TW201815868A - Epoxy compound, method for producing epoxy compound, composition containing epoxy compound, coating material and cured product - Google Patents

Abstract

The present invention relates to an epoxy compound having a divalent group represented by the following formula (1) and a divalent group represented by the following formula (2) wherein epoxy equivalent is 200 g/equivalent or more and 200,000 g/equivalent or less: (In the formulae (1) and (2), R1 to R4 and X represent the same meanings as described in the specification.).

Description

 Epoxy compound, method for producing epoxy compound, composition containing epoxy compound, paint and cured product  

The present invention relates to an epoxy compound which can form a coating film excellent in light resistance, hardness and dissolution resistance, and a method for producing the same. Further, the present invention relates to a composition, a coating material and a cured product containing an epoxy compound obtained by using the epoxy compound.

Since epoxy compounds are excellent in heat resistance, adhesion, flexibility, electrical properties, and the like, they are widely used in coatings, civil engineering, bonding, electrical materials, and the like. Patent Document 1 describes the reaction product of a high halogen content epoxy resin and a hindered amine compound. Further, Patent Documents 2 to 4 disclose compositions of an epoxy resin and a hindered amine compound.

 [Previous Technical Literature]    [Patent Literature]  

Patent Document 1: Japanese Patent Laid-Open No. Hei 8-165437

Patent Document 2: Japanese Patent Laid-Open Publication No. 2009-108301

Patent Document 3: Japanese Patent Laid-Open No. 2016-113564

Patent Document 4: Japanese Patent Laid-Open No. Hei 9-176284

However, according to the study by the inventors of the present invention, the coating film of the epoxy compound described in Patent Document 1 is insufficient in light resistance. Further, the coating film of the composition described in Patent Documents 2 to 4 has problems such as low hardness and bleeding.

The present invention has been made in view of the above-mentioned technical problems. That is, an object of the present invention is to provide an epoxy compound which can form a coating film which is excellent in light resistance, hardness, and dissolution resistance, and a method for producing the same. Moreover, the present invention provides a composition, a coating material and a cured product containing an epoxy compound obtained by using the epoxy compound.

In order to solve the above problems, the inventors of the present invention have intensively studied and found that an epoxy compound having a piperidine ring and an epoxy compound having an epoxy equivalent of 200 g/eq or more and 200,000 g/eq or less can solve the above problems. Complete the invention. That is, the gist of the present invention is as follows [1] to [13].

[1] An epoxy compound containing a divalent group represented by the following formula (1) and a divalent group represented by the following formula (2), and an epoxy equivalent of 200 g/eq or more and 200,000 g/eq or less;

(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.)

[Chemical 2]

(In the formula (2), X represents a divalent hydrocarbon group having 1 to 50 carbon atoms which may have a substituent.)

[2] The epoxy compound according to [1], wherein the total chlorine amount and the total bromine amount are 3% by weight or less.

[3] The epoxy compound according to [1] or [2], wherein the divalent group represented by the above formula (1) contains two or more kinds of different groups.

[4] The epoxy compound according to any one of [1] to [3], wherein the divalent group represented by the above formula (2) contains two or more kinds of different groups.

The epoxy compound according to any one of the above formulas (3) to (8), wherein the X-form has a structure of any one of the following formulas (3) to (8); Each of the aromatic rings or the cycloalkyl groups in the formulae (3) to (8) may be substituted by an alkyl group, respectively.

(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 alkyl group having 1 to 5 carbon atoms.)

(In the formula (8), R ¹¹ and R ¹² may be the same or different, and represent a direct bond or an alkyl group having a carbon number of 1 to 5.)

[6] A coating material, which comprises the epoxy compound according to any one of [1] to [5].

[7] The method for producing an epoxy compound according to any one of [1] to [5], which comprises a compound containing a piperidine ring and a total amount of chlorine and a total amount of bromine of 5% by weight or less. A compound of an epoxy group, the step of carrying out the reaction.

