JP6900634B2 - Internal epoxy compound and thermosetting composition - Google Patents

Description

The present invention relates to an epoxy compound having excellent thermal responsiveness to high temperature and storage stability, and a thermosetting composition using the same.

Since the cured product of an epoxy compound exhibits excellent properties such as optical properties, mechanical properties, electrical properties, heat resistance, adhesiveness, moisture resistance, water resistance, and chemical resistance, for example, optical applications, opt device applications, etc. It is widely used as a constituent material for various applications such as display device applications, machine parts materials, electrical / electronic parts materials, automobile parts materials, civil engineering and building materials, molding materials, paints, and adhesives.

Epoxy compounds that are usually used are benzene rings in the molecular skeleton, such as so-called epi-bis type epoxy resins produced by the reaction of bisphenol and epichlorohydrin, and novolac epoxy resins produced by the reaction of novolak phenol and epichlorohydrin. It has. Generally, an epoxy compound is cured by a heat addition reaction using an active hydrogen compound as a curing agent to exhibit various properties. As the curing agent for the epoxy compound, amines, polyethercaptans, acid anhydrides, polycarboxylic acid resins, phenol / novolac resins and the like are used.

Generally, when amines and polyethercaptans are used, curing is fast, and curing is completed at low temperature and in a short time. Since storage stability cannot be ensured with a single liquid, it is usually used by mixing a main agent and a curing agent immediately before use. Further, in order to ensure storage stability in one liquid, a latent curing agent that produces an active hydrogen compound by light or heat is used.

On the other hand, when acid anhydrides and polycarboxylic acid resins are used, curing is slow and high temperature and long-term heating are required. Therefore, usually, a curing accelerator is used in combination to lower the curing temperature and shorten the curing time. As a curing accelerator, a tertiary amine is the most common. However, when the tertiary amine is used in combination, there is a problem in thermal responsiveness such that a partial curing reaction proceeds even when the solvent in the compounding solution is dried at a low temperature. In addition, there is a problem that the melt viscosity increases when a tertiary amine is used in combination. That is, the thermosetting composition containing the epoxy compound and the acid anhydride had room for improvement in terms of storage stability.

International Publication No. 2012/046553 Pamphlet

The present invention has been made in view of the above-mentioned current situation, and has excellent storage stability when blended with an acid anhydride or a polycarboxylic acid resin, and has excellent heat that does not react at low temperature heating but reacts only at high temperature heating. It is an object of the present invention to provide an epoxy compound and a thermosetting composition which are responsive.

As a result of diligent studies to solve the above problems, the thermosetting composition containing an internal epoxy compound having an aliphatic substance and having a plurality of epoxy groups inside the molecule and a polycarboxylic acid resin or an acid anhydride curing agent has been found. It has been found that it exhibits excellent storage stability and thermal responsiveness. The present invention has been completed based on these findings.

That is, the present invention relates to an internal epoxy compound having an epoxy group inside the molecule, which is represented by the following general formula (1).

General formula (1)

(In the formula, R represents an alkylene group.
The alkylene group may be a linear alkylene or a branched alkylene, and may be interrupted by an ether bond or an ester bond.
X and Y each independently represent a monovalent aliphatic hydrocarbon group.
In addition, m represents an integer of 1 to 4, and represents
n represents an integer from 0 to 3.
However, the value of m + n is an integer of 2 to 4. )

The present invention also relates to the internal epoxy compound according to claim 1, wherein X and Y are independently monovalent aliphatic hydrocarbon groups having 1 to 10 carbon atoms.

The present invention also relates to a thermosetting composition containing the above internal epoxy compound and a polycarboxylic acid resin or an acid anhydride-based curing agent.

The present invention also relates to a thermosetting composition further containing an epoxy compound other than the internal epoxy compound.

The present invention also claims 3 or 4 in which the molar ratio of the epoxy group in the composition to the carbonyl group of the polycarboxylic acid resin or acid anhydride-based curing agent is 1: 0.4 to 1: 1.5. With respect to the thermosetting composition described.

The present invention also relates to a cured product obtained by curing the thermosetting composition.

According to the present invention, an epoxy compound and thermosetting which are excellent in storage stability when blended with an acid anhydride or a polycarboxylic acid resin, and exhibit excellent thermal responsiveness that does not react at low temperature heating but reacts only at high temperature heating. The composition could be provided.

