent heat. Therefore, an object of the present invention is to provide a weatherable, surface-hardenable, and surface-hardenable resin composition. That is, the purpose of providing a non-producing 匕 为 为 、 、 、 、 、 、 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 ( ( ( ( ( ( ( ( = = = = = = = = (3) The following (1), (ii), (iii), and (iv) (i) ((y), (m) acrylate compound represented by the formula (1) 323095 6 201202276 of the copolymer of the (meth)propane-compound, the polymerizable double obtained by reacting the (meth) acrylate compound having an epoxy group represented by the general formula (3) Key (meth) acrylate resin; Ri T R2 ( 1 ) (except that R! represents a hydrogen atom or a fluorenyl group. 匕 represents a hydrocarbon group having 1 to 20 carbon atoms, and may also contain an oxygen atom in its interior, or A urethane bond) into C02H, (only h represents a hydrogen atom or a methyl group)

(惟, 匕 represents a hydrogen atom or a fluorenyl group. R3 represents a divalent hydrocarbon group having 2 to 1 carbon atoms, and P represents a number of 0 or 1). (ii) a polymerizable compound having at least one polymerizable double bond other than the (meth) acrylate resin containing a polymerizable double bond; (iii) a thermal polymerization initiator; and (iv) a decane coupling agent. Preferred embodiments of the invention are as follows. In the above-mentioned thermosetting resin composition, R2 in the formula (1) is a hydrocarbon group having 1 to 20 carbon atoms which may further contain an etheric oxygen atom or a urethane bond, and is preferably straight. Further, the chain or cyclic aliphatic hydrocarbon group, and r3 in the formula (3) is a divalent hydrocarbon group having a carbon number of 2 to 10, preferably an aliphatic hydrocarbon group having 2 to 10 carbon atoms. 323095 7 201202276 In addition, the present invention may be a thermosetting resin composition containing, in addition to the above components (1) to (IV), an epoxy resin having two or more epoxy groups. Epoxy compound. Further, the present invention is a cured product obtained by applying and hardening the above thermosetting resin composition. (Effects of the Invention) The thermosetting resin composition of the present invention contains a (meth)acrylic acid compound represented by the formula (2) and a (meth)acrylic acid compound represented by the formula (2). A part of a carboxyl group in the copolymer is a (fluorenyl) acrylate resin containing a polymerizable double bond obtained by reacting an epoxy group-containing (mercapto) acrylic acid vinegar compound represented by the formula (3). When it is used in the field of electronic materials and the like, it is possible to obtain a cured product which is excellent in heat resistance, flatness, surface hardness, adhesion, and the like while maintaining transparency. Therefore, the thermosetting resin composition of the present invention is extremely useful as a protective film or a sealing material for a semiconductor device such as a color filter-related material. [Embodiment] Hereinafter, the thermosetting resin composition of the present invention will be described in detail. The thermosetting resin composition of the present invention contains a part of a carboxyl group in a copolymer of a (fluorenyl) acrylate compound represented by the formula (1) and a (fluorenyl) acrylate compound represented by the formula (2). A resin composition containing a polymerizable double bond-containing (fluorenyl) acrylate resin obtained by reacting an epoxy group-containing (meth) acrylate compound represented by the formula (3) as a main component. The (meth) acrylate resin containing a poly 8 323095 201202276 conjugated double bond contained as a main component in the thermosetting resin composition of the present invention has a (meth) group derived from an epoxy group as described later. The polymerizable double bond of the acrylate compound has a radical polymerizability. The (fluorenyl) acrylate resin containing a polymerizable double bond of the present invention is a part of a carboxyl group in a copolymer of a (meth) acrylate compound and a (meth) acryl compound, and has an epoxy group. The acrylate compound is reacted to obtain a (fluorenyl) acrylate resin containing a polymerizable double bond. The method for producing a (meth) acrylate resin containing a polymerizable double bond of the present invention will be described in detail. First, the (meth) acrylate resin containing a polymerizable double bond of the present invention is obtained by using a (meth) acrylate compound represented by the formula (1) and a thiol group represented by the formula (2). The polyvalent carboxylic acid compound represented by the following formula (4) obtained by copolymerization of an acrylic compound is derived. This polycarboxylic acid is substantially composed of a constituent component derived from a (meth) acrylate compound represented by the formula (1) and a constituent component derived from a (fluorenyl) acrylate compound represented by the formula (2). The (random) way is combined into a copolymer. As the method of copolymerization, a known copolymerization method can be employed. The constituent unit k of the (meth) acrylate compound represented by the formula (1) and the (meth) acrylate compound represented by the formula (2) in the polyvalent carboxylic acid compound represented by the formula (4) When the constituent unit n (k, η represents an arbitrary integer), the total of k and η is 100 in consideration of the reaction of the (fluorenyl) acrylate compound having an epoxy group represented by the following formula (3). k is preferably from 20 to 70.

S 323095 201202276

(wherein L each independently represents a hydrogen atom or a fluorenyl group. R2 each independently represents a hydrocarbon group having 1 to 20 carbon atoms, and may further contain an etheric oxygen atom or an amino phthalate bond in the interior thereof. k, η Represents an arbitrary integer). Ri of the (fluorenyl) acrylate compound represented by the formula (1) each independently represents a hydrogen atom or a methyl group. Further, 匕 represents a hydrocarbon group having 1 to 20 carbon atoms, and may also contain an etheric oxygen atom or a urethane bond in its interior. Examples of such hydrocarbon groups include mercapto, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, isooctyl, decyl, dodecyl, and tetradecane. Linear hydrocarbon group such as tetradecyl or eicosyl; cyclohexyl, norbornyl, isobornyl, tricyclodecyl fluorenyl, decahydronaphthyl, the following formula (5) a cyclic aliphatic hydrocarbon group such as a substituent; an aliphatic ether such as a nonyloxyethyl group or a 2-(methoxyethoxy group); or an aliphatic group such as a 2-(ethoxycarbonylamino)ethyl group; Amine esters are not limited to these. R2 of the formula (1) is preferably an anthracenyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a cyclohexyl group, a norbornyl group, an isobornyl group, or a tricyclodecylfluorenyl group. Two or more kinds of the (meth) acrylate compounds represented by the above formula (1) may be used. Further, Ri of the (fluorenyl)acrylic acid compound represented by the formula (2) each independently represents a hydrogen atom or a methyl group, and one type or two types may be used. 10 323095 201202276 I Ri C>iHX) (5) (However, R! represents an argon atom or a methyl group.) Next, a compound of the (meth)acrylic acid S represented by the formula (1) is used. A polycarboxylic acid compound represented by the formula (4) obtained by copolymerization of a (fluorenyl)acrylic acid compound represented by the formula (2), and a (fluorenyl) acrylate compound having an epoxy group represented by the formula (3) A method for producing a (meth) acrylate resin containing a polymerizable double bond obtained by the reaction will be described. When a part of the carboxyl group in the polyvalent carboxylic acid compound represented by the formula (4) is reacted with a (fluorenyl) acrylate compound having an epoxy group represented by the formula (3), the following formula (6) is obtained. ) A (fluorenyl) acrylate resin containing a polymerizable double bond. In the following general formula (6), the constituent component of the (meth) acrylate compound represented by the formula (1), the component derived from the (meth) acrylate compound represented by the formula (2), and The constituent component of the (meth) acrylate compound having an epoxy group represented by the general formula (3), the order of bonding of the three constituent components is not particularly regular, and basically consists of three constituent components. The method is combined into a copolymer.