[8] The method for producing an epoxy compound according to any one of [1] to [5], which comprises containing a piperidine ring-containing compound, a total chlorine amount, and a total bromine amount in an amount of 5% by weight or less. A step of reacting a compound of an epoxy group and a phenol compound.

[9] A composition containing an epoxy compound, which comprises the epoxy compound according to any one of [1] to [5], and a curing agent.

[10] The composition containing an epoxy compound according to [9], wherein the curing agent is contained in an amount of 0.1 to 1000 parts by weight based on 100 parts by weight of the epoxy compound.

[11] The composition containing an epoxy compound according to [9] or [10], wherein the curing agent is a polyfunctional phenol, a polyisocyanate compound, an amine compound, an acid anhydride compound, or an imidazole system. At least one selected from the group consisting of a compound, a guanamine compound, a thiol compound, a cationic polymerization initiator, and an organic phosphine.

[12] A coating material containing the epoxy compound-containing composition according to any one of [9] to [11].

[13] A cured product obtained by curing the composition containing an epoxy compound according to any one of [9] to [11].

According to the present invention, it is possible to provide an epoxy compound which can form a coating film excellent in light resistance, hardness and dissolution resistance, and a method for producing the same. Further, according to the present invention, there can be provided a composition, a coating material and a cured product containing an epoxy compound obtained by using the epoxy compound.

Because of such characteristics, the epoxy compound, the epoxy compound-containing composition, and the cured product of the present invention can be applied to fields such as electric ‧ electronic materials, FRP (fiber reinforced resins), adhesives, and coatings.

The embodiments of the present invention are described in detail below, but the present invention is not limited to the following description, and may be arbitrarily changed without departing from the spirit and scope of the invention. In this manual, when "~" is used to interpret numerical values or physical property values before and after, it is assumed to include the values shown before and after.

In addition, the carbon number of each base described in this specification, when this group has a substituent, means the total carbon number which contains the carbon number of this 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 an epoxy equivalent of 200 g/eq or more and 200,000 g/eq or less. Oxygen compound. The coating film using the epoxy compound of the present invention is excellent in light resistance, hardness, and dissolution resistance by having a divalent group represented by the following formula (1) and a divalent group represented by the following formula (2). By having an epoxy equivalent of 200 g/eq or more and 200,000 g/eq or less, it is possible to achieve both excellent flexibility and hardness of the coating film.

(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.)

In the above 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 preferred, and a methyl group is more preferred. Further, each of R ¹ to R ⁴ is preferably a methyl group.

In addition, the epoxy compound of the present invention is preferably a divalent group represented by the above formula (1) from the viewpoints of workability at the time of production of the epoxy compound and physical properties such as corrosion resistance and weather resistance at the time of forming a coating film. It contains two or more different groups.

(In the formula (2), X represents a divalent hydrocarbon group having 1 to 50 carbon atoms which may have a substituent.)

In the divalent group represented by the above formula (2), X represents a divalent hydrocarbon group which may have a substituent and has a carbon number of 1 to 50, preferably 1 to 40 carbon atoms, more preferably 1 to 35 carbon atoms. The X system may, for example, be a linear hydrocarbon chain, a branched chain or a cyclic aliphatic hydrocarbon group or an aromatic hydrocarbon group. Further, the combination of a cyclic aliphatic hydrocarbon group and an aromatic hydrocarbon group is referred to as "a hydrocarbon group having a cyclic structure". X is preferably a hydrocarbon group having a cyclic structure.

The epoxy compound of the present invention has a divalent group represented by the above formula (2) and is excellent in chemical resistance, adhesion, and flexibility.

In addition, the epoxy compound of the present invention is preferably a divalent group represented by the above formula (2) from the viewpoints of workability at the time of production of the epoxy compound and physical properties such as corrosion resistance and weather resistance at the time of forming a coating film. It contains two or more different groups.

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

(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 alkyl group having a carbon number of 1 to 5.)

(In the formula (8), R ¹¹ and R ¹² may be the same or different, and represent a direct bond or an alkyl group having a carbon number of 1 to 5.)