FIG. 1 is a ¹ H-NMR spectrum of compound (5).

The internal epoxy compound having an epoxy group inside the molecule in the present invention will be described below.

The internal epoxy compound having an epoxy group inside the molecule in the present invention has a structure represented by the above general formula (1). In the formula, R represents an alkylene group. The alkylene group may be a linear alkylene or a branched alkylene, and may be interrupted by an ether bond or an ester bond.

Specific examples of the linear alkylene group in R include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group and a decylene group, and ethylene is preferable. Examples thereof include a group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group and an octylene group, and more preferably an ethylene group, a propylene group, a butylene group, a pentylene group and a hexylene group.

Specific examples of the branched alkylene group in R include the following structures.

Specific examples of the alkylene group in R being interrupted by an ether bond include, for example, − (CH ₂ ) _m −O − (CH ₂ ) _m − (m is an integer of 2 to 5).
− [(CH ₂ ) _m −O−] _n − (CH ₂ ) _p − (m is an integer of 2 to 5, n is an integer of 1 to 5, and p is an integer of 1 to 3. It is an integer.). Preferably, m is an integer of 2-4, n is an integer of 1-4, and p is an integer of 1-2.

Specific examples of the alkylene group in R being interrupted by an ester bond include, for example, − [(CH ₂ ) _m −COO− (CH ₂ ) _m −] _n − (m is an integer of 2 to 5 and also. n is an integer of 1 to 3). Preferably, m is an integer of 2-4 and n is an integer of 1-2.

X and Y each independently represent a monovalent aliphatic hydrocarbon group. Examples of the monovalent hydrocarbon group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group and octyl. Examples thereof include a group, a nonyl group, a decyl group, a lauryl group, a tetradecyl group, a cetyl group, a stearyl group, a behenyl group and the like. In terms of the reactivity of the internal epoxy, a linear aliphatic hydrocarbon group with less steric hindrance is preferable. In particular, a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms is preferable.

m represents an integer of 1 to 4, and n represents an integer of 0 to 3. However, the value of m + n is an integer of 2 to 4.

Specific examples of the internal epoxy compound of the present invention include the following compounds.

The method for producing an internal epoxy compound having an epoxy group inside the molecule represented by the general formula (1) in the present invention will be described below.

The internal epoxy compound having an epoxy group inside the molecule represented by the general formula (1) in the present invention can be synthesized by various methods. A method of synthesizing by bonding an aliphatic compound and a compound having an internal epoxy group, after bonding an aliphatic compound and an unsaturated aliphatic compound having a carbon-carbon double bond inside the molecule, carbon inside the molecule. -A method of introducing an epoxy group by bonding a carbon double bond and oxygen can be mentioned. Examples of the method for binding the two compounds include esterification and etherification.

A particularly preferable example is a method of bonding an aliphatic halide and an unsaturated aliphatic alcohol having a carbon-carbon double bond at the β-position of a hydroxyl group by etherification to epoxidize the resulting olefin, or an aliphatic. A method of bonding an alcohol and an unsaturated aliphatic halide having a carbon-carbon double bond at the β-position of a halogen atom by etherification to epoxidize the resulting olefin, an aliphatic carboxylic acid halide and a hydroxyl group. A method of bonding an unsaturated aliphatic alcohol having a carbon-carbon double bond at the β-position of the above by etherification and esterification to epoxidize the resulting olefin, an aliphatic carboxylic acid having a hydroxyl group, and a halogen atom. An unsaturated aliphatic halide having a carbon-carbon double bond at the β-position is bonded by etherification, and an aliphatic carboxylic acid having an olefin formed by etherification and an aliphatic carboxylic acid having a carbon-carbon double bond at the β-position of the hydroxyl group are not present. Examples thereof include a method of bonding with a saturated aliphatic alcohol by esterification and epoxidizing the resulting olefin.

