JP2019194275A - Epoxy compound, method for producing epoxy compound, epoxy compound-containing composition and cured product thereof - Google Patents

Abstract

To provide an epoxy compound excellent in light resistance and coating film hardness and to provide an epoxy compound-containing composition and a cured product thereof.SOLUTION: The epoxy compound has a divalent group represented by formula (1) and a divalent group represented by -O-X-OCH2CH(OH)CH2- (X is a chlorine- and bromine-free 1-50C divalent group) and has an epoxy equivalent of 200 to 200,000 g/equivalent. The epoxy compound-containing composition includes the epoxy compound and a curing agent. The cured product of the epoxy compound-containing composition is provided. (Rto Reach independently represent H or a 1-4C aliphatic hydrocarbon group.)SELECTED DRAWING: None

Description

  The present invention relates to an epoxy compound having excellent light resistance and a method for producing the same. The present invention also relates to an epoxy compound-containing composition and a cured product obtained by using the epoxy compound.

  Epoxy compounds are widely used in the fields of paints, civil engineering, adhesion, electrical materials and the like because they are excellent in heat resistance, adhesiveness, flexibility, electrical properties and the like. Patent Document 1 describes a reaction product of a high halogen content epoxy resin and a hindered amine compound, but the high halogen content epoxy compound has insufficient light resistance.

JP-A-8-165437

  The present invention has been made in view of the above problems of the prior art. That is, the subject of this invention is providing the epoxy compound excellent in light resistance and coating-film hardness, the manufacturing method of an epoxy compound, an epoxy compound containing composition, and its hardened | cured material.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a non-chlorine / non-bromine type epoxy compound having a piperidine ring having an epoxy equivalent of 200 g / equivalent to 200,000 g / equivalent or less. The inventors have found that a compound can solve the above-mentioned problems, and have completed the invention. That is, the gist of the present invention resides in the following [1] to [11].
[1] It has a divalent group represented by the following formula (1) and a divalent group represented by the following formula (2), and an epoxy equivalent is 200 g / equivalent or more and 200,000 g / equivalent or less. Epoxy compound.

(In formula (1), R ^{1 to} R ⁴ may be the same or different and each represents a hydrogen atom or a saturated or unsaturated aliphatic hydrocarbon group having 1 to 4 carbon atoms.)

(In the formula (2), X represents a divalent group having 1 to 50 carbon atoms which does not contain chlorine and bromine and may have a substituent.)
[2] The epoxy compound according to [1], wherein the total amount of chlorine and total bromine is 3% by weight or less.
[3] The epoxy compound according to [1] or [2], comprising two or more different groups as the divalent group represented by the formula (1).
[4] The epoxy compound according to any one of [1] to [3], including two or more different groups as the divalent group represented by the formula (2).
[5] X represents a structure represented by any of the following formula (3), the following formula (4), the following formula (5), the following formula (6), the following formula (7), or the following formula (8). The aromatic ring or cycloalkylene group in the following formulas (3) to (8), each of which is optionally substituted with an alkyl group, according to any one of [1] to [4] Epoxy compound.

(In the formula (3), R ⁵ and R ⁶ may be the same or different and each represents a hydrogen atom or an alkyl group.)

(In the formula (4), R ⁷ and R ⁸ may be the same or different and each represents a hydrogen atom or an alkyl group.)

(In the formula (7), R ⁹ and R ¹⁰ may be the same or different and represent a direct bond or an alkylene group having 1 to 5 carbon atoms.)

(In formula (8), R ¹¹ and R ¹² may be the same or different, and represent a direct bond or an alkylene group having 1 to 5 carbon atoms.)
[6] The method according to any one of [1] to [5], which is obtained by reacting a piperidine ring-containing compound with an epoxy group-containing compound in which the total amount of total chlorine and total bromine is 5% by weight or less. A method for producing an epoxy compound.
[7] Any one of [1] to [5] obtained by reacting a piperidine ring-containing compound, an epoxy group-containing compound in which the total amount of chlorine and total bromine is 5% by weight or less, and a phenol compound The manufacturing method of the epoxy compound of description.
[8] An epoxy compound-containing composition comprising the epoxy compound according to any one of [1] to [5] and a curing agent.
[9] The epoxy compound-containing composition according to [8], including 0.1 to 1000 parts by weight of a curing agent with respect to 100 parts by weight of the epoxy compound.
[10] The curing agent comprises a polyfunctional phenol, a polyisocyanate compound, an amine compound, an acid anhydride compound, an imidazole compound, an amide compound, a mercaptan compound, a cationic polymerization initiator, and an organic phosphine. The epoxy compound-containing composition according to [8] or [9], which is at least one selected from the group.
[11] A cured product obtained by curing the epoxy compound-containing composition according to any one of [8] to [10].

  According to the present invention, an epoxy compound and an epoxy compound-containing composition excellent in light resistance and coating film hardness are provided. Due to these features, the epoxy compound, the epoxy compound-containing composition and the cured product of the present invention can be applied in the fields of electrical / electronic materials, FRP (fiber reinforced resin), adhesives, paints, and the like. is there.

Embodiments of the present invention will be described in detail below, but the present invention is not limited to the following descriptions, and can be arbitrarily modified and implemented without departing from the gist of the present invention. In this specification, when a value or physical property value is put before and after using “to”, the value before and after that is used.
Moreover, the carbon number of various groups demonstrated in this specification means the total carbon number including the carbon number of the substituent, when the said group has a substituent.

[Epoxy compound]
The epoxy compound of the present invention has a divalent group represented by the following formula (1) and a divalent group represented by the following formula (2), and the epoxy equivalent exceeds 200 g / equivalent to 200,000 g / An epoxy compound having an equivalent weight or less. By having a divalent group represented by the following formula (1) and a divalent group represented by the following formula (2), it is excellent in light resistance and coating film hardness. When the epoxy equivalent is more than 200 g / equivalent and 200,000 g / equivalent or less, both the flexibility and hardness of the coating film are excellent.

(In formula (1), R ^{1 to} R ⁴ may be the same or different and each represents a hydrogen atom or a saturated or unsaturated aliphatic hydrocarbon group having 1 to 4 carbon atoms.)
In the formula (1), R ^{1 to} R ⁴ may be the same or different and each represents a hydrogen atom or a saturated or unsaturated aliphatic hydrocarbon group having 1 to 4 carbon atoms. Among these, a hydrogen atom, a methyl group, or an ethyl group is preferable, and a methyl group is more preferable. R ^{1 to} R ⁴ are more preferably the same and a methyl group.