In the above 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, more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. In the above 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, more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

In the above formula (7), R ⁹ and R ^{10 each} represent a direct bond or an alkylene group having 1 to 5 carbon atoms. R ⁹ and R ^{10 are} preferably directly bonded.

In the above formula (8), R ¹¹ and R ^{12 each} represent a direct bond or an alkylene group having 1 to 5 carbon atoms. R ¹¹ and R ^{12 are} preferably directly bonded.

When the aromatic ring or the extended cyclohexyl group represented by the above formulas (3) to (8) has a substituent, the substituent is not particularly limited, and may be, for example, an alkyl group having 1 to 2 carbon atoms, preferably 1 each. The number of substituents of the cyclohexylene group is 2 or less.

 [epoxy equivalent]  

The epoxy compound of the present invention has an epoxy equivalent of 200 g/eq or more, preferably 250 g/eq or more, more preferably 300 g/eq or more. Thereby, the softness can be made better.

Further, the epoxy equivalent of the epoxy compound of the present invention is preferably 200,000 g / equivalent or less, more preferably 100,000 g / equivalent or less, and particularly preferably 50,000 g / equivalent or less from the viewpoint of compatibility with other materials.

In the present invention, the "epoxy equivalent" is defined as "the mass of the epoxy compound containing one equivalent of an epoxy group", and can be measured in accordance with JIS K7236.

 [Total amount of total chlorine and total bromine]  

The total amount of chlorine and the total amount of bromine in the epoxy compound of the present invention are preferably from the viewpoint of light resistance and weather resistance of the coating film using the epoxy compound of the present invention, and preferably 3 parts by weight based on the epoxy compound. % or less, more preferably 2% by weight or less, and particularly preferably 1% by weight or less. The lower limit is preferably 0% by weight, and may actually be 0.0001% by weight.

Further, the chlorine and bromine in the epoxy compound of the present invention are contained in the form of a part of the structure.

The method of setting the total chlorine amount and the total bromine amount of the epoxy compound of the present invention in the above range is not particularly limited, and for example, the epoxy group-containing compound (A) will be used as the total chlorine amount and the total bromine amount. A method of adding an epoxy compound in an amount of 5% by weight or less, preferably 4% by weight or less.

 [Weight average molecular weight (Mw)]  

The weight average molecular weight (Mw) of the epoxy compound of the present invention is preferably 240 or more, more preferably 300 or more, and particularly preferably 400 or more from the viewpoint of good flexibility. Further, 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 particularly preferably 100,000 or less from the viewpoint of compatibility with other materials.

Further, the weight average molecular weight of the epoxy compound can be measured by gel permeation chromatography (GPC method). A more detailed method example will be described in the examples to be described later.

 [Method for producing epoxy compound]  

The epoxy compound of the present invention can be produced by copolymerizing a compound (A) containing an epoxy group which will be described later as a raw material of an epoxy compound, and a compound (B) containing a piperidine ring.

In addition, the epoxy compound of the present invention is obtained by using an epoxy group-containing compound (A), a piperidine ring-containing compound (B), and a phenol compound (C) which will be described later as a raw material of an epoxy compound. Polymerization can also be produced.

In the above-mentioned copolymerization reaction, the epoxy group-containing compound (A), the piperidine ring-containing compound (B), and the phenol compound (C) may be used alone or in combination of two or more.

 [Epoxy group-containing compound (A)]  

The epoxy group-containing compound (A) is a compound having two or more epoxy groups in its molecule. The epoxy group-containing compound (A) used in the present invention is a total amount of chlorine and a total bromine amount of 5% by weight or less, and is introduced into the divalent group represented by the above formula (2).