Examples of the aliphatic halide include 1,2-dichloropropane, 1,3-dichloropropane, 2,2-dimethyl-1,3-dichloropropane, 1,4-dichlorobutane, and bis (2-chloroethyl) ether. , 1,5-Dichloropentane, 1,6-dichlorohexane, 1,7-dichloroheptane, 1,8-dichlorooctane, bis (4-chlorobutyl) ether, 1,9-dichlorononane, 1,10-dichlorodecane , 1,11-dichloroundecane, 1,12-dichlorododecane, 1,3-dibromopropane, 2,2-dimethyl-1,3-dibromopropane, 1,4-dibromobutane, bis (2-bromoethyl) ether, 1,5-Dibromopentane, 1,6-dibromohexane, 1,7-dibromoheptane, 1,8-dibromooctane, bis (4-bromobutyl) ether, 1,9-dibromorononane, 1,10-dibromodecane , 1,11-dibromoundecane, 1,12-dibromododecane, 1,3-diiodopropane, 1,4-diiodobutane 1,5-diiodopentane, 1,6-diiodohexane, 1,2,3- Examples thereof include trichloropropane, 1,2,3-tribromopropane, 1,2,3-triiodopropane, pentaerythrityl tetrachloride, pentaerythrityl tetrabromid and pentaethyrotilyl tetraiodide.

Examples of the aliphatic alcohol include 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-ethyl-2-methyl-1,3-propanediol, 2, and so on. 2-Dimethyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,3-butanediol, 1,2-Pentanediol, 1,3-Pentanediol, 1,5-Pentanediol, 2,4-dimethyl-2,4-Pentanediol, 2,4-Diethyl-1,5-Pentanediol, 2-Methyl Pentan-2,4-diol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 2,5-dimethyl-2,5-hexanediol, 2-ethyl-1,3- Hexanediol, 1,2-heptanediol, 1,7-heptanediol, 1,8-octanediol, 3,6-octanediol, 1,9-nonanediol, 1,2-decanediol, 1,10-decane Diol, 1,11-undecanediol, 1,12-dodecanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, neopentyl glycol mono (hydroxypivalate), trimethylol Examples thereof include ethane, trimethylolpropane, 1,2,4-butanediol, 1,2,5-pentanetriol, 1,2,6-hexanetriol, 1,2,7-heptanetriol and pentaerythritol.

Examples of aliphatic carboxylic acid halides include chloroacetic acid, 3-chlorobutyric acid, 4-chlorobutyric acid, 5-chlorovaleric acid, 6-chlorohexanoic acid, 3-chloroisobutyric acid, 3-chloropropionic acid, and 2-chloro. Propionic acid, 3-chloropivalic acid, bromoacetic acid, 2-bromopropionic acid, 2-bromoisobutyric acid, 3-bromopropionic acid, 3-bromopyruvic acid, 3-bromoisobutyric acid, 4-bromobutyric acid, 5-bromovaleric acid , 6-Bromohexanoic acid, 7-bromoheptanic acid, 2,3-dichloroisobutyric acid, 2,3-dichloropropionic acid, 2,3-dibromopropionic acid, 3-bromo-2- (bromomethyl) propionic acid, etc. Be done.

Examples of unsaturated aliphatic alcohols having a carbon-carbon double bond at the β-position of the hydroxyl group include crotyl alcohol, cis-2-penten-1-ol, trans-2-penten-1-ol, and cis-2-hexene. -1-ol, trans-2-hexen-1-ol, cis-2-hepten-1-ol, trans-2-hepten-1-ol, cis-2-octen-1-ol, trans-2-octen -1-ol, cis-2-nonen-1-ol, trans-2-nonen-1-ol, trans-2-decene-1-ol, trans-2-undecene-1-ol, 2-dodecenol, trans -2-tridecene-1-ol, etc. may be mentioned.

Examples of unsaturated aliphatic halides having a carbon-carbon double bond at the β-position of the halogen atom include crotyl chloride, crotyl bromide, 1-chloro-2-pentene, 1-bromo-2-pentene, and 1-chloro. -2-hexene, 1-bromo-2-hexene, 1-chloro-2-heptene, 1-bromo-2-heptene, 1-chloro-2-octene, 1-bromo-2-octene, 1-chloro-2 -Nonene, 1-bromo-2-nonene, 1-chloro-2-decene, 1-bromo-2-decene, 1-chloro-2-undecene, 1-bromo-2-undecene, 1-chloro-2-tridecene , 1-Bromo-2-tridecene, and the like.