(In the formula (2), X represents a divalent group having 1 to 50 carbon atoms which does not contain chlorine and bromine.)
In the divalent group represented by the formula (2), X may have a substituent having 1 to 50 carbon atoms, preferably 1 to 40 carbon atoms, more preferably 1 to 35 carbon atoms. A divalent hydrocarbon group is shown. X may be a linear, branched or cyclic chain hydrocarbon group, but is preferably a hydrocarbon group containing a cyclic structure. X may have a substituent. X must be free of chlorine and bromine. By having the structure of Formula (2), it is excellent in chemical resistance, adhesiveness and flexibility.

  X is preferably a group having a structure represented by any of the following formulas (3) to (8), and each aromatic ring or cyclohexylene group in the following formulas (3) to (8) is It may be substituted with an alkyl group.

(In the formula (3), R ⁵ and R ⁶ may be the same or different and each represents a hydrogen atom or an alkyl group.)

(In the formula (4), R ⁷ and R ⁸ may be the same or different and each represents a hydrogen atom or an alkyl group.)

(In the formula (7), R ⁹ and R ¹⁰ may be the same or different and represent a direct bond or an alkylene group having 1 to 5 carbon atoms.)

(In formula (8), R ¹¹ and R ¹² may be the same or different, and represent a direct bond or an alkylene group having 1 to 5 carbon atoms.)
In the formula (3), R ⁵ and R ⁶ may be the same or different and each represents a hydrogen atom or an alkyl group. R ⁵ and R ⁶ are preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

In the formula (4), R ⁷ and R ⁸ may be the same or different and each represents a hydrogen atom or an alkyl group. R ⁷ and R ⁸ are preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
In the formula (7), R ⁹ and R ¹⁰ represent a direct bond or an alkylene group having 1 to 5 carbon atoms. R ⁹ and R ¹⁰ are preferably a direct bond.

In the formula (8), R ¹¹ and R ¹² represent a direct bond or an alkylene group having 1 to 5 carbon atoms. R ¹¹ and R ¹² are preferably a direct bond.
When the aromatic ring or cyclohexylene group represented by the formulas (3) to (8) has a substituent, the substituent is not particularly limited, and examples thereof include an alkyl group having 1 to 2 carbon atoms. The number of substituents per cyclohexylene group is preferably 2 or less.

[Method for producing epoxy compound]
Although the manufacturing method of the epoxy compound of this invention is not specifically limited, The epoxy group containing compound (A) mentioned later as a raw material of an epoxy compound, a piperidine ring containing compound (B), and a phenol compound (C) as needed. A technique of copolymerization is mentioned. In this copolymerization reaction, two or more kinds of the following epoxy group-containing compound (A), piperidine ring-containing compound (B) and phenol compound (C) can be used.

[Epoxy group-containing compound (A)]
The epoxy group-containing compound (A) is a compound having two or more epoxy groups in the molecule. The epoxy group-containing compound (A) of the present invention is not particularly limited as long as it introduces a divalent group represented by the formula (2).
For example, as a bifunctional epoxy group-containing compound, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol E diglycidyl ether, bisphenol Z diglycidyl ether, bisphenol S diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol acetophenone diglycidyl Ether, bisphenol trimethylcyclohexane diglycidyl ether, bisphenol fluorenediglycidyl ether, tetramethylbisphenol A diglycidyl ether, tetramethylbisphenol F diglycidyl ether, tetra-t-butylbisphenol A diglycidyl ether, tetramethylbisphenol S diglycidyl ether, etc. Bisphenol diglycidyl Tellurides; biphenol diglycidyl ethers such as biphenol diglycidyl ether, tetramethylbiphenol diglycidyl ether, dimethyl biphenol diglycidyl ether, tetra-t-butylbiphenol diglycidyl ether; hydroquinone diglycidyl ether, dihydroanthracene diglycidyl ether, Benzenediol diglycidyl ethers such as methyl hydroquinone diglycidyl ether, dibutyl hydroquinone diglycidyl ether, resorcin diglycidyl ether, methyl resorcin diglycidyl ether; dihydroanthrahydroquinone diglycidyl ether, dihydroxydiphenyl ether diglycidyl ether, thiodiphenol diglycidyl ether Ether, dihydroxynaphthalene Aromatic diglycidyl ethers such as glycidyl ether; diglycidyl ethers selected from bisphenol diglycidyl ethers, biphenol diglycidyl ethers, benzenediol diglycidyl ethers and aromatic diglycidyl ethers; Epoxy compounds with hydrogen added to the aromatic ring; various carboxylic acids such as adipic acid, succinic acid, phthalic acid, tetrahydrophthalic acid, methylhexahydrophthalic acid, terephthalic acid, isophthalic acid, orthophthalic acid, biphenyldicarboxylic acid, dimer acid, etc. And an epoxy resin produced from epihalohydrin; ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol Diglycidyl ether, 1,4-butanediol diglycidyl ether, polytetramethylene glycol diglycidyl ether, 1,5-pentanediol diglycidyl ether, polypentamethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, Polyhexamethylene glycol diglycidyl ether, 1,7-heptanediol diglycidyl ether, polyheptamethylene glycol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2- (Poly) alkylene glycol diglycidyl ethers consisting only of a chain structure such as dimethyl-1,3-propanediol diglycidyl ether;
Examples include alkylene glycol diglycidyl ethers having a cyclic structure such as 4-cyclohexanedimethanol diglycidyl ether.

Moreover, as a trifunctional or more than trifunctional epoxy group containing compound, the following are mentioned, for example. In the following examples, the type epoxy resin refers to a hydroxy group substituted with a glycidyl ether group.
α, α-bis (4-hydroxyphenyl) -4- (4-hydroxy-α, α-dimethylbenzyl) -ethylbenzene type epoxy resin, 4,4 ′, 4 ″ -trihydroxytriphenylmethane type epoxy resin, 4 , 4 ′, 4 ″ -Ethyridinetris (2-methylphenol) type epoxy resin, 4,4 ′-(2-hydroxybenzylidene) bis (2,3,6-trimethylphenol) type epoxy resin, 2,3 , 4-Trihydroxydiphenylmethane type epoxy resin, 2,4,6-tris (4, hydroxyphenyl) -1,3,5-triazine type epoxy resin, 1,3,5-tris (4-hydroxyphenyl) benzene type Epoxy resin, 1,1,1-tris (4-hydroxyphenyl) ethane type epoxy resin, 4,4 '-[1- [4- [1- (4-hydroxy- , 5-Dimethylphenyl) -1-methylethyl] phenyl] ethylidene] bis (2-methylphenol) type epoxy resin, 2,6-bis (4-hydroxy-3,5-dimethylbenzyl) -4-methylphenol type Trifunctional epoxy resins such as epoxy resin; 2,2′-methylenebis [6- (2-hydroxy-5-methylbenzyl) -p-cresol type epoxy resin, 4- [bis (4-hydroxy-3-methylphenyl) ) Methyl] benzene-1,2-diol type epoxy resin, 1,1,2,2-tetrakis (p-hydroxyphenyl) ethane type epoxy resin, α, α, α ′, α ′,-tetrakis (4-hydroxy) Tetrafunctional epoxy resins such as phenyl) -p-xylene type epoxy resin; 2,4,6-tris [(4-hydroxyphenyl) methyl] -1,3 Pentafunctional epoxy resins such as benzenediol type epoxy resins; epoxy compounds produced from various amine compounds such as diaminodiphenylmethane, aminophenol, xylenediamine and the like, and epihalohydrin, epoxy compounds produced from an aliphatic polyol and epihalohydrin , Phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, naphthol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, phenol-modified xylene type epoxy resin, and these various phenols Polyphenols obtained by condensation reaction of aldehydes with various aldehydes such as hydroxybenzaldehyde, crotonaldehyde, and glyoxal Resins, polyfunctional epoxy resins such as epoxy resin used co-condensation resin various phenolic compounds of such like of the heavy oil or pitch such phenols with formaldehydes, and the like.