The epoxy group-containing compound (A) used in the present invention, for example, a compound having a bifunctional epoxy group, for example, 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 quinone diglycidyl ether, tetramethyl bisphenol A diglycidyl ether, tetramethyl bisphenol F diglycidyl ether, tetrabutyl butyl Bisphenol diglycidyl ethers such as bisphenol A diglycidyl ether and tetramethyl bisphenol S diglycidyl ether; biphenol diglycidyl ether, tetramethyl biphenol diglycidyl ether, Biphenol-based diglycidyl ethers such as dimethylbiphenol diglycidyl ether and tetra-tert-butylbiphenol diglycidyl ether; hydroquinone diglycidyl ether, indoline diglycidyl ether , phenylhydrogen diglycidyl ether, dibutylhydroquinone diglycidyl ether, resorcinol diglycidyl ether, methyl resorcinol diglycidyl ether and other benzene glycol bicyclic rings Oxypropyl ethers; indoline hydroquinone diglycidyl ether, dihydroxydiphenyl ether diepoxy An aromatic diglycidyl ether such as thiodiphenol diglycidyl ether or dihydroxynaphthalene diglycidyl ether; in the above bisphenol diglycidyl ether, biphenol diglycidyl ether An epoxy compound to which hydrogen is added to an aromatic ring of a diglycidyl ether selected from the group consisting of benzene glycol diglycidyl ethers and aromatic diglycidyl ethers; for example, adipic acid, Various carboxylic acids such as succinic acid, citric acid, tetrahydrofurfuric acid, methyl hexahydrophthalic acid, p-nonanoic acid, isophthalic acid, o-nonanoic acid, biphenyl dicarboxylic acid, dimer acid, and epihalohydrin Epoxy resin produced; ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,4-butanediol Glycidyl ether, polybutanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether, pentylene glycol diglycidyl ether, 1,6-hexanediol epoxide Propyl ether, poly(hexane) diglycidyl ether, 1,7-heptanediol diglycidyl ether, polyheptanediol diglycidyl ether, 1,8-octanediol diglycidyl ether 1,10-nonanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diepoxypropyl a (poly)alkylene glycol diglycidyl ether composed only of a chain structure; a cyclic alkyl diol bicyclic ring such as 1,4-cyclohexanedimethanol diglycidyl ether Oxypropyl ethers and the like.

Further, the trifunctional or higher epoxy group-containing compound can be, for example, the following. In the following examples, the "~ epoxy resin" means a group in which a hydroxyl group is substituted by a glycidyl ether group.

For example, α,α-bis(4-hydroxyphenyl)-4-(4-hydroxy-α,α-dimethylbenzyl)-ethylbenzene type epoxy resin, 4,4', 4" - trishydroxytriphenylmethane type epoxy resin, 4,4',4"-ethylidene tris(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-three 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-3,5-dimethylphenyl)-1-methylethyl]phenyl]ethylidene]bis(2-methylphenol) type ring Oxygen resin, trifunctional epoxy resin such as 2,6-bis(4-hydroxy-3,5-dimethylbenzyl)-4-methylphenol type epoxy resin; 2,2'-methylene Bis[6-(2-hydroxy-5-methylbenzyl)]-p-cresol 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-hydroxyphenyl)-pair a tetrafunctional epoxy resin such as a xylene type epoxy resin; a pentafunctional ring such as a 2,4,6-tris[(4-hydroxyphenyl)methyl]-1,3-benzenediol type epoxy resin Oxygen resin; various amine compounds such as diaminodiphenylmethane, aminophenol, xylene diamine, epoxy compounds produced from epihalohydrin; rings made of aliphatic polyols and epihalohydrin Oxygen compound; phenol novolak type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, naphthol novolac type epoxy resin, phenol aralkyl group Epoxy resin, biphenyl aralkyl type epoxy resin, phenol-modified xylene type epoxy resin; condensation reaction of various phenols from various aldehydes such as hydroxybenzaldehyde, crotonaldehyde and glyoxal The polyhydric phenol resin obtained is a polyfunctional epoxy resin such as an epoxy resin such as a heavy oil or a pitch, a condensed resin such as a phenol or a formaldehyde, or the like.