(H represents a hydrogen atom or a fluorenyl group. R2 represents a hydrocarbon group having 1 to 20 carbon atoms, and may also contain an etheric oxygen atom or an amino phthalate bond in the interior thereof. R3 represents a carbon 11 323095 201202276 number 2 to 10 A divalent hydrocarbon group, p represents a number of 〇 or 1. k, l, m represent an arbitrary integer). In the epoxy group-containing (meth) acrylate compound represented by the formula (3), Rs represents a divalent hydrocarbon group having 2 to 10 carbon atoms. Examples of such a hydrocarbon group include an ethyl group (6: 716116), a 1,2-propyl group, a 1,4-butylene group, a 1,6-extension group, etc., preferably an ethyl group, a 1,2- Propylene, or 1,4-butylene. p represents the number of 0 or 1. When a (meth) acrylate compound having an epoxy group represented by the formula (3) is reacted with a part of a carboxyl group in the polyvalent carboxylic acid compound represented by the formula (4), the solvent to be used, The reaction conditions such as a catalyst are not particularly limited, but a solvent having a boiling point higher than the reaction temperature is preferably used as a reaction solvent. As such a solvent, for example, ethyl cellosolve acetate may be used. Ethylene glycol butyl (cellosolve acetate) such as butyl (cellosolve) solvent or diglyme, ethyl carbi to 1 acetate a high-boiling ether or vinegar-based solvent such as butyl carbitol acetate, propylene glycol mono-methyl ether acetate, methyl lactate or butyl acetate, or a cyclohexane A ketone-based solvent such as a ketone or diisobutyl ketone. Further, as the catalyst to be used, for example, tetraethylammonium bromide, vaporized triethylbenzoquinone, and the like, triphenylphosphine, tris(2,6-dimethoxyphenyl) can be used. A well-known person such as a phosphine such as a phosphine. These are described in detail in Japanese Patent Laid-Open No. Hei 9-325494. The general formula (6) is produced by reacting a polyvalent carboxylic acid compound represented by the formula (4) with an epoxide group-containing (meth) λ τ roll acrylate compound represented by the formula (3): 323095 12 201202276 The reaction temperature = 1 ^ in the case of Yushe &amp; polyfluorene double-bonded (fluorenyl) acrylate resin is added to the range of U 〇 ° C, more preferably 40 to 130 ° C. At the time of manufacture: (S) of the (M) acrylic acid vinegar resin having a polymerizable double bond in the rain, and the Tr-containing compound represented by the formula (6) The ratio of the loading ratio can be arbitrarily changed in the polybasic phthalic acid compound of the (meth) propyl sulphate of the above-mentioned acid value and the curable target double bond. At this time, the ratio of the epoxy group having 50 mM of the epoxy group shown in the above-mentioned "fluorenyl group" is preferably 1 Torr to the other. f : Mole%. The number of (meth) units containing a polymerizable double bond in all of the acrylic resin resins can be adjusted by adjusting the acid value and hardness as 1〇&quot;, and each composition is preferably: (1^ </ RTI> arbitrarily change == in the unit of k, the unit k is from 20 to 70; the constituent unit of the formula of the formula C2, the base of the acrylic acid brewing compound is 10 to 5{f; (4) Acid compound-based (meth) acrylate compound The epoxy group represented by the formula (3) has a larger epoxy resin than the above range, and there is a fear that polymerization == two to the problem that the adhesion and hardness of the material are lowered. Further, when the solid content is large, the water absorption rate of the cured product becomes high, and the right side has a lower solubility than the above. Further, if m occurs, the volume shrinkage of the organic solvent becomes large, and the problem of deterioration in flatness with the substrate: = : hardening occurs. Further, the average molecular weight of the (meth)acrylic resin-containing resin having a polymerizable double bond 323095 13 201202276 represented by the formula (6) having a low general formula f or a surface is preferably 1 〇, _ 100, 000. If the average molecular weight is less than the above range, the density may be lowered. Further, when the average molecular weight is larger than the above range, the hardenability may be lowered. The resin component of the thermosetting resin composition of the present invention may contain a (meth) acrylate resin containing a polymerizable double bond represented by the formula (6) as an essential component, and the formula (6) The component other than the resin may be a resin component or a non-resin component such as a solvent or a filler. Here, the resin component means a component which becomes a resin by polymerization or hardening, and examples thereof include an epoxy resin or an acrylic resin which is polymerized or cured by light or heat. ^ In addition, the component of the tree a contains oligomers and monomers in addition to the resin. In order to utilize the characteristics of the thermosetting resin composition, the following (i), (ii), (iii) and (iv) are contained as essential components. In other words, the following (i), (ii), (iii), and (iv) are included as essential components: (i) (meth) acrylate resin containing a polymerizable double bond, (ii) the above-mentioned polymerization-containing A polymerizable compound having at least one polymerizable double bond, (iii) a thermal polymerization initiator, and (iv) a decane coupling agent other than a (fluorenyl) acrylate resin having a double bond. Here, as the polymerizable compound having at least one polymerizable double bond as the component (ii), first, a polymerizable monomer having at least one polymerizable double bond (ii-a), for example, may be exemplified. Such as: (mercapto) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate and other monomers having a hydroxyl group; or pentaerythritol triacrylate 14 323095 201202276 and Liu Ya An adduct of hexamethylene diisocyanate, an adduct of dipentaerythritol pentaacry late and a hexamethylene diisocyanate, and an amine (meth)acrylic acid Urethane (meth)acrylate; ethylene glycol di(meth)acrylate, diethylene glycol di(mercapto)acrylate, triethylene glycol di(meth)acrylate, tetraethylene Alcohol bis(indenyl) acrylate, tetramethylene glycol bis(indenyl) acrylate, trishydroxypropyl propane tris(decyl) acrylate, trimethylolethane tris(decyl) acrylate, new Pentaerythritol bis(indenyl) acrylate, neopentyl alcohol three ( Mercapto) acrylate, pentaerythritol tetrakis(mercapto) acrylate, dipentaerythritol tetrakis(mercapto) acrylate, dipentaerythritol hexa(meth) acrylate, glycerol A (mercapto) acrylate of a polyhydric alcohol such as a methyl acrylate may be used alone or in combination of two or more. Further, in addition to the above (ii-a), the (i-b) polymerizable oligomer or resin component having at least one polymerizable double bond (except for the structure of (i)) may, for example, be as follows: Epoxy acrylate of bisphenol A type epoxy resin, epoxy acrylate of bisphenol fluorene type epoxy resin, epoxy acrylate of phenol novolac type epoxy resin, epoxy group An epoxy (acrylic) acrylate resin such as epoxy acrylate or the like; a reactant of an epoxy acrylate of an bisphenol A epoxy resin and an acid anhydride a reaction of an epoxy acrylate of an bisphenol type epoxy resin with an acid anhydride, a reaction of an epoxy acrylate of an phenol novolak type epoxy resin with an acid anhydride, and an epoxy of an epoxy polyoxo resin An acid anhydride modified resin of an epoxy (meth)acrylic resin such as a reactant of an acrylate and an acid anhydride; poly(diallyl phthalate) 15 323095 201202276 (poly(diallyl phthalate)), poly(diethylene Base benzene), etc. containing allyl or ethylene Vinyl resin. These compounds may be used alone or in combination of two or more. As the polymerizable compound having at least one polymerizable double bond as the (Π) component, either one of the above-mentioned (ii-a) and (ii-b) may be used, or both may be used in combination. When the exemplified ones are used together with the exemplified ones, the ratio of (ii-a) and (ii-b) can impart transparency and light resistance to the cured product obtained by curing the thermosetting resin composition of the present invention. The weight ratio [(ii-a)/(ii-b)] of the component and the component (ii_b) is preferably arbitrarily changed for the purpose of weather resistance, heat resistance, flatness, surface hardness, adhesion, and the like. 20/80 to 70/30. Here, in the case of producing a thermosetting resin composition for obtaining a cured product having a surface hardness, the above (Io-a) is preferably an amine ester (mercapto) acrylate or a polyol (曱) Base) acrylates. Further, in the case of producing a thermosetting resin composition for obtaining a cured product having both transparency and low gas yield, the above (ii-b) is preferably a bisphenol represented by the following formula (7). A double-type epoxy such as a reaction of an epoxy (mercapto) acrylate of an epoxy resin with an acid anhydride, a reaction of an epoxy (meth) acrylate with a bisphenol type epoxy resin, and an acid needle A reaction of an epoxy (methyl) (tetra) (iv) resin with an acid anhydride. Here, the low gas-producing system of the present invention means that the cured product obtained by hardening the thermosetting (10) test material of the present invention has a reduced weight when heated, and is, for example, a protective film for a color filter, a hard coated material, or an organic One of the indicators of the reliability of a surface protective material such as a sealing material for a device. 323095 16 201202276

-y H02c C〇2H

(7 (only, each independently represents a hydrogen atom or a double-radical 7 derived from a double-epoxy group represented by the table (8)), and a new residue of the formula 4, wherein Z represents a hydrogen atom or a group below. .a is a substitution of 1 to 50)

(Rightly, 'R5, R6, R7 and R8 each independently represent a hydrogen atom, an alkyl group to which a carbon number is bonded, a halogen atom or a phenyl group. X represents _c〇1, -S 腾, -, 卿, 一. 9 9-fluorene-diyl) or direct bond. b represents 〇 to 15 —?-.2H)q (9) (only 'L represents a 2 or 3 carboxylic acid residue. q is 1 or 2). The compounding weight ratio [(i)/(ii)] of the component (i) to the component (ii) is preferably 5/95 to 60/40, more preferably 5/95 to 50/50. When the proportion of the (fluorenyl) acrylate resin containing a polymerizable double bond (i) is small, the cured product after hardening has a problem of embrittlement. In contrast, when the proportion of the (fluorenyl) acrylate resin containing a polymerizable double bond in (i) is more than the above range, there is a fear that the proportion of the curable functional group in the resin is reduced. A problem that the formation of the crosslinked structure is insufficient. 323095 17 201202276 Further, as the thermal polymerization initiator of the component (iii), for example, benzoyl peroxide, laurel peroxide, and di(t-butylperoxide) hexahydrop-benzoquinone can be used. Organic peroxides such as acid esters, tert-butyl-2-ethylhexanoate peroxide, 1, 1-butyl-1-butyl-3,3,5-trimethylcyclohexane; azobis Azobisisobutyronitrile, azobis-4-decyloxy-2,4-dimercapto valeronitrile, azobiscyclohexanone-1-indene nitrile, azodibenzoquinone, 2, 2-couple An azo compound such as nitrogen bis(1-acetoxy-1-phenylethane); a water-soluble catalyst such as potassium persulfate or ammonium persulfate; and an oxidation of a peroxide or a persulfate combined with a reducing agent Reducing catalysts and the like can generally be used for cationic polymerization. The thermal polymerization initiator of the component (iii) can be selected in consideration of the storage stability of the thermosetting resin composition of the present invention or the formation conditions of the cured product. (iii) The amount of the thermal polymerization initiator used as the component, the (mercapto) acrylate resin (component (i)) containing a polymerizable double bond, and the polymerizable compound having at least one polymerizable double bond In the total of the component (ii), the weight ratio of the component (iii) {(iii)/[(i + ii)]} is preferably 〇〇〇〇5 to 〇· 2 'better 〇· 〇〇〇 5 to 0.1. When the proportion of the polymerization initiator is small, the polymerization rate is slow and the hardenability is lowered. On the other hand, when the amount is too large, the ratio of the component (i) and the component (ii) in the thermosetting resin composition of the present invention is reduced, and the strength of the hard product is lowered. Further, the decane coupling agent of the component (iv) may, for example, be 3-glycidoxypropyltrimethoxysi lane or 3-glycidoxypropyltriethoxysulfonate 323. 