  Among these, it is preferable to use a bifunctional epoxy group-containing compound from the viewpoint of preventing gelation during production. In addition, from the viewpoint of obtaining good film hardness, epoxy group-containing compounds in which hydrogen is added to the aromatic ring of bisphenol diglycidyl ethers, biphenol diglycidyl ethers, bisphenol diglycidyl ethers, biphenol diglycidyl ethers It is preferable to use an epoxy group-containing compound obtained by adding hydrogen to the aromatic ring.

  The epoxy group-containing compound (A) mentioned above can be used alone or in combination of two or more. Preferred combinations include bisphenol diglycidyl ethers, biphenol diglycidyl ethers, epoxy group-containing compounds with hydrogen added to the aromatic ring of bisphenol diglycidyl ethers, and hydrogen added to the aromatic ring of biphenol diglycidyl ethers. A combination selected from epoxy group-containing compounds.

[Piperidine ring-containing compound (B)]
The piperidine ring-containing compound (B) is a compound having one or more piperidine rings in the molecule and one or more NH groups in the molecule and / or one or more OH groups in the molecule.
The piperidine ring-containing compound (B) of the present invention is not particularly limited as long as it introduces a divalent group represented by the above formula (1), but it is preferable that neither a chlorine nor bromine is contained. For example, 2,2,6,6-tetramethyl-4-piperidyl methacrylate and the like are listed as compounds having one NH group in the molecule. Examples of the compound having one OH group in the molecule include dimethyl succinate / 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate. Examples of the compound having two NH groups in the molecule include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate. Compounds having three or more NH groups in the molecule include tetrakis (2,2,6,6-tetramethyl-4-piperidyl) butane-1,2,3,4-tetracarboxylate, poly [(6-morpholino -S-triazine-2,4-diyl) [2,2,6,6-tetramethyl-4-piperidyl] imino] -hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino ] Etc. are mentioned. Among these, a compound in which the total number of OH groups and NH groups is 2 is preferable from the viewpoint of polymerizability.
The piperidine ring-containing compound (B) mentioned above can be used alone or in combination of two or more. When two or more kinds of piperidine ring-containing compounds (B) are used, preferred combinations include a compound having one OH group, a compound having two OH groups, a compound having one NH group, and a compound having two NH groups. It is a combination selected from.

[Phenol compound C]
The phenol compound (C) of the present invention is a compound having two or more hydroxyl groups bonded to an aromatic ring. By copolymerizing the phenol compound (C), it is useful for adjusting the viscosity of the production process and controlling the physical properties of the resulting epoxy compound.
The phenolic compound (C) of the present invention needs to contain neither chlorine nor bromine. For example, bisphenol A, bisphenol F, bisphenol E, bisphenol Z, bisphenol S, bisphenol AD, bisphenol acetophenone, bisphenol trimethylcyclohexane, bisphenol fluorene, tetramethyl bisphenol A, tetramethyl bisphenol are compounds having two hydroxyl groups bonded to an aromatic ring. Bisphenols such as F, tetra-t-butylbisphenol A, and tetramethylbisphenol S; biphenols such as biphenol, tetramethylbiphenol, dimethylbiphenol, and tetra-t-butylbiphenol; hydroquinone, methylhydroquinone, dibutylhydroquinone, resorcin, methyl Benzenediols such as resorcinol (here, “benzenediols” A compound having one benzene ring, in which two hydroxyl groups are directly bonded to the benzene ring.); Dihydroanthrahydroquinones; dihydroxydiphenyl ethers such as dihydroxydiphenyl ether; and thiodiphenols such as thiodiphenol Phenols; Dihydroxynaphthalenes such as dihydroxynaphthalene; and dihydroxystilbene compounds such as dihydroxystilbene.

Examples of the compound having three or more hydroxyl groups bonded to an aromatic ring include α, α-bis (4-hydroxyphenyl) -4- (4-hydroxy-α, α-dimethylbenzyl) -ethylbenzene, 4,4 ′, 4. "-Trihydroxytriphenylmethane, 4,4 ', 4" -ethylidinetris (2-methylphenol), 4,4'-(2-hydroxybenzylidene) bis (2,3,6-trimethylphenol), 2,3,4-trihydroxydiphenylmethane, 2,4,6-tris (4, hydroxyphenyl) -1,3,5-triazine, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1 , 1-tris (4-hydroxyphenyl) ethane, 4,4 ′-[1- [4- [1- (4-hydroxy-3,5-dimethylphenyl) -1-methylethyl] phenyl] e Ridene] bis (2-methylphenol), trifunctional phenolic compounds such as 2,6-bis (4-hydroxy-3,5-dimethylbenzyl) -4-methylphenol; 2,2′-methylenebis [6- (2-hydroxy-5-methylbenzyl) -p-cresol, 4- [bis (4-hydroxy-3-methylphenyl) methyl] benzene-1,2-diol, 1,1,2,2-tetrakis (p -Hydroxyphenyl) ethane, tetrafunctional phenolic compounds such as α, α, α ′, α ′,-tetrakis (4-hydroxyphenyl) -p-xylene; 2,4,6-tris [(4-hydroxyphenyl ) Methyl] -1,3-benzenediol and other pentafunctional phenolic compounds, phenol novolac resins, cresol novolac resins, bisphenol A novolac Bisphenol novolak resins such as resins; various phenol resins such as naphthol novolak resins, phenol aralkyl resins, terpene phenol resins, dicyclopentadiene phenol resins, phenol biphenylene resins, phenol-modified xylene resins, and various phenols thereof And polyfunctional phenols such as polyphenol resins obtained by condensation reaction with various aldehydes such as hydroxybenzaldehyde, crotonaldehyde, and glyoxal, and co-condensation resins of heavy oil or pitches with phenols and formaldehyde System compounds and the like.