Among these, from the viewpoint of preventing gelation during production, it is preferred to use a compound containing a bifunctional epoxy group. Further, from the viewpoint of obtaining good coating film hardness, it is preferred to use, for example, a bisphenol-based diglycidyl ether; a biphenol-based diglycidyl ether; a bisphenol-based diglycidyl ether. An epoxy group-containing compound in which hydrogen is added to the ring; and an epoxy group-containing compound in which hydrogen is added to an aromatic ring of a biphenol-based diglycidyl ether.

The epoxy group-containing compound (A) exemplified above may be used singly or in combination of plural kinds. The preferred combination is an epoxy group-containing epoxy group which is added with an aromatic ring such as a bisphenol-based diglycidyl ether, a biphenol-based diglycidyl ether or a bisphenol-based diglycidyl ether. A compound selected from the group consisting of an epoxy group-containing compound in which hydrogen is added to an aromatic ring of a biphenol-based diglycidyl ether.

 [Compound (B) containing piperidine ring]  

The compound (B) containing a piperidine ring is a compound having one or more piperidine rings in the molecule and having one or more NH groups in the molecule and/or one or more OH groups in the molecule.

The piperidine ring-containing compound (B) used in the present invention is not particularly limited as long as it is introduced before the introduction of the divalent group represented by the above formula (1), and it is preferred that neither chlorine nor bromine is contained. For example, a compound having one NH group in the molecule may be, for example, 2,2,6,6-tetramethyl-4-piperidyl methacrylate or the like. The compound having one OH group in the molecule may be, for example, dimethyl succinate ‧ 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate or the like. The compound having two NH groups in the molecule may be, for example, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate or the like. A compound having three or more NH groups in the molecule may be, for example, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)butane-1,2,3,4-tetracarboxylate, poly {(6- phenyl-S-three -2,4-diyl)[2,2,6,6-tetramethyl-4-piperidinyl]imine}-hexamethylene[[2,2,6,6-tetramethyl-4 -piperidinyl)imine] and the like. Among these, from the viewpoint of polymerizability, a compound having a total number of OH groups and NH groups of 2 is preferred.

The piperidine ring-containing compound (B) listed above may be used singly or in combination of plural kinds. When two or more compounds containing a piperidine ring (B) are used, it is preferred to combine a compound having one OH group, a compound having two OH groups, a compound having one NH group, and having two NH salts. A selected combination of the base compounds.

 [phenolic compound (C)]  

The phenol compound (C) is a compound having two or more hydroxyl groups bonded to an aromatic ring. By copolymerizing the phenol compound (C), the viscosity of the manufacturing process can be effectively adjusted, and the physical properties of the obtained epoxy compound can be controlled.

The phenolic compound (C) used in the present invention does not contain chlorine or bromine. For example, a compound having two hydroxyl groups bonded to an aromatic ring may, for example, be bisphenol A, bisphenol F, bisphenol E, bisphenol Z, bisphenol S, bisphenol AD, bisphenol acetophenone , bisphenol trimethylcyclohexane, bisphenol oxime, tetramethyl bisphenol A, tetramethyl bisphenol F, tetrabutyl bisphenol A, tetramethyl bisphenol S and other bisphenols; biphenol , biphenols such as tetramethylbiphenol, dimethylbiphenol, tetra-tert-butylbiphenol; hydroquinone, methylhydroquinone, dibutylhydroquinone, resorcinol, methyl resorcinol Isophthalenes (herein, "benzenediols" are compounds having one benzene ring and having two hydroxyl groups bonded directly to the benzene ring); indoline hydroquinones; dihydroxy groups Dihydroxydiphenyl ethers such as phenyl ether; thiodiphenols such as thiodiphenol; dihydroxynaphthalenes such as dihydroxynaphthalene; dihydroxy guanidines such as dioxins; and the like.