The etherification method is a method of etherifying an aliphatic halide and an unsaturated aliphatic alcohol having a carbon-carbon double bond at the β-position of a hydroxyl group in the presence of a strong base. Examples thereof include a method of etherifying an unsaturated aliphatic halide having a carbon-carbon double bond at the β-position in the presence of a strong base. Examples of the base used at this time include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium alkoxide, potassium alkoxide, alkylmagnesium halide, sodium hydride, butyl lithium and the like. Sodium hydride and sodium hydroxide are preferable as bases having few side reactions and sufficient reactivity.

In the above etherification reaction, a solvent can be used if necessary. The solvent used can be any other than the reaction substrate and the solvent that reacts with the strong base. For example, hexane, heptane, octane, cyclohexane, benzene, toluene, ethylbenzene, xylene, ethyl acetate, butyl acetate, isobutyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dichloromethane, chloroform, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, tetrahydrofuran, Examples include dimethyl ether. In particular, when sodium hydride or the like, which is a strong base, is used, it is preferable to use hydrocarbons such as hexane, heptane, octane, cyclohexane, benzene, toluene, ethylbenzene and xylene, and ethers such as tetrahydrofuran and dimethyl ether.

The reaction conditions for etherification vary depending on the solvent used, the type and the amount, but are preferably in the range of 0 to 100 ° C. Further, 20 to 70 ° C. is more preferable.

Examples of the esterification method include a method in which an aliphatic substituted with halogen and an unsaturated fatty alcohol having a carbon-carbon double bond at the β-position of the hydroxyl group are dehydrated and condensed to esterify.

In the dehydration condensation reaction, a solvent or a catalyst can be used if necessary. The solvent used can be any solvent other than a solvent that reacts with the reaction substrate, such as alcohol, amine, and carboxylic acid. For example, hexane, heptane, octane, cyclohexane, benzene, toluene, ethylbenzene, xylene, ethyl acetate, butyl acetate, isobutyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dichloromethane, chloroform, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, etc. Be done.

The catalysts used are acid catalysts such as sulfuric acid, hydrochloric acid, methanesulfonic acid and p-toluenesulfonic acid, base catalysts such as sodium hydroxide and sodium carbonate, triethylamine, tributylamine, trioctylamine, tetramethylethylenediamine, N and N. -Amines such as dimethylethanolamine, N, N-dimethylbenzylamine, pyridine, 4- (dimethylamino) pyridine, imidazole, N-methylimidazole, iron (III), zirconium (IV), scandium (III), titanium Examples thereof include salts and complexes containing metal ions such as (IV), tin (IV) and hafnium (IV), and ammonium salts such as diphenylammonium triflate and pentafluorophenylammonium triflate.

The dehydration condensation reaction can be carried out using a condensing agent. The condensing agent can activate the carboxylic acid or alcohol and carry out the esterification reaction under mild conditions, and at the same time, the by-product water combines with the condensing agent to form another compound. It is a compound that has both a catalytic action and a water removing action. Examples of such condensing agents include dicyclohexylcarbodiimide, diidopropylcarbodiimide, 1-ethyl-3- (N, N-dimethylaminopropyl) carbodiimide hydrochloride, carbonyldimidazole, ethyl chloroaterate, isobutyl kiloloate, p-. Toluenesulfonyl chloride, 2,4,6-trichlorobenzoic acid chloride, 2-methyl-6-nitrobenzoic acid anhydride, o- (7-azabenzotriazole-1-yl) -N, N, N, N-tetra Examples thereof include methyluronium hexafluorophosphate.

The reaction conditions for the dehydration condensation reaction differ depending on the solvent used, the type and amount of the catalyst. For example, when dehydration condensation is performed without a catalyst, a high temperature is required, so 70 to 250 ° C. is preferable. In the dehydration condensation reaction using a condensing agent, the reaction is preferably carried out in the range of -20 to 50 ° C.

For epoxidation of olefins, a commonly used method using an oxidizing agent can be used.