Among these, it is preferable to use a compound having two hydroxyl groups bonded to an aromatic ring from the viewpoint of preventing gelation during production. Moreover, it is preferable to use bisphenols and biphenols from the viewpoint of obtaining good film hardness.
The compounding ratio of the epoxy group-containing compound (A), piperidine ring-containing compound (B) and phenolic compound (C) used in the production of the epoxy compound of the present invention is such that the theoretical epoxy equivalent of the resulting epoxy compound is 200,000 g / equivalent. The blending ratio is preferably 150,000 g / equivalent or less, more preferably 100,000 g / equivalent or less, and the blending ratio of 100,000 g / equivalent or less ensures compatibility with other materials. This is particularly preferable. On the other hand, the upper limit of the theoretical epoxy equivalent exceeds 100 g / equivalent, and is preferably 120 g / equivalent or more, particularly 150 g / equivalent or more, particularly 200 g / equivalent or more. .

Here, the theoretical epoxy equivalent means that all the epoxy groups, NH groups and / or OH groups contained in the bifunctional epoxy group-containing compound (A), the piperidine ring-containing compound (B) and the phenol compound (C) are 1: 1. Means the epoxy equivalent of the reaction product when reacted with.
In the present invention, “epoxy equivalent” is defined as “mass of an epoxy compound containing one equivalent of an epoxy group” and can be measured according to JIS K7236.

[Catalyst (D)]
A catalyst (D) may be used in the reaction step for producing the epoxy compound of the present invention. The catalyst (D) is not particularly limited as long as it is usually used as a catalyst for the advance method in the epoxy resin production method.
Examples of the catalyst (D) include alkali metal compounds, organic phosphorus compounds, tertiary amines, quaternary ammonium salts, cyclic amines, imidazoles and the like.

  Specific examples of the alkali metal compound include alkali metal hydroxides such as sodium hydroxide, lithium hydroxide and potassium hydroxide; alkali metal salts such as sodium carbonate, sodium bicarbonate, sodium chloride, lithium chloride and potassium chloride; sodium Examples thereof include alkali metal alkoxides such as methoxide and sodium ethoxide; alkali metal hydrides such as alkali metal phenoxide, sodium hydride and lithium hydride; alkali metal salts of organic acids such as sodium acetate and sodium stearate.

Specific examples of the organic phosphorus compound include triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tri-2,4-xylylphosphine, tri-2,5- Xylylphosphine, tri-3,5-xylylphosphine, tris (p-tert-butylphenyl) phosphine, tris (p-methoxyphenyl) phosphine, tris (p-tert-butoxyphenyl) phosphine, tri (pn) -Octylphenyl) phosphine, tri (pn-nonylphenyl) phosphine, triallylphosphine, tributylphosphine, trimethylphosphine, tribenzylphosphine, triisobutylphosphine, tri-tert-butylphosphine, tri-n-octylphosphine, tri Cyclohex Ruphosphine, tri-n-propylphosphine, di-t-butylmethylphosphine, tri-n-butylphosphine, cyclohexyldi-tert-butylphosphine, diethylphenylphosphine, di-n-butylphenylphosphine, di-tert-butyl Phenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, diphenylpropylphosphine, isopropyldiphenylphosphine, cyclohexyldiphenylphosphine, tetramethylphosphonium bromide, tetramethylphosphonium iodide, tetramethylphosphonium hydroxide, trimethylcyclohexylphosphonium chloride, trimethylcyclohexylphosphonium bromide, Trimethylbenzylphosphonium chloride, Limethylbenzylphosphonium bromide, tetraphenylphosphonium bromide, triphenylmethylphosphonium bromide, triphenylmethylphosphonium iodide, triphenylethylphosphonium chloride, triphenylethylphosphonium bromide, triphenylethylphosphonium iodide, triphenylbenzylphosphonium chloride, triphenyl Examples thereof include phenylbenzylphosphonium bromide.

Specific examples of the tertiary amines include triethylamine, tri-n-propylamine, tri-n-butylamine, triethanolamine, N, N-dimethylbenzylamine and the like.
Specific examples of the quaternary ammonium salt include tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium hydroxide, triethylmethylammonium chloride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrapropylammonium bromide, Tetrapropylammonium hydroxide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium hydroxide, benzyltributylammonium chloride Id, and phenyl trimethylammonium chloride and the like.

Specific examples of cyclic amines include 1,8-diazabicyclo (5,4,0) -7-undecene, 1,5-diazabicyclo (4,3,0) -5-nonene.
Specific examples of imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and the like.
The catalyst (D) mentioned above may be used alone or in combination of two or more.
When using a catalyst (D), it is preferable that the usage-amount is normally 10,000 weight ppm or less with respect to the usage-amount of the said epoxy group containing compound (A), for example, 10-5000 weight ppm.

[Reaction solvent (E)]
In the reaction step for producing the epoxy compound of the present invention, a reaction solvent (E) may be used. The reaction solvent (E) is not particularly limited as long as it dissolves the raw material, but is usually an organic solvent.
Examples of the organic solvent include aromatic solvents, ketone solvents, amide solvents, glycol ether solvents, and the like. Specific examples of the aromatic solvent include benzene, toluene, xylene and the like. Examples of ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, 2-octanone, cyclopentanone, cyclohexanone, and acetylacetone. Specific examples of the amide solvent include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, 2-pyrrolidone, N-methylpyrrolidone and the like. Specific examples of the glycol ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol. Examples include mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate and the like.
The reaction solvent (E) mentioned above may be used alone or in combination of two or more. When a highly viscous product is produced during the reaction, the reaction can be continued by further adding a reaction solvent (E).

[Reaction conditions]
The reaction of the epoxy group-containing compound (A), the piperidine ring-containing compound (B), and the phenol compound (C) can be performed under any of normal pressure, pressurized pressure, and reduced pressure conditions.
Moreover, reaction temperature is 60-240 degreeC normally, Preferably it is 80-220 degreeC, More preferably, it is 100-200 degreeC. It is preferable that the reaction temperature is equal to or higher than the above lower limit because the reaction can easily proceed. Moreover, side reaction is hard to advance that reaction temperature is below the said upper limit, and it is preferable from a viewpoint of obtaining a highly purified epoxy compound.
Although it does not specifically limit as reaction time, Usually, it is 0.5 to 24 hours, Preferably it is 1 to 22 hours, More preferably, it is 1.5 to 20 hours. When the reaction time is not more than the above upper limit, it is preferable from the viewpoint of improving production efficiency, and when it is not less than the above lower limit, it is preferable from the viewpoint that unreacted components can be reduced.