〇95 18 201202276 (3-glycidoxypropyltriethoxysi lane), epoxy such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane; 3-propenyloxypropyltrimethoxydecane, 3- (meth)propionate such as 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropylpropyl, 3-methacryloxypropyltriethoxysi lane Vinyl trimethoxysilane, vinyl triethoxysilane, vinyl compound such as p-styryl tridecyloxydecane; 3-isocyanatopropyltrimethyl Isodecanoic acid esters such as oxydecane, 3-isocyanatopropyltriethoxysulfonate; 3-ureidopropyltrimethoxysilane, 3-ureidopropyltri A sulphur coupling agent such as ureide such as ethoxylate. The amount of the sulphur coupling agent to be used in the component (iv) is preferably from 〇.丨 to 2% by weight, more preferably from 5% to 10% by weight, based on the thermosetting resin composition of the present invention. a (meth) acrylate resin containing a polymerizable double bond of component (i), a polymerizable compound having at least one polymerizable double bond of component (ii), a thermal polymerization initiator of component (iii), and Ingredient (iv) The stone-lighting coupling agent is a thermosetting resin composition which must be 77, and may be dissolved in a solvent or a variety of additives as needed. In the case of the present invention, when an alcohol such as propylene glycol or an α- or a dot-form alcohol-hardening (tetra) lipid composition is used for filtration, coloring or the like, it is preferred to use a solvent other than the above. The solvent may, for example, be n-propanol, isopropanol, ethyl hydrazine ethanol 323095 19 201202276 alcohol (terpineol), etc.; terpene; acetone, mercaptoethyl ketone, cyclohexanone, N-mercapto-2-0 Ketones such as N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, tetradecylbenzene; ethylene glycol (cellosolve), ethylene glycol (iKmethyl cellosolve), Glycol diethyl ether, carbitol, decyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monoterpene ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dioxime Diol ethers such as ether, triethylene glycol monoterpene ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, ethyl lactate, glycol ether acetate, ethylene glycol ethyl ether acetate , ethylene glycol butyl ether acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monoterpene ether acetate, propylene glycol monoethyl ether acetate, etc. The esters can be obtained by using these solvents, dissolving and mixing to obtain a uniform solution-like composition. These solvents may be used in combination of two or more kinds in order to have the necessary properties such as coating properties. Further, an additive such as a curing accelerator, a plasticizer, a filler, a solvent, a leveling agent, or an antifoaming agent may be blended in the thermosetting resin composition of the present invention as needed. Among them, the plasticizer may, for example, be dibutyl phthlate, dioctyl phthalate or tricresyl phosphate. Examples of the filler include glass fiber, silica, mica, alumina, and the like. Further, examples of the antifoaming agent and the leveling agent include a silicon-based, fluorine-based, and acrylic-based compound. In the thermosetting resin composition of the present invention, a polymerizable double bond-containing (meth)acrylic acid of the component (i) is desired in the solid component of the removal solution (the solid component contains a monomer which becomes a solid component after curing). The ester resin and the component 323095 20 201202276 The total amount of the polymerizable compound having one polymerizable double bond and the thermal polymerization initiator of the component (ii) is 7 G% by weight or more, and more preferably 90% by weight or more. The amount of the solvent varies depending on the degree of the drop, but it is a relatively heavy range with respect to the total amount. 1% by weight of the thermosetting resin composition of the present invention, in addition to the above-mentioned (meth)acrylic acid (tetra) containing a polymerizable double bond, having at least one linear double bond (tetra) compound, 3 = heat and t Other resin components that are combined or hardened. As another resin, it is preferable that (7) an epoxy eutectic having two or more epoxy groups, for example, 3, 3, 5, 5, _ tetramethyl may be associated with 2 (3, 3) , 5,5-tetramethyl-4,4,-biphenol) epoxy resin, double bismuth A type epoxy resin, (iv) g type epoxy resin, viscous varnish type epoxy resin, 3, 4-epoxycyclohexene Methyl 3,4,_epoxy cyclohexane vinegar, 2'2-bis(radiomethyl)-butin-1, 2_epoxy_4_(2_oxiranyl (oxiranyl)) cyclohexene fines, county silk Wei resin. By adding such an epoxy resin, a composition which can be designed to satisfy the necessary characteristics of the cured product of each use, for example, can be lowered in comparison with the surface hardness of the cured product to improve the adhesion to the substrate. With the tendency to use the composition of the present invention, it is possible to secure a necessary surface hardness and to exhibit sufficient adhesion. Further, for example, from the viewpoint of imparting weather resistance, Nike resistance, and heat recovery, a polyoxyxylene compound such as an epoxy polyoxyxylene resin is preferably used as a physical property for the purpose of use. In combination with the essential lipid component, it is desirable that the obtained cured product (coating film) does not produce ± turbidity and is uniformly 323095 21 201202276. The present invention finds that the domain component (1) contains a silky bond. The most suitable mixing ratio of the (mercapto) acrylic acid _ lipid to these resin components can thereby suppress the turbidity of the cured product (coating film). In addition, the coating film (cured material) of the present invention can be obtained by, for example, applying a curable resin composition to a predetermined substrate or the like, drying it, and heating it to cure it. Next, a coating film (cured material, = method) using a thermosetting resin composition will be described below. First, after applying a thermosetting resin composition on the surface of a substrate or the like, the i-stage is performed. Baking to evaporate the solvent, and to promote the thermal polymerization reaction in the second stage of the baking to form a cured product. When the thermosetting resin composition is applied to the substrate, in addition to the known solution dipping method and spraying method, Alternatively, a method using a pro-coater, a floor coater (Land (10) te 〇, a spinner, etc.) may be employed, and after coating to a desired thickness, the solvent may be removed for baking. The heat