Examples of the oxidizing agent include gas containing oxygen, hydrogen peroxide, inorganic peroxides such as sodium peroxide, peracetic acid, perbenzoic acid, m-chloroperbenzoic acid, p-nitro perbenzoic acid, and monoperoxyphthal. Examples thereof include organic peroxides such as magnesium acid, peroxymaleic acid, peroxytrifluoroacetic acid, peroxyphthalic acid, peroxylauric acid, tert-butylhydroperoxide, cumenehydroperoxide, menthylhydroperoxide, and 1-methylhexanehydroperoxide.

A catalyst can be used in the epoxidation reaction if desired. For example, metal compounds including tungsten, molybdenum, vanadium, titanium, renium, ruthenium, etc., aldehydes such as acetaldehyde, isobutylaldehyde, isovaleroaldehyde, trimethylacetaldehyde, α-aminomethylphosphonic acid, α-aminoethylphosphonic acid, etc. Examples thereof include quaternary onium salts such as α-aminophosphonic acids, trioctylmethylammonium chloride, trioctylethylammonium bromide, dilauryldimethylammonium iodide, and stearyldimethylbenzylammonium hydrogen phosphate.

As the solvent used in the epoxidation reaction, a solvent that does not react with the above-mentioned oxidizing agent can be used. For example, hexane, heptane, octane, cyclohexane, benzene, toluene, ethylbenzene, xylene, ethyl acetate, butyl acetate, isobutyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dichloromethane, chloroform, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, etc. Be done.

The reaction temperature of the epoxidation reaction varies depending on the oxidizing agent, catalyst and solvent used, but is preferably 0 to 150 ° C, more preferably 0 to 50 ° C.

The thermosetting composition of the present invention will be described.

Examples of the curing agent used in the present invention include polycarboxylic acid resins and acid anhydrides.

The polycarboxylic acid resin is not particularly limited as long as it is a resin having an acid value. For example, an acrylic resin having an acid value, a urethane resin having an acid value, a polyester resin having an acid value, and the like can be mentioned. The more cross-linking points, the stronger the cured product can be obtained. Therefore, those having an acid value of 10 mgKOH / g or more are preferable. Further, from the viewpoint of storage stability, those having an acid value lower than 80 mgKOH / g are preferable.

As the acid anhydride, an anhydride of a compound having a plurality of carboxyl groups in one molecule is preferable. Examples of these acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, ethylene glycol bistrimerite, glycerol tristrimerite, maleic anhydride, tetrahydrophthalic anhydride, and methyl anhydride. Tetrahydro phthalic anhydride, endomethylene tetrahydrohydride phthalic acid, methylendomethylene tetrahydrohydride phthalic acid, methylbutenyltetrahydrohydride phthalic acid, dodecenyl anhydride succinic acid, hexahydrohydride anhydride, methylhexahydrohydride phthalic acid, succinic anhydride, methyl Cyclohexene dicarboxylic acid anhydride, chlorendic acid anhydride and the like can be mentioned. Among these, methyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, methylhexahydrophthalic anhydride, and a mixture of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride, which are liquid at normal temperature and pressure, are preferable.

The content of the curing agent is preferably such that the molar ratio of the epoxy group in the composition to the carbonyl group of the polycarboxylic acid resin or the acid anhydride-based curing agent is 1: 0.01 to 1: 2.0. It is 1: 0.4 to 1: 1.5.

The thermosetting composition of the present invention may be appropriately used in combination with a curing accelerator. Examples of the curing accelerator include organic phosphorus compounds such as triphenylphosphine and tributylphosphine, quaternary phosphonium salts such as ethyltriphenylphosphine bromide and diethyl tetrabutylphosphonium dithiophosphate, and 1,8-diazabicyclo [5. 4.0] Undecane-7-ene, 1,8-diazabicyclo [5.4.0] Undecane-7-ene and salts of octyl acid, quaternary ammonium salts such as zinc octylate, tetrabutylammonium bromide, etc. Be done. These curing aids can be contained in a ratio of 0.001 to 0.1 parts by weight with respect to 1 part by weight of the curing agent.

Further, the thermosetting composition of the present invention may further contain an epoxy compound different from the internal epoxy compound having an epoxy group inside the molecule.

The above-mentioned epoxy compound is not particularly limited, and examples of the epoxy compound include bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, phenol novolac type epoxy compound, cresol novolac type epoxy compound, and fat. Examples thereof include a cyclic epoxy compound, a hidden toin type epoxy compound, a hydrogenated bisphenol A type epoxy compound, an aliphatic epoxy compound, a glycidyl ether type epoxy compound, a biphenyl type epoxy compound, a dicyclocyclic epoxy compound, and a naphthalene type epoxy compound. These can be used alone or in combination of two or more.