[Diluted solvent (F)]
The epoxy compound of the present invention may be mixed with a diluting solvent (F) after completion of the reaction to adjust the solid content concentration. As the diluting solvent (F), any solvent can be used as long as it usually dissolves an epoxy compound, but it is usually an organic solvent. Specific examples of the organic solvent can be the same as those mentioned as the reaction solvent (E).
In the present invention, the terms “solvent” and “solvent” are used as the “solvent” when used in the reaction of the epoxy compound, and as the “solvent” as used after the completion of the reaction. Alternatively, different types may be used.

[Epoxy equivalent]
The epoxy equivalent of the epoxy compound of the present invention is preferably 200 g / equivalent or more, more preferably 250 g / equivalent or more, and still more preferably 300 g / equivalent or more. Thereby, the flexibility can be further improved.
The upper limit of the epoxy equivalent of the epoxy compound of the present invention is not particularly limited, but is 200,000 g / equivalent from the viewpoint of compatibility with other materials, preferably 100,000 g / equivalent, More preferably, it is 1,000 g / equivalent.

[Total of total chlorine and bromine]
The total of the total chlorine amount and the total bromine amount in the epoxy compound of the present invention is preferably 3% or less, more preferably 2% or less, more preferably the total of the epoxy compound and the total chlorine amount and the total bromine amount. It is preferably 1% or less from the viewpoint of improving light resistance. The lower limit is preferably 0%, but may actually be 0.0001%.
The method of bringing the total of the total chlorine amount and the total bromine amount of the epoxy compound of the present invention into the above range is not particularly limited. For example, the total of the total chlorine amount and the total bromine amount is 5% as the epoxy group-containing compound (A). % Or less, preferably 4% by weight or less is used.

[Weight average molecular weight (Mw)]
240 or more are preferable, as for the weight average molecular weight (Mw) of the epoxy compound of this invention, 300 or more are more preferable, and 400 or more are especially preferable at the point which makes a softness | flexibility favorable. The weight average molecular weight (Mw) of the epoxy compound of the present invention is preferably 200,000 or less, more preferably 150,000 or less, and 100,000 or less being compatible with other materials. From the viewpoint of
In addition, the weight average molecular weight of an epoxy compound can be measured by the gel permeation chromatography method (GPC method). An example of a more detailed method will be described in the examples described later.

[Epoxy compound-containing composition]
The epoxy compound-containing composition of the present invention contains at least the above-described epoxy compound of the present invention and a curing agent. Moreover, the epoxy compound containing composition of this invention can mix | blend suitably another epoxy compound, a hardening accelerator, another component, etc. as needed.

[Curing agent]
The curing agent used in the epoxy compound-containing composition of the present invention is a substance that contributes to a crosslinking reaction and / or chain length extension reaction between epoxy groups of the epoxy compound. In the present invention, even if what is usually called a “curing accelerator” is a substance that contributes to a crosslinking reaction and / or chain extension reaction between epoxy groups of an epoxy compound, it is regarded as a curing agent. To do.

The content of the curing agent in the epoxy compound-containing composition of the present invention is preferably 0.1 to 1000 parts by weight, more preferably 100 parts by weight or less, with respect to 100 parts by weight of the epoxy compound of the present invention. The amount is preferably 80 parts by weight or less, and particularly preferably 60 parts by weight or less.
Moreover, in the epoxy compound containing composition of this invention, when other epoxy compounds mentioned later other than the epoxy compound of this invention are contained, content of a hardening | curing agent is with respect to 100 weight part of all the epoxy compound components as solid content. It is preferably 0.1 to 1000 parts by weight, more preferably 100 parts by weight or less, still more preferably 80 parts by weight or less, and particularly preferably 60 parts by weight or less.

More preferable amounts of the curing agent are as described below depending on the type of the curing agent.
In the present invention, the “solid content” means a component excluding a solvent, and includes not only a solid epoxy compound but also a semi-solid or viscous liquid material. Further, the “total epoxy compound component” means the total of the epoxy compound of the present invention and other epoxy compounds described later.

In the epoxy compound-containing composition of the present invention, polyfunctional phenols, polyisocyanate compounds, amine compounds, acid anhydride compounds, imidazole compounds, amide compounds, cationic polymerization initiators, and organic phosphines are used as curing agents. Preferably, at least one of the group consisting of:
Examples of polyfunctional phenols include bisphenol A, bisphenol F, bisphenol S, bisphenol B, bisphenol AD, bisphenol Z, tetrabromobisphenol A, bisphenols, 4,4′-biphenol, 3,3 ′, 5, Biphenols such as 5′-tetramethyl-4,4′-biphenol; catechol, resorcin, hydroquinone, dihydroxynaphthalene; and hydrogen atoms bonded to the aromatic ring of these compounds are halogen groups, alkyl groups, aryl groups, ethers And those substituted with a non-interfering substituent such as an organic substituent containing a hetero element such as a group, an ester group, sulfur, phosphorus or silicon.

Furthermore, novolaks and resoles which are polycondensates of monofunctional phenols such as phenols, phenols, cresols, alkylphenols, and aldehydes can be used.
Examples of polyisocyanate compounds include tolylene diisocyanate, methylcyclohexane diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, dimer acid diisocyanate, trimethylhexamethylene diisocyanate, And polyisocyanate compounds such as lysine triisocyanate. Furthermore, the polyisocyanate compound obtained by the reaction of these polyisocyanate compounds with a compound having at least two active hydrogen atoms such as amino group, hydroxyl group, carboxyl group and water, or 3 to 5 amount of the above polyisocyanate compound The body etc. can be mentioned.

  Examples of amine compounds include aliphatic primary, secondary, tertiary amines, aromatic primary, secondary, tertiary amines, cyclic amines, guanidines, urea derivatives, and the like. Ethylenetetramine, diaminodiphenylmethane, diaminodiphenyl ether, metaxylenediamine, dicyandiamide, 1,8-diazabicyclo (5,4,0) -7-undecene, 1,5-diazabicyclo (4,3,0) -5-nonene, dimethyl Examples include urea and guanylurea.

Examples of the acid anhydride compound include phthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, and a condensate of maleic anhydride and an unsaturated compound.
Examples of imidazole compounds include 1-isobutyl-2-methylimidazole, 2-methylimidazole, 1-benzyl-2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, benzimidazole and the like. It is done. The imidazole compound also functions as a curing accelerator described later, but in the present invention, it is classified as a curing agent.