polymerization reaction is promoted to form a cured product. The baking in the 帛丨 stage is carried out by heating with (4), a hot plate, or the like, vacuum drying, or a combination thereof. The heating temperature in the first stage of the baking is performed. And the heating time can be suitably selected according to the solvent to be used, for example, 1 to 20 minutes at a temperature of 8 () to 12 ° C. The second stage - roasting, and (4) 15 to 300 ° C temperature 10 Up to 120 minutes. (4) The substrate can be made into a hardened material, such as glass, a transparent film (such as polycarbonate, polyethylene terephthalate, polyether oxime, etc.). In addition, 323095 22 201202276 can also be used. It is necessary to apply a suitable pretreatment such as a second product treatment, an electric coating treatment, an ion coating, a sputtering method, a reaction method, or a vacuum steaming, which are carried out by using a sulphur coupling agent or the like. Further, it is a matter of course that a cured product can be obtained by a procedure different from that described above. (Example) Synthesis of a (meth) acrylate resin containing a polymerizable double bond represented by the general formula (6) The present invention will be further described in detail, and the present invention is not limited to the scope of the synthesis examples and the like. The evaluation of the resin of the following synthesis examples is carried out as follows, unless otherwise specified. Component concentration] The resin solution (including the reaction product and the (fluorenyl) acrylate resin containing a polymerizable double bond) obtained in the synthesis example (and the comparative synthesis example) The glass filter [weight: WD (g)], weighed [W / g)], and then 16 (TC heated 2 hours [WXg)], according to the following formula. 1 Solid content concentration (weight %)=1〇〇&gt;&lt;(Evaluation 2-1())/(1嘈(〇[epoxide equivalent]] After dissolving the resin solution in dioxane, it is added to the desert tetraethylammonium. The acetic acid solution was obtained by titration with a 1/10 N~peroxy acid solution using a potentiometric titration apparatus (manufactured by Hiranuma Co., Ltd., trade name: COM-1600). [Acid value] The resin solution was dissolved in dioxane, and used. The potentiometric titration was determined by the titration of 1/10 N-KOH aqueous solution (manufactured by Hirohuma 323095 23 201202276, manufactured by Seiko Co., Ltd., trade name: COM-1600). [Molecular weight] A gel permeation chromatography (GPC) (HLC-8220GPC manufactured by T0S0H Co., Ltd., solvent: tetrahydrofuran, column: TSKgel SuperH-2000 (2 HTSKgel Super H-3000C1) + TSKgel Super H-) 4000 (1 HTSKgel Super-H5000 (1) (T0S0H Co., Ltd.), temperature: 40 ° C, speed: 0.6 ml / min) was measured with standard polystyrene (T0S0H Co., Ltd. 'PS- The value of the weight average molecular weight (Mw) was determined by the conversion value of the 〇lig〇mer kit. The code used in the synthesis example and the comparative synthesis example is as follows. MAA: mercaptoacrylic acid MMA: mercaptoacrylic acid Methyl methacrylate CHMA: cyclohexyl methacrylate GMA: glycidyl methacrylate AIBN : azobisisobutyronitrile TPP: triphenylphosphine ( Triphenylphosphine) DMDG : diethylene glycol dioxime [synthesis example 1]

In a 1000 ml four-necked flask equipped with a nitrogen gas introduction tube and a reflux tube, 51.65 g (〇.60 mol) of mercaptoacrylic acid, 38.44 g (0.38 mol) of methyl methacrylate, and 36.33 g of cyclohexyl methacrylate were charged. (0.22 mol), AIBN 24 323095 201202276 5. 91 g (0. 036 mol) and DMDG 368 g were polymerized by stirring at 80 to 85 ° C for 8 hours under a nitrogen stream. 055g,,,,,,,,, The mixture was stirred at 80 to 85 ° C for 16 hours to obtain a (fluorenyl) acrylate resin (i)-1 containing a polymerizable double bond. The obtained (fluorenyl) acrylate resin containing a polymerizable double bond had a solid content concentration of 32.0% by mass, an acid value (in terms of solid content) of 11 mgKOH/g, and a Mw of G80 of 18080. Further, from the IR measurement of the obtained (meth) acrylate resin containing a polymerizable double bond, a peak was observed at 1409 cm -1 (vinyl) and 1186 cnf1 (carboxyl). Thus, it was confirmed that the (meth) acrylate resin having a polymerizable double bond and a carboxyl group and having a polymerizable double bond was used. [Synthesis Example 2] In a 1000 ml four-necked flask equipped with a nitrogen gas introduction tube and a reflux tube, 51.65 g (0.60 mol), methyl methacrylate, 38.44 g (0.38 mol), 36. 33 g (0.22 mol) of hexyl methacrylate, AIBN 7.39 g (〇.〇45 mol), and 371 g of DMDG were polymerized by stirring at 80 to 85 ° C for 8 hours under a nitrogen stream. Further, the flask was charged with glycidyl methacrylate 39.23 g (0.28 mol), TPP 1.44 g (0.055 mol), and 2,6-di-t-butyl-p-phenolphthalein. 558, at 80 to 85° (: stirring for 16 hours to obtain a (fluorenyl) acrylate resin (i)-2 containing a polymerizable double bond. The obtained (fluorenyl) acrylate resin containing a polymerizable double bond The solid content concentration was 31.5% by mass, the acid value (calculated as solid content) was 109 mgKOH/g, and the Mw analyzed by GPC was 14,400. Further, from the obtained 25 323095 201202276 (polymerizable) double bond-containing (fluorenyl) acrylic acid In the IR measurement of the ester resin, it was observed that there were peaks in 1410〇11_1 (vinyl) and 1185cin_1 (carboxyl group), and it was confirmed that it was a polymerizable double bond-containing (methyl) having a polymerizable double bond and a carboxyl group. The acrylic acid S is a resin. [Synthesis Example 3] In a 1000 ml four-necked flask equipped with a nitrogen gas introduction tube and a reflux tube, a mercaptopropionic acid was added in an amount of 51.65 g (0.60 mol), bismuth methacrylate Ester 38. 44g (0.38mol), cyclohexyl methacrylate 36.34g (0.22mol), AIBN 3. 35g (0· 020mol), and DMDG 363g, at 80 The mixture was stirred at 85 ° C for 8 hours under a nitrogen stream, and the flask was charged with glycidyl methacrylate 37.53 g (〇. 26 mol), TPP 1.38 g (0.053 mol), and 2,6 -Di-t-butyl-p-nonylphenol 0.053 Torr at 80 to 85° (: stirring for 16 hours to obtain a (fluorenyl) acrylate resin (i)-3 containing a polymerizable double bond. The solid content of the (fluorenyl) acrylate resin having a double bond was 31.7% by mass, the acid value (in terms of solid content) was 117 mgKOH/g, and the Mw of GPC analysis was 28,280. Further, the obtained polymerization was contained. The IR measurement of the (meth) acrylate resin of the double bond was observed to have a peak at 1409 〇 11-1 (vinyl) and 1185 cm '1 (carboxyl group). Thus, it was confirmed that it had a polymerizable double bond. A (meth)propionic acid vinegar resin containing a polymerizable double bond with a carboxyl group. [Synthesis Example 4]