The thermosetting composition of the present invention can be added with a solvent, if necessary. For example, alcohols such as methanol and ethanol, ethers such as tetrahydrofuran, glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, and diethylene glycol monomethyl ether. , Diethylene glycols such as diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monoalkyl ethers such as propylene glycol propyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, propylene Propropylene glycol alkyl ether acetates such as glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether Propionates, propylene glycol alkyl ether propionates such as propylene glycol butyl ether propionates, royal hydrocarbons such as toluene and xylene, and ketones such as methyl ethyl ketone, cyclohexanone and 4-hydroxy-4-methyl-2-pentanone. Kind, and methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, lactic acid Methyl, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methoxy Methyl acetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, propoxyacetate Ethyl, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-methoxy Butyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-butoxypropion Propyl acid, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionate Ethyl, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate , Ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate and the like.

The thermosetting composition of the present invention is, if necessary, an inorganic filler such as titanium oxide, alumina, silica, a surface conditioner such as a silane coupling agent, a phenolic antioxidant, a phosphorus-based antioxidant, and a sulfur-based one. It may further contain additives such as antioxidants.

The method for producing the thermosetting composition of the present invention is not particularly limited, but for example, an internal epoxy compound having an epoxy group inside the molecule, an acid anhydride curing agent or a polycarboxylic acid resin is used as an organic solvent. It can be obtained by dissolving it, adding other epoxy compounds, additives and the like as necessary, and mixing them.

The resin composition of the present invention is cured by heating. It is usually kept at a temperature of 100 ° C. or higher, preferably 150 ° C. or higher, usually 250 ° C. or lower, preferably 200 ° C. or lower for 0.1 to 24 hours.

Examples of the method for shaping the resin composition of the present invention include a method of molding using a mold, a method of coating on a base material, and the like. As a method of molding using a mold, a molded product made of the composition of the present invention can be obtained by injecting the composition of the present invention into a molding mold, curing the composition by the above method, and removing the mold. it can. When molding using a mold, it is also possible to obtain a molded product in which the surface shape of the mold is transferred. At this time, if the composition of the present invention, which is liquid at the time of molding, is used, precision molding can be performed. The molded product thus obtained has a refractive index of usually 1.5 or more, preferably 1.6 or more, and can be used as an optical component such as a lens, a prism, a waveguide, or a substrate.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto. Unless otherwise specified, "%" means "% by weight" and "part" means "part by weight".

Synthesis example 1

(Aetherization process)
12.3 parts of sodium hydride (purity of 60% or more), 90 parts of tetrahydrofuran, and 16.2 parts of 1,3-dibromopropane were charged into a reaction vessel equipped with a stirrer and a thermometer, and the mixture was stirred at room temperature. 21.6 parts of crotyl alcohol and 60 parts of tetrahydrofuran were mixed and slowly added dropwise over 1 hour. The reaction was carried out under heating and reflux for 2 hours, ^{and it was confirmed by 1 1} H-NMR that the reaction was completed. The mixture was cooled to 4 ° C. or lower, water was added to inactivate sodium hydride, and then neutralized with 1N hydrochloric acid. The reaction solution was transferred to a separatory funnel, and toluene was added to separate the phases. After washing with water and drying with magnesium sulfate, the solvent was distilled off with an evaporator. Twelve parts of the reaction intermediate (1-1) were obtained.

(Epoxidation process)
In a reaction vessel equipped with a stirrer and a thermometer, 12 parts of the intermediate (1-1), 55.5 parts of sodium hydrogen carbonate, 110 parts of acetone and 85 parts of water were charged and stirred at room temperature. To this, 75 parts of oxone (potassium peroxysulfate double salt) was divided into 4 parts and added every hour. The reaction was carried out overnight at room temperature, ^{and it was confirmed by 1 1} H-NMR that the reaction was completed. The reaction solution was transferred to a separatory funnel, water was added, and the mixture was extracted with ethyl acetate. After washing with water and drying with magnesium sulfate, the solvent was distilled off with an evaporator to obtain 7.1 parts of compound (1). The structure of the obtained compound (1) was ^{confirmed by 1 1} H-NMR.