Examples of amide compounds include dicyandiamide and its derivatives, polyamide resins, and the like.
Cationic polymerization initiators generate cations by heat or active energy ray irradiation, and include aromatic onium salts. Specifically, it consists of an anion component such as SbF6-, BF4-, AsF6-, PF6-, CF3SO32-, B (C6F5) 4- and an aromatic cation component containing atoms such as iodine, sulfur, nitrogen, and phosphorus. Compounds and the like. In particular, diaryl iodonium salts and triaryl sulfonium salts are preferred.

  Examples of organic phosphines include tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine and the like, and phosphonium salts include tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / ethyltriphenylborate, Examples include tetrabutylphosphonium / tetrabutylborate, and examples of the tetraphenylboron salt include 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmorpholine / tetraphenylborate, and the like.

When polyfunctional phenols, amine compounds, and acid anhydride compounds are used as the curing agent, the functional groups in the curing agent with respect to all epoxy groups in the epoxy compound-containing composition (hydroxy groups of polyfunctional phenols, amine compounds) It is preferable to use it so that it may become the range of 0.8-1.5 in the equivalent ratio of the amino group of this, or the acid anhydride group of an acid anhydride type compound. When using a polyisocyanate compound, the number of isocyanate groups in the polyisocyanate compound relative to the number of hydroxyl groups in the epoxy compound-containing composition may be used in an equivalent ratio of 1: 0.01 to 1: 1.5. preferable. When using an imidazole-type compound, it is preferable to use in the range of 0.5-10 weight part with respect to 100 weight part of all the epoxy compound components as solid content in an epoxy compound containing composition. When using an amide type compound, it is preferable to use it in the range of 0.1-20 weight% with respect to the total amount of all the epoxy compound components and amide type compounds as solid content in an epoxy compound containing composition. When using a cationic polymerization initiator, it is preferable to use in 0.01-15 weight part with respect to 100 weight part of all the epoxy compound components as solid content in an epoxy compound containing composition. When using organic phosphines, it is preferably used in the range of 0.1 to 20% by weight based on the total amount of all epoxy compound components and organic phosphines as a solid content in the epoxy compound-containing composition.
In addition to the curing agents listed above, for example, mercaptan compounds, organic acid dihydrazides, boron halide amine complexes, and the like can be used as the curing agent in the epoxy compound-containing composition of the present invention. These curing agents may be used alone or in combination of two or more.

[Other epoxy compounds]
In the epoxy compound-containing composition of the present invention, an epoxy compound other than the epoxy compound of the present invention (sometimes referred to as “other epoxy compound” in the present specification) can be used.
Other epoxy compounds include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin. , Glycidyl ether type epoxy resins such as tetrabromobisphenol A type epoxy resins, other polyfunctional phenol type epoxy resins, epoxy resins obtained by hydrogenating aromatic rings of the above aromatic epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxies Examples thereof include epoxy compounds such as resins, linear aliphatic epoxy resins, alicyclic epoxy resins, and heterocyclic epoxy resins. The other epoxy compounds mentioned above may be used alone or in combination of two or more.

  When the epoxy compound-containing composition of the present invention contains the epoxy compound of the present invention and another epoxy compound, the ratio of the other epoxy compounds in the total epoxy compound component as a solid content in the epoxy compound-containing composition is The amount is preferably 1% by weight or more, more preferably 5% by weight or more, and preferably 99% by weight or less, more preferably 95% by weight or less. When the ratio of the other epoxy compound is not less than the above lower limit value, the effect of improving physical properties by blending the other epoxy compound can be sufficiently obtained. On the other hand, when the ratio of the other epoxy compound is not more than the above upper limit value, the light resistance and the coating film hardness improving effect by the epoxy compound of the present invention can be obtained.

[solvent]
The epoxy compound-containing composition of the present invention may be diluted by blending a solvent in order to appropriately adjust the viscosity of the epoxy compound-containing composition during handling such as coating film formation. In the epoxy compound-containing composition of the present invention, the solvent is used to ensure the handleability and workability in the molding of the epoxy compound-containing composition, and the amount used is not particularly limited. As described above, in the present invention, the term “solvent” and the term “solvent” are distinguished from each other depending on the form of use, but the same or different ones may be used independently.
As a solvent which the epoxy compound of this invention can contain, the 1 type (s) or 2 or more types of the organic solvent illustrated as reaction solvent (E) used for manufacture of the epoxy compound of this invention can be used.

[Other ingredients]
The epoxy compound-containing composition of the present invention may contain other components in addition to the components listed above. Examples of other components include a curing accelerator (except for those corresponding to the curing agent), a coupling agent, a flame retardant, an antioxidant, a light stabilizer, a plasticizer, a reactive diluent, a pigment, An inorganic filler, an organic filler, etc. are mentioned. The other components listed above can be used in appropriate combination depending on the desired physical properties of the epoxy compound-containing composition.

[Cured product]
A cured product can be obtained by curing the epoxy compound-containing composition of the present invention. The term “curing” as used herein means that the epoxy compound is intentionally cured by heat and / or light or the like, and the degree of curing may be controlled by desired physical properties and applications.

  The curing method of the epoxy compound-containing composition when making the cured product obtained by curing the epoxy compound-containing composition of the present invention varies depending on the blending component and blending amount in the epoxy compound-containing composition, and the shape of the blend. Usually, the heating conditions are 50 to 200 ° C. for 5 seconds to 180 minutes. This heating is performed by a two-stage process of primary heating at 50 to 160 ° C. for 5 seconds to 30 minutes and secondary heating at 90 to 200 ° C. that is 40 to 120 ° C. higher than the primary heating temperature for 1 to 150 minutes. However, it is preferable in terms of reducing poor curing.

  When producing the cured product as a semi-cured product, the curing reaction of the epoxy compound-containing composition may be advanced to such an extent that the shape can be maintained by heating or the like. When the epoxy compound-containing composition contains a solvent, most of the solvent is removed by techniques such as heating, reduced pressure, and air drying, but 5% by weight or less of the solvent may be left in the semi-cured product. .

[Usage]
The epoxy compound of the present invention is excellent in light resistance and coating film hardness. From this, the epoxy compound of this invention and the epoxy compound containing composition which mix | blended it can be used suitably in field | areas, such as a coating material, an electrical / electronic material, an adhesive agent, and fiber reinforced resin (FRP).

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited at all by the following example. In addition, the value of various manufacturing conditions and evaluation results in the following examples has a meaning as a preferable value of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above-described upper limit or lower limit value. A range defined by a combination of values of the following examples or values of the examples may be used.