In a l〇〇〇ml four-necked flask equipped with a nitrogen gas introduction tube and a reflux tube, 51.65 g (〇.60 m〇l) of methacrylic acid and 38.44 g (0.38 mol) of decyl acrylate were added. Dilute cyclohexyl ester 36.34 g (0.22 mol), AIBN 26 323095 201202276 2·36 g (0. 〇14 mol), and DMDG 357 g were polymerized by stirring at 80 to 85 ° C for 8 hours under a nitrogen stream. Further, the flask was charged with glycidyl methacrylate 35.82 g (0.25 mol), TPP 1.32 g (0.050 mol), and 2,6-di-t-butyl-p-cresol 0.053. From 80 to 85. (7) The solid content concentration of the (meth) acrylate resin containing a polymerizable double bond was 31. 7 The mass %, the acid value (calculated as solid content) was 120 mgKOH/g 'The Mw analyzed by GPC was 44,380. Further, from the IR measurement of the obtained (fluorenyl) acrylate resin containing a polymerizable double bond, it was observed. There are peaks in Mllcm, Ethyl) and ΙΙδδαιΓ1 (鲅). Thus, it was confirmed that it is a (meth) acrylate resin having a polymerizable double bond and a carboxyl group and having a polymerizable double bond. [Chemical Example 5] In a 1000 ml four-necked flask equipped with a gas introduction tube and a reflux tube, 63. 02 g (0.73 mol), decyl isopropyl acrylate 46. 86 g (0 47 mol), AIBN 5.91 g (0.336 mol), and DMDG 340 g were polymerized by stirring at 80 to 85 ° C for 8 hours under a nitrogen stream. Further, the flask was charged with methyl acetoacetate glycidol from the purpose of 46. 06 g (0.32 mol), TPP 1.70 bogey (0.0065111〇1), and 2,6-di-t-butyl group-to-bee 0.065 This was stirred at 80 to 85 ° C for 16 hours to obtain (mercapto) acrylate resin (i)-5 containing a polymerizable double bond. The solid content concentration of the obtained (fluorenyl) acrylate resin containing a polymerizable double bond was 32.7% by mass, the acid value (calculated as solid content) was 146 mgKOH/g, and the Mw of GPC analysis was 16,600. Further, from the measurement of 27 323095 201202276 IR of the obtained (meth) acrylate resin containing a polymerizable double bond, it was observed that there were peaks at 1411 cm_1 (vinyl) and 1185 CHT1 (carboxyl). From this, it was confirmed that it is a (mercapto)acrylic acid-containing resin having a polymerizable double bond and a carboxyl group and having a polymerizable double bond. [0. [0086] [0. [0086] [0] [0] [0·5······································· 42 mol), cyclohexyl methacrylate 20.19 g (0.12 mol), AIBN 5.91 g (0.336 mol), and DMDG 352 g were polymerized by stirring at 80 to 85 ° C for 8 hours under a nitrogen stream. Further, in the crucible, 45.6 g (0.30 mol), TPP 1.57 g (0.060 mol), and 2,6-di-t-butyl-p-phenolphthalein were charged. 〇6〇g, stirred at go to 85〇c for 16 hours to obtain a (fluorenyl) acrylate resin (i)-6 containing a polymerizable double bond. The solid content concentration of the obtained (meth) acrylate resin containing a polymerizable double bond was 32.6% by mass, and the acid value (in terms of solid content) was 123 mgKOH/g'. The Mw of GPC analysis was 16,290. Further, from the I R measurement of the obtained (fluorenyl) acrylic acid resin containing a polymerizable double bond, it was observed that there were peaks in the vinyl group and (carboxy group). Thus, it was confirmed that the (meth) acrylate resin having a polymerizable double bond and a repellent group had a polymerizable double bond. [Synthesis Example 7] In a l〇〇〇ml four-necked flask equipped with a nitrogen gas introduction tube and a reflux tube, 44.42 g (0.52 mol), methyl methacrylate 32. 44 g (0.32 mol) was charged. ), cyclohexyl methacrylate 60.56 g (0.36 mol), AIBN 5.91 g (0.036 mol), and DMDG 375 g were polymerized by stirring at 80 to 85 Torr under a nitrogen gas 323095 28 201202276 for 8 hours. Further, the flask was charged with glycidyl methacrylate 35.82 g (〇·25m〇1), Tpp L 32g (〇〇〇5〇m〇1), and 2, di-t-butyl-p-quinone Phenol 0. 050 g, stirred at 80 to 85 ° C for 16 hours to obtain a (meth) acrylate resin containing a polymerizable double bond-containing (fluorenyl) acrylate resin (i) _7 ° containing a polymerizable double bond The solid content concentration was 32.7% by mass, and the acid value (in terms of solid content) was 86 mgKOH/g'. The Mw analyzed by GPC was 15,370. Further, from the IR measurement of the obtained (meth) acrylate resin containing a polymerizable double bond, peaks were observed at 1410 cm (vinyl) and 1186 cm-i (carboxyl). Thus, it is confirmed that it is a (fluorenyl) acrylate resin having a polymerizable double bond and a carboxyl group and having a polymerizable double bond. (Examples 1 to 2, Comparative Examples 1 to 3) Next, the present invention will be specifically described based on examples and comparative examples regarding the production of a thermosetting resin composition and a cured product thereof, but the present invention is not limited thereto. These examples. The materials and codes used in the production of the thermosetting resin composition and the cured product of the subsequent examples and comparative examples are as follows. Component (i)-l: thermosetting resin component (I)-2 obtained in the above Synthesis Example 1: thermosetting resin component (i)-3 obtained in the above Synthesis Example 2: obtained in the above Synthesis Example 3 Thermosetting Resin Component (i)-4: Thermosetting Resin Component (I)-5 obtained in Synthesis Example 4: Thermosetting Resin Component (i)-6 obtained in Synthesis Example 5: Synthesis Example 6 obtained thermosetting resin component (I)-7: thermosetting resin obtained in the above Synthesis Example 29 323095 201202276 Component (ii)-1: Pentaerythritol triacrylate ester prepolymer (total Rongshi Chemical Manufacturing, trade name UA-306H) Ingredient (ii)-2: 56.5 mass% propylene glycol monomethyl ether acetate solution of an anhydride adduct of bisphenol oxime epoxy diacrylate (Nippon Steel Chemical Co., Ltd. Manufactured, trade name V-259ME;) Ingredient (ii)-3: 2-hydroxyethyl methacrylate adduct of a stupid ethylene/maleic anhydride copolymer (Mw=4350, acid value = 138 mg K0H/g, Solid content concentration 72« Component (ii)-4: Acrylic