Synthesis example 2

Except for using 18.5 parts of 1,3-dibromo-2,2-dimethylpropane in place of 16.2 parts of 1,3-dibromopropane in Synthesis Example 1 in the same manner as in Synthesis Example 1 Compound (2) Synthesized. The structure of the obtained compound (2) was ^{confirmed by 1 1} H-NMR.

Synthesis example 3

The Kurochiruburomido 24 parts instead of in Synthesis Example 1 1,3-dibromopropane 16.2 parts, also the synthesis examples except for using 15.5 parts of tripropylene glycol instead of 21.6 parts of crotyl alcohol Compound (3) was synthesized in the same manner as in 1. The structure of the obtained compound (3) was ^{confirmed by 1 1} H-NMR.

Synthesis example 4

In Synthesis Example 1, 24 parts of crotyl bromide was used instead of 16.2 parts of 1,3-dibromopropane, and 5-[(5-hydroxypentanoyl) oxy] pentanoic acid was used instead of 21.6 parts of crotyl alcohol. Compound (4) was synthesized in the same manner as in Synthesis Example 1 except that 17.5 parts were used. The structure of the obtained compound (4) was ^{confirmed by 1 1} H-NMR.

Synthesis example 5

The Kurochiruburomido 36 parts instead of 16.2 parts of 1,3-dibromopropane in Synthesis Example 1, also the synthesis examples except for using 7.1 parts of trimethylolpropane instead of 21.6 parts of crotyl alcohol Compound (5) was synthesized in the same manner as in 1. The structure of the obtained compound (5) was ^{confirmed by 1 1} H-NMR. ^{A 1} H-NMR chart of compound (5) is shown in FIG.

Synthesis example 6

Except for using 31.1 parts of pentaerythrityl tetrabromide in place of 16.2 parts of 1,3-dibromopropane in Synthesis Example 1 compound in the same manner as in Synthesis Example 1 (6) was synthesized. The structure of the obtained compound (6) was ^{confirmed by 1 1} H-NMR.

Synthesis example 7

In Synthesis Example 1 , 15.3 parts of 1-bromooct-2-ene was used instead of 16.2 parts of 1,3-dibromopropane, and 2- [3- (2-) was used instead of 21.6 parts of crotyl alcohol. Compound (7) was synthesized in the same manner as in Synthesis Example 1 except that 50 parts of hydroxyethoxy) propoxy] ethane-1-ol was used. The structure of the obtained compound (7) was ^{confirmed by 1 1} H-NMR.

Synthesis example 8

In Synthesis Example 1, 18.5 parts of 1,3-dibromo-2,2-dimethylpropane was used instead of 16.2 parts of 1,3-dibromopropane, and 2-octene was used instead of 21.6 parts of crotyl alcohol. Compound (8) was synthesized in the same manner as in Synthesis Example 1 except that 38.4 parts of -1-ol was used. The structure of the obtained compound (8) was ^{confirmed by 1 1} H-NMR.

Subsequently, Table 1 shows a compounding example of the resin composition. In the table, "molar" indicates the number of moles of functional groups, the epoxy compound of the general formula (1) and the epoxy compound other than the general formula (1) have an epoxy group amount, and the curing agent has a carbonyl group amount in the curing agent. It was blended in the amount shown in Table 1.

Table 1

The compounds used in Table 1 are shown below.
jER828 (bisphenol A type epoxy resin) ・ ・ ・ jER630 (N, N-diglycidyl-4-glycidyloxyaniline) manufactured by Mitsubishi Chemical Corporation ・ ・ ・ MHHPA (methylhexahydrophthalic anhydride) manufactured by Mitsubishi Chemical Corporation ・ ・ ・ New Japan Rikasid MH700
THPA (Tetrahydrophthalic anhydride) ・ ・ ・ Recasid TH, manufactured by Shin Nihon Rika Co., Ltd.
SG-700AS (acid value-containing acrylic resin): manufactured by Nagase ChemteX (acid value: 34 mgKOH / g)
BDMA (N, N-benzyldimethylamine) ... manufactured by Wako Pure Chemical Industries, Ltd.