[Raw materials]
The raw materials, catalysts, solvents and solvents used in the following examples and comparative examples are as follows.
[Epoxy group-containing compound (A)]
A-1: Bisphenol A diglycidyl ether (JER (registered trademark) 828US manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 186 g / equivalent, total chlorine amount: 0.16%)
A-2: Hydrogenated bisphenol A type liquid epoxy resin (manufactured by Shin Nippon Chemical Co., Ltd. HBE-100, epoxy equivalent: 215 g / equivalent, total chlorine amount: 5%)

[Piperidine ring-containing compound (B)]
B-1: Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (manufactured by BASF, Tinuvin 770DF)
[Phenol compound (C)]
C-1: Bisphenol A (Mitsubishi Chemical Corporation)
C-2: Tetrabromobisphenol A (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Catalyst (D)]
D-1: 50% aqueous solution of tetramethylammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.)
[Diluted solvent (F)]
F-1: Methyl ethyl ketone (manufactured by Tokyo Chemical Industry Co., Ltd.)
[Evaluation methods]
Evaluation methods in the following Examples and Comparative Examples are as follows.

[Epoxy equivalent]
About the epoxy compound obtained in Examples 1-4 and Comparative Examples 1-3, the epoxy equivalent was measured based on JISK7236.
[Total chlorine and total bromine]
About the epoxy compounds obtained in Examples 1 to 4 and Comparative Examples 1 to 3, a sample was taken on a magnetic board and heated in a quartz tube tubular furnace, and the chlorine and bromine contents in the combustion gas were 0.1%- Absorbed with aqueous H2O2. The chlorine content and bromine content in the absorbing solution were measured by ion chromatography.
Apparatus: Quartz tube tubular furnace: Mitsubishi Chemical Corporation, AQF-100 type Ion chromatograph: Dionex, ICS-1000 type

[Weight average molecular weight (Mw)]
About the epoxy compound obtained in Examples 1-4 and Comparative Examples 1-3, the weight average molecular weight was measured by gel permeation chromatography (GPC). The apparatus and measurement conditions used for GPC measurement are as follows.
Device: GPC
Model: HLC-8120GPC (manufactured by Tosoh)
Column: TSKGEL HM-H + H4000 + H4000 + H3000 + H2000 (manufactured by Tosoh Corporation)
Detector: UV-8020 (manufactured by Tosoh), 254 nm
Eluent: THF (0.5 mL / min, 40 ° C.)
Sample: 1% tetrahydrofuran solution (10μ injection)
Calibration curve: Standard polystyrene (manufactured by Tosoh)

[Light resistance]
20 parts by weight of cyclohexanone, 2-ethyl-4-methylimidazole (manufactured by Mitsubishi Chemical Corporation) with respect to 100 parts by weight of the epoxy compound solution obtained in Examples 1 to 4 and Comparative Examples 1 to 3 (epoxy compound in Comparative Example 1) jER Cure (registered trademark) EMI24) 0.2 parts by weight is mixed on a steel plate described in JIS K5600-1-4 using a 150 μm film applicator and heated at 150 ° C. for 90 minutes. A coating was created. The obtained coating film was irradiated with light by the following weather meter for 167 hours, and then the yellowing degree (ΔYI) measured by the following color difference meter was evaluated as an evaluation index of light resistance.
・ Weather meter device: Atlas weather meter Ci4000 (manufactured by Toyo Seiki Seisakusho)
Light source: 6500W water-cooled xenon arc lamp Test conditions:
Black panel temperature 89 ℃
Room humidity 50%
Irradiation intensity 100 W / m ² (300 to 400 nm)
Colorimetric color difference meter: ZE6000 (Nippon Denshoku)

[Coating hardness]
Using the epoxy compound solutions or epoxy compounds obtained in Examples 1 to 4 and Comparative Examples 1 to 3, a coating film was formed on the steel sheet by the same method as in the light resistance evaluation. About the obtained coating film, pencil hardness was measured based on JIS K5600-5-4 using a pencil hardness tester (manufactured by Taiho Kogyo Co., Ltd.) and used as an index of coating film hardness.

[Manufacture and evaluation of epoxy compounds]
Example 1
1,200 parts by weight of bisphenol A diglycidyl ether (A-1), 24.9 parts by weight of bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (B-1), bisphenol A (C-1 460 parts by weight, tetramethylammonium chloride 50% aqueous solution (D-1)
0.72 part by weight was placed in a 5 L flask, and a polymerization reaction was performed at 165 ° C. for 6 hours under a nitrogen gas atmosphere to obtain a target epoxy compound. This was dissolved in 1685 parts by weight of methyl ethyl ketone (F-1) (solid content: 50% by weight). About the obtained epoxy compound solution, the epoxy equivalent, the total of the total chlorine amount and the total bromine amount, the weight average molecular weight (Mw), the light resistance and the coating film hardness were evaluated by the above methods, and the results are shown in Table 1. Indicated.

(Example 2)
200 parts by weight of bisphenol A diglycidyl ether (A-1), 14.5 parts by weight of bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (B-1), bisphenol A (C-1) ) 72 parts by weight, tetramethylammonium chloride 50% aqueous solution (D-1)
0.12 part by weight was placed in a 1 L flask and subjected to a polymerization reaction at 165 ° C. for 6 hours under a nitrogen gas atmosphere to obtain the desired epoxy compound. This was dissolved in 287 parts by weight of methyl ethyl ketone (F-1) (solid content: 50% by weight). About the obtained epoxy compound solution, the epoxy equivalent, the total of the total chlorine amount and the total bromine amount, the weight average molecular weight (Mw), the light resistance and the coating film hardness were evaluated by the above methods, and the results are shown in Table 1. Indicated.

(Example 3)
200 parts by weight of bisphenol A diglycidyl ether (A-1), 29.5 parts by weight of bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (B-1), bisphenol A (C-1 ) 65 parts by weight, tetramethylammonium chloride 50% aqueous solution (D-1) 0.12 part by weight was placed in a 1 L flask and subjected to a polymerization reaction at 165 ° C. for 6 hours in a nitrogen gas atmosphere to obtain the desired epoxy compound. It was. This was dissolved in 295 parts by weight of methyl ethyl ketone (F-1) (solid content: 50% by weight). About the obtained epoxy compound solution, the epoxy equivalent, the total of the total chlorine amount and the total bromine amount, the weight average molecular weight (Mw), the light resistance and the coating film hardness were evaluated by the above methods, and the results are shown in Table 1. Indicated.