acid 2-thioethyl ester adduct of styrene/maleic anhydride copolymer (Mw=4070, acid value=14 5mgK0H/g, solid concentration 55« Ingredient (iii): Thermal polymerization initiator (manufactured by Nippon Oil, trade name NYPER BMT-K40) Ingredient (iv): decane coupling agent (3-isocyanatopropyltriethyl) Oxygen oxane) Component (v) : 3, 3', 5, 5' - tetradecyl-4, 4'-biphenyldiol type epoxy resin (manufactured by Japan Epoxy Resin, trade name YX-4000H) (vi): phenyl decyl methacrylate / methacrylic acid copolymer (Mw = 10100, acid value = 102 mg KOH / g) Solvent - 1 : diethylene glycol dioxime ether solvent - 2: propylene glycol monomethyl ether acetate Additive: Surfactant (manufactured by Dow Corning Co., Ltd., trade name FZ-2122) Further, (vi) is a resin component which does not contain a polymerizable double bond and does not contain an epoxy group such as an anti-30 323095 201202276 functional group. The above-mentioned compounding components were blended in the proportions shown in Table 1, and the thermosetting resin compositions of Examples 1 to 3 and Comparative Example 1 were prepared. The numerical values in Table 1 are all parts by weight. 31 323095 201202276 [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Ingredient (i) (0-1 (i)-2 (i)-3 (i)-4 ( i)-5 22. 28 22. 63 18. 33 18. 33 17. 88 Ingredient (ii) (ii)-l (ii)-l (ii)-l (ii)-1 (ii)-l 7. 72 7. 72 8. 72 8. 72 8. 72 Composition (iii) 0. 19 0. 19 0. 04 0. 04 0. 04 Composition (iv) 1. 49 1.49 0. 91 0. 91 0. 91 Composition (v) 3. 53 3. 53 Solvent-1 64. 74 64. 39 59. 15 59. 15 59. 15 Solvent-2 12. 81 12. 81 13. 26 Additive 0. 06 0. 06 0. 05 0 05 0. 05 Example 6 Example 7 Example 8 Example 9 Ingredient (i) (i)-6 (0-7 (0-1 (i)-l 17. 88 17. 88 4. 67 4. 70 Ingredients (ii) (ii)-l (ii)-l (ii)-l (ii)-l 8. 72 8. 72 6. 73 3. 76 (ii)-2 (ii)-2 11. 91 14. 64 Composition (iii) 0. 04 0. 04 0. 19 0. 17 Composition (iv) 0. 91 0. 91 0. 94 0. 94 Composition (V) 1. 50 Solvent-1 59. 15 59. 15 58. 8 58. 8 Solvent-2 13. 26 13. 26 16. 73 15. 47 Additive 0. 05 0. 05 0. 03 0. 02 32 323095 201202276 [Table 2] Comparative Example 1 Comparative Example 2 Comparative Example 3 Ingredients (i) Ingredients (ii) (ii)-l (ii)-l (ii)-l 7. 72 7. 72 7. 72 (ϋ)-3 (ϋ)-4 9. 90 12. 96 Ingredients (iii) 0. 19 0. 19 0. 19 Ingredients Iv) 1.49 1.49 1.49 Ingredient (V) 3. 53 3. 53 3. 53 Ingredient (vi) 7. 13 Solvent-1 77. 12 74. 06 79.89 Solvent-2 Additive 0. 06 0. 06 0. 06 [Cure Preparation of the material] The thermosetting resin composition shown in Tables 1 and 2 was applied to a glass substrate of 125 mm x 25 mm using a spin coater so that the film thickness after the second baking was 1.3. On the other hand, the coating was carried out, and the first stage baking was performed at 90 ° C for 1 minute using a hot air dryer to prepare a coated sheet. Then, the second stage baking was carried out at 230 ° C for 30 minutes using a hot air dryer to obtain the hard coats (coating films) of Examples 1 to 9 and Comparative Examples 1 to 3. The cured product (coating film) composed of the thermosetting resin composition of Examples 1 to 9 and Comparative Examples 1 to 3 obtained above was evaluated as a result of evaluating the properties and hardness of 33 323095 201202276. Table 2. These evaluation methods are as follows. Thickness: The measurement was carried out using a stylus type step shape measuring device (manufactured by KLA-Tencor Co., Ltd., trade name P-10). Adhesion: A cured product prepared on a glass substrate was allowed to stand under the conditions of a temperature of 121 ° C, a humidity of 100%, and a gas pressure of 2 atm for 5 hours. In addition, using the Super Cutter Guide manufactured by Taiyo Machinery Co., Ltd., the placed hardened material is cut into 100 square checkers, and a cellophane tap (made by NICHIBAN) is attached to the checkerboard. Tape stripping test for stripping tape. The state in which the hardened material in the checkerboard is not peeled off is 〇, the condition of the hardened material in the checkerboard is less than 1 / 3 peeling is Δ, and the condition of 1/3 or more peeling is x. Coating film hardness 1: A cured product prepared on a glass substrate, according to the test method of JIS_K54, is expressed by the highest erroneous hardness which does not cause scratches on the coating film when a load of 1 kg is applied using a pencil hardness tester. The used pen is "Two-way

Hi-uni". Here, this evaluation was carried out as an index of resistance to lateral force (scratch) on the surface of the coating film. Coating film hardness 2: A cured product prepared on a glass substrate was measured using a microfilm hardness meter (manufactured by Fischer Instruments 'HM2000). The indenter uses a Vickers indenter's load to load the load with a load of 323095 34 201202276 0. 25mN/sec. After holding the load for 1 second, the load is removed and the Markov is measured. Martens hardness (according to ISO 14577). The Martens hardness referred to herein means the hardness calculated by the load-entry depth curve, and is evaluated as 〇 when the Martens hardness is 65 N/L 2 or more, and △ when it is less than 65 N/mm 2 to 60 N/mm 2 or more. 'It is evaluated as X when it is less than 60N/nmi2. Here, the evaluation was carried out as an index of resistance to the longitudinal force (pressing in) of the surface of the coating film. Transmittance: A cured product prepared on a glass substrate, and the transmittance was measured using a transmittance meter (manufactured by Nippon Denshoku Industries Co., Ltd., trade name Spectro Photometer SD5000), and evaluated when the transmittance at a wavelength of 400 nm was 95% or more. For 〇, it is evaluated as △ when it is less than 95% to 95% or more, and when it is less than 90%, it is evaluated as x. Heat-resistant discoloration property: A cured product prepared on a glass substrate was heat-dried at 230 ° C for 3 hours using a hot air dryer. And 'The cured product after the heat drying treatment is a transmittance meter (manufactured by Nippon Denshoku Industries Co., Ltd., trade name)