Examples 9 to 20 , Comparative Examples 1 to 3
2-Butanone was added to the resin composition of the formulation example shown in Table 1 to prepare a solution having a solid content of 80%, and a curable material was obtained. The PET film was coated with a 10 mil applicator and dried at 120 ° C. for 10 minutes to form a resin composition layer. Next, it was cured by heating in an oven at 200 ° C. for 30 minutes.

The properties of the resin composition and the cured product were evaluated by the following methods.

≪Gel fraction≫
After measuring the weight of the resin composition obtained by drying at 120 ° C. for 10 minutes or the cured product obtained by further heating at 200 ° C. for 30 minutes (weight 1), it is cured by sandwiching it between metal meshes. The objects were refluxed in methyl ethyl ketone (MEK) for 3 hours so that they did not overlap with each other. Further, it was dried at 80 ° C. for 30 minutes, and the weight of the cured product was measured (weight 2). The gel fraction was calculated from the following formula and evaluated in two stages.

Gel fraction (%) = {1- (weight 1-weight 2) / weight 1}}} x 100

◯: Gel fraction is 90% or more Δ: Gel fraction is 30% or more to less than 90% ×: Gel fraction is less than 30%

≪Heat responsiveness≫
Based on the result of gel fraction measurement, the thermal responsiveness was evaluated in two stages.
◯: Gel fraction at 120 ° C. for 10 minutes is less than 30% and gel fraction at 200 ° C. for 30 minutes is 90% or more ×: Gel fraction at 120 ° C. for 10 minutes is 30% or more and 200 ° C. for 30 minutes Gel fraction in 90% or more

≪Storage stability≫
After storing the prepared curable material at 60 ° C. for 5 days, the state of the curable material was visually observed.
○: No change ×: Thickening or gelling

The results are shown in Table 2.

In Comparative Examples 1 to 3, the curing proceeded under the solvent drying condition. In addition, the storage stability at 60 ° C. was extremely poor. It is considered that this is because the structure has an epoxy group at the end of the molecule.

From the above results, by using an internal epoxy compound having an epoxy group inside the molecule of the present invention, it is excellent in storage stability when blended with an acid anhydride or a polycarboxylic acid resin, and it does not react at low temperature heating and is high temperature. It has been possible to provide an epoxy compound and a thermosetting composition that exhibit excellent thermal responsiveness that reacts only when heated.

Applications of the resin composition of the present invention include coating agents, adhesives, sealing materials for the purpose of antireflection and protection, and raw materials for molded products such as parts, sheets, laminated boards, and composite materials. ..
Further, as an application of the cured product obtained by curing the composition of the present invention, use as a material for optical parts such as lenses, prisms, waveguides, substrates, laminated materials, composite materials, and electronic parts is exemplified. To.
In particular, by taking advantage of the characteristics such as transparency and high refraction of the obtained cured product, it can also be used for optical components such as lenses and waveguides, and their adhesives and sealants.

Claims (6)

A thermosetting composition containing an internal epoxy compound having an epoxy group inside the molecule represented by the following general formula (1) and a polycarboxylic acid resin or an acid anhydride-based curing agent.
General formula (1)

(In the formula, R represents an m + n-valent aliphatic hydrocarbon group.
The m + n-valent aliphatic hydrocarbon group may be interrupted by an ether bond or an ester bond.
X and Y each independently represent a monovalent aliphatic hydrocarbon group.
In addition, m represents an integer of 1 to 4, and represents
n represents an integer from 0 to 3.
However, the value of m + n is an integer of 2 to 4. ) The thermosetting composition according to claim 1, wherein X and Y are independently monovalent aliphatic hydrocarbon groups having 1 to 10 carbon atoms. The thermosetting composition according to claim 1 or 2, further comprising a curing accelerator. The thermosetting composition according to any one of claims 1 to 3, further comprising an epoxy resin other than the internal epoxy compound. The heat according to any one of claims 1 to 4, wherein the molar ratio of the epoxy group in the composition to the carbonyl group of the polycarboxylic acid resin or the acid anhydride-based curing agent is 1: 0.01 to 1: 2.0. Curable composition. A cured product obtained by curing the thermosetting composition according to any one of claims 1 to 5.

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