Example 4
175 parts by weight of bisphenol A diglycidyl ether (A-1), 145 parts by weight of bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (B-1), 50% aqueous solution of tetramethylammonium chloride ( D-1) 0.105 weight part was put into a 1 L flask, and the polymerization reaction was performed at 165 degreeC under nitrogen gas atmosphere for 6 hours, and the target epoxy compound was obtained. This was dissolved in 295 parts by weight of methyl ethyl ketone (F-1) (solid content: 50% by weight). About the obtained epoxy compound solution, the epoxy equivalent, the total of the total chlorine amount and the total bromine amount, the weight average molecular weight (Mw), the light resistance and the coating film hardness were evaluated by the above methods, and the results are shown in Table 1. Indicated.

(Comparative Example 1)
200 parts by weight of bisphenol A diglycidyl ether (A-1), 80 parts by weight of bisphenol A (C-1) and 0.12 parts by weight of a 50% aqueous solution of tetramethylammonium chloride (D-1) are placed in a 1 L flask, and nitrogen gas is added. A polymerization reaction was performed at 165 ° C. for 6 hours in an atmosphere to obtain an epoxy compound. This was dissolved in 280 parts by weight of methyl ethyl ketone (F-1) (solid content: 50% by weight). About the obtained epoxy compound solution, the epoxy equivalent, the total of the total chlorine amount and the total bromine amount, the weight average molecular weight (Mw), the light resistance and the coating film hardness were evaluated by the above methods, and the results are shown in Table 1. Indicated.

(Comparative Example 2)
Hydrogenated bisphenol A type liquid epoxy resin (A-2) 200 parts by weight, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (B-1) 29.5 parts by weight, bisphenol A ( C-1) 55 parts by weight and tetramethylammonium chloride 50% aqueous solution (D-1) 0.12 part by weight were placed in a 1 L flask, and subjected to a polymerization reaction at 165 ° C. for 6 hours in a nitrogen gas atmosphere. A compound was obtained. This was dissolved in 285 parts by weight of methyl ethyl ketone (F-1) (solid content 50% by weight). About the obtained epoxy compound solution, the epoxy equivalent, the total of the total chlorine amount and the total bromine amount, the weight average molecular weight (Mw), the light resistance and the coating film hardness were evaluated by the above methods, and the results are shown in Table 1. Indicated.

(Comparative Example 3)
200 parts by weight of bisphenol A diglycidyl ether (A-1), 36 parts by weight of bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (B-1), tetrabromobisphenol A (C-2) ) 125 parts by weight, 0.12 part by weight of tetramethylammonium chloride 50% aqueous solution (D-1) is placed in a 1 L flask, and subjected to a polymerization reaction at 165 ° C. for 6 hours in a nitrogen gas atmosphere to obtain the desired epoxy compound. It was. This was dissolved in 361 parts by weight of methyl ethyl ketone (F-1) (solid content: 50% by weight). About the obtained epoxy compound solution, the epoxy equivalent, the total of the total chlorine amount and the total bromine amount, the weight average molecular weight (Mw), the light resistance and the coating film hardness were evaluated by the above methods, and the results are shown in Table 1. Indicated.

[Evaluation results]
As can be seen from Table-1, it has a divalent group represented by the formula (1) and a divalent group represented by the formula (2), and an epoxy equivalent is 200 g / equivalent or more, 200,000 g / The epoxy compound having an equivalent weight or less showed high light resistance and high coating film hardness. On the other hand, the epoxy compound of Comparative Example 1 that does not have the structure of Formula (1) has insufficient light resistance, and the compound of Comparative Example 2 has insufficient coating strength. The compound of Comparative Example 3 having no structure of formula (2) was insufficient in light resistance. The epoxy compound of the present invention is considered to have good light resistance and coating film hardness by having both the structures of formulas (1) and (2).

  The epoxy compound of the present invention has excellent weather resistance and flexibility. Therefore, the epoxy compound of the present invention, the epoxy compound-containing composition containing the epoxy compound, and the cured product thereof are suitably used in the fields of paints, electrical / electronic materials, adhesives, fiber reinforced resins (FRP), and the like. be able to.

Claims (11)

An epoxy compound having a divalent group represented by the following formula (1) and a divalent group represented by the following formula (2), and having an epoxy equivalent of 200 g / equivalent to 200,000 g / equivalent.

(In formula (1), R ^{1 to} R ⁴ may be the same or different and each represents a hydrogen atom or a saturated or unsaturated aliphatic hydrocarbon group having 1 to 4 carbon atoms.)

(In the formula (2), X represents a divalent group having 1 to 50 carbon atoms which does not contain chlorine and bromine and may have a substituent.)   The epoxy compound according to claim 1, wherein the total amount of total chlorine and total bromine is 3% by weight or less.   The epoxy compound according to claim 1 or 2, comprising two or more different groups as the divalent group represented by the formula (1).   The epoxy compound according to any one of claims 1 to 3, comprising two or more different groups as the divalent group represented by the formula (2). X is a group having a structure represented by any of the following formula (3), the following formula (4), the following formula (5), the following formula (6), the following formula (7), or the following formula (8). The epoxy compound according to any one of claims 1 to 4, wherein each aromatic ring or cycloalkylene group in the following formulas (3) to (8) may be substituted with an alkyl group.

(In the formula (3), R ⁵ and R ⁶ may be the same or different and each represents a hydrogen atom or an alkyl group.)

(In the formula (4), R ⁷ and R ⁸ may be the same or different and each represents a hydrogen atom or an alkyl group.)

(In the formula (7), R ⁹ and R ¹⁰ may be the same or different and represent a direct bond or an alkylene group having 1 to 5 carbon atoms.)

(In formula (8), R ¹¹ and R ¹² may be the same or different, and represent a direct bond or an alkylene group having 1 to 5 carbon atoms.)   The production of an epoxy compound according to any one of claims 1 to 5, which is obtained by reacting a piperidine ring-containing compound with an epoxy group-containing compound whose total chlorine amount and total bromine amount are 5% by weight or less. Method.   The epoxy according to any one of claims 1 to 5, obtained by reacting a piperidine ring-containing compound, an epoxy group-containing compound in which the total amount of chlorine and total bromine is 5% by weight or less, and a phenol compound. Compound production method.   The epoxy compound containing composition containing the epoxy compound of any one of Claim 1 to 5, and a hardening | curing agent.   The epoxy compound containing composition of Claim 8 containing 0.1-1000 weight part of hardening | curing agents with respect to 100 weight part of said epoxy compounds.   The curing agent is selected from the group consisting of polyfunctional phenols, polyisocyanate compounds, amine compounds, acid anhydride compounds, imidazole compounds, amide compounds, mercaptan compounds, cationic polymerization initiators, and organic phosphines. The composition containing an epoxy compound according to claim 8 or 9, wherein the composition is at least one selected from the group consisting of:   Hardened | cured material formed by hardening | curing the epoxy compound containing composition of any one of Claims 8-10.