The Spectro Photometer SD5000) was measured for transmittance, and when the transmittance at a wavelength of 4 〇〇 nm was 95% or more, it was evaluated as 〇 when the 〇' was less than 95% to 95% or more, and when it was not 90%, it was evaluated as X. Heat-resistant film thickness: The thickness of the cured product prepared on the glass substrate was measured [Li (after 'heat-drying at 230 ° C using a hot air dryer for 3 hours). Further, the film thickness of the cured product after the heat drying treatment was measured. [L2 (//m)] The following formula determines the film thickness change rate of the cured product before and after the heat drying treatment, and evaluates to 〇 when the film thickness of heat 323095 35 201202276 is 90% or more, and 评价 when it is less than 90%. Heat-resistant film thickness (%) = 1 〇〇 x (L2-Li) / Li Gas-generating property: The cured product prepared on the glass substrate is cut by a scraper or the like, and the obtained powdery cured product 4 is obtained. The thermal weight loss to 6 mg was measured by a differential thermal weight measuring device (TG/DTA) (manufactured by SII Co., Ltd., EXSTER 6000) under the conditions of a pretreatment of 30 minutes at 120 ° C under the atmosphere. °C was maintained for 2 hours. The gas-producing property was evaluated based on the weight reduction rate. The smaller the weight reduction rate, the better the low gas-producing property. The weight reduction rate was calculated from the weight loss before and after heating, and the weight reduction rate was less than 5%. When the evaluation is ◎' 5% or more and less than 1%%, the evaluation is 〇, 10 When it is less than 15%, it is evaluated as eight, and when it is 15% or more, it is evaluated as X. 323095 36 201202276 - Table 3] Example 1 Example 2 Example 3 Example 4 Example 5 Thermosetting resin (i) - l (ii) -l (i) -2 (ii) -l (1)-3 (ii)-l (i) -4 (ii) -l (i) -5 (ii) -l film thickness (em) 1.5 1. 5 1.5 1. 5 1.5 Adhesive 〇〇〇〇〇 coating hardness 1 4H 4H 4H 4H 4H coating hardness 2 〇〇〇〇〇 penetration rate 〇〇〇〇〇 heat discoloration 〇〇〇〇〇 Heat-resistant film thickness 〇〇〇〇〇 gassing 〇〇〇〇〇 Example 6 Example 7 Example 8 Example 9 Thermosetting resin (i)-6 (i)-7 (i)-l (i) -l (ii)-l (ii)-l (ii)-l (ii)-l (ii)-2 (ii)-2 Film thickness (/zm) 1.5 1. 5 1.5 1.5 Adhesion 〇〇〇 〇 coating film hardness 1 4H 4H 4H 4H coating film hardness 2 〇〇〇〇 transmittance 〇〇〇〇 heat resistance 〇〇〇〇 heat resistant film thickness 〇〇〇〇 gas production 〇〇 ◎ ◎ 37 323095 201202276 [Table 4] Comparative Example 1 Comparative Example 2 Comparative Example 3 Thermosetting Resin (ii)-1 (ii)-3 (ii)-l (ii)- 4 (ϋ)-1 Film thickness (in m) 1.5 1.5 1. 5 Adhesion 〇Δ 〇Coat film hardness 1 3H 3H 3H Film hardness 2 Δ Δ X Penetration 〇〇Δ Heat discoloration 〇〇Δ Heat resistance Film thickness 〇〇Δ gas-producing property Δ Δ Δ As shown in the results of Tables 3 and 4 above, the cured products of Examples 1 to 9 were excellent in various properties, particularly in comparison with Comparative Examples 1 to 3, Adhesion and film hardness, and a cured product having high transmittance can be formed. In other words, it is understood that the present invention can provide a cured film having transparency, light resistance, weather resistance, heat resistance, surface hardness, adhesion, and low gas yield. (Industrial Applicability) The thermosetting resin composition of the present invention can be formed by imparting a polymerizable double bond to a (fluorenyl) acrylate resin having transparency, weather resistance, light resistance, and heat resistance. A cured product excellent in adhesion and surface hardness. Therefore, it can be suitably used as various display elements such as a color liquid crystal display device, a color facsimile, an image sensor, or a color filter protective film material, or an organic device such as an organic semiconductor 38 323095 201202276 Use of protective layer, sealing material and adhesive. [Simple description of the diagram] None. [Main component symbol description] None. 39 323095

Claims (1)

201202276 VII. Patent application scope: 1. A thermosetting resin composition characterized by containing the following (i), (ii), (iii) and (iv) as essential components: (1) 1) a part of a carboxyl group in a copolymer of a (fluorenyl) acrylate compound and a (meth)acrylic compound represented by the formula (2), which has an epoxy group represented by the formula (3) A (meth) acrylate resin containing a polymerizable double bond obtained by reacting a (meth)acrylic acid vine compound; A 1 (1) (only 'R! represents a hydrogen atom or a methyl group; 匕 represents a carbon number of 1 to 2 Å Hydrocarbyl group, which may also contain an etheric oxygen atom or an amino phthalate bond in its interior. Human CO2H (only 'R represents a hydrogen atom or a methyl group)-R7 Ο Ό (3) (only 'L represents a hydrogen atom or a fluorenyl group; 匕 represents a divalent ketone group with a carbon number of 2 to 1 '' p represents the number of 〇 or 1); (ii) the above-mentioned polymerizable double bond ( a polymerizable compound having at least one polymerizable double bond other than the acrylate resin; (iii) a thermal polymerization initiator; and (iv) a decane coupling agent. 1. The thermosetting resin composition according to the above aspect of the invention, wherein the above-mentioned (mercapto) acrylate resin containing a polymerizable double bond has an average molecular weight of 1 Å, 〇〇〇 to 丨00, 〇〇〇. 3. The thermosetting resin composition according to claim 1 or 2, wherein the total of all the constituent units of the (fluorenyl) acrylate resin containing the polymerizable double bond is 100, The constituent unit of the (fluorenyl) acrylate compound represented by the formula (1) is 20 to 7 Å; and the carboxyl group-containing constituent unit derived from the (meth)acrylic compound represented by the formula (2) is 10 to 50; The (fluorenyl) acrylate compound having an epoxy group represented by the formula (3) has a polymerizable double bond-constituting unit of 10 to 40. 4. The thermosetting resin composition according to any one of claims 1 to 3, wherein the weight ratio [(i)/(ii)] of the component (丨) to the component (ii) is 5 0005至0. 0005至0. 0005至0. The ratio of the weight ratio of the component (i) to the total of the component (i) of the component (iii) {(iii) / [(i) + (π)]} is 0. 0005 to 0. 2, and the ratio of the component (iv) in the thermosetting resin composition is 〇·1 to 2% by weight. 5. A hardened material obtained by curing the thermosetting resin composition according to any one of the above claims. 6. A color filter comprising a cured product as described in claim 5, as a protective layer. 2 323095 201202276 IV. Designated representative map: (1) The representative representative of the case is: There is no schema in this case. (2) A brief description of the symbol of the representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 4 323095