A compound having three or more hydroxyl groups bonded to an aromatic ring may, for example, be α,α-bis(4-hydroxyphenyl)-4-(4-hydroxy-α,α-dimethylbenzyl). -ethylbenzene, 4,4',4"-trishydroxytriphenylmethane, 4,4',4"-ethylidenetris(2-methylphenol), 4,4'-(2-hydroxybenzamine Methyl) bis(2,3,6-trimethylphenol), 2,3,4-trihydroxydiphenylmethane, 2,4,6-tris(4-hydroxyphenyl)-1,3,5- three 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]ethylidene]bis(2-methylphenol), 2,6-bis(4-hydroxy-3,5 a trifunctional phenolic compound such as -dimethylbenzyl)-4-methylphenol; 2,2'-methylenebis[6-(2-hydroxy-5-methylbenzyl)]-p- Phenol, 4-[bis(4-hydroxy-3-methylphenyl)methyl]benzene-1,2-diol, 1,1,2,2-tetrakis(p-hydroxyphenyl)ethane, α, a tetrafunctional phenolic compound such as α,α',α'-tetrakis(4-hydroxyphenyl)p-xylene; 2,4,6-tris[(4-hydroxyphenyl)methyl]-1,3 - pentafunctional phenolic compounds such as benzenediol; bisphenol phenolic resins such as phenolic phenolic resin, cresol novolac resin, bisphenol A phenolic resin; naphthol phenolic resin, phenol aralkyl resin, terpene Various phenol resins such as phenol resin, dicyclopentadiene phenol resin, phenol-extended biphenyl resin, and phenol-modified xylene resin; and various phenols, such as hydroxybenzaldehyde, crotonaldehyde, glyoxal, etc. Polyphenols obtained by condensation reaction of aldehydes; polyfunctional phenols such as heavy oil or asphalt, co-condensation resins with phenols and formaldehyde Compounds and so on.

Among these, from the viewpoint of preventing gelation from occurring in production, it is preferred to use a compound having two hydroxyl groups bonded to an aromatic ring. Further, from the viewpoint of obtaining good coating film hardness, bisphenols and biphenols are preferably used.

The epoxy compound-containing compound (A) used in the production of the epoxy compound of the present invention, the blend ratio of the compound containing the piperidine ring (B), or the epoxy compound used in the production of the epoxy compound of the present invention The blend ratio of the compound (A), the piperidine ring-containing compound (B), and the phenol compound (C) is preferably a theoretical epoxy of the epoxy compound from the viewpoint of ensuring compatibility with other materials. The blending ratio of the equivalent amount of 200,000 g/eq or less, more preferably the blend ratio of 150,000 g/eq or less, and the blend ratio of 100,000 g/eq or less.

On the other hand, the lower limit of the theoretical epoxy equivalent is preferably from 100 g/eq, more preferably from 120 g/equivalent to more than 150 g/equivalent, and most preferably from the viewpoint of obtaining an excellent epoxy compound. It is 200 g/eq or more.

The blend ratio of the epoxy group-containing compound (A) to the piperidine ring-containing compound (B), for example, to 100 parts by weight of the epoxy group-containing compound (A), may be set to a compound containing a piperidine ring ( B) 1 to 100 parts by weight.

Further, the blending ratio of the epoxy group-containing compound (A), the piperidine ring-containing compound (B), and the phenol compound (C) may be, for example, 100 parts by weight based on the epoxy group-containing compound (A). The compound (B) containing a piperidine ring is set to be 1 to 100 parts by weight, and the phenol compound (C) is used in an amount of 1 to 100 parts by weight.

The term "theoretical epoxide equivalent" as used herein means all epoxy groups and NH groups contained in the epoxy group-containing compound (A), the piperidine ring-containing compound (B) and the phenol compound (C). / or OH group, the epoxy equivalent of the reaction product when the reaction is carried out in accordance with 1:1.

In the present invention, the "epoxy equivalent" is defined as "the mass of the epoxy compound containing one equivalent of an epoxy group", and can be measured in accordance with JIS K7236.

 [catalyst (D)]  

In the reaction step of producing the epoxy compound of the present invention, a catalyst (D) can also be used. The catalyst (D) is not particularly limited as long as it is a two-step advancement process catalyst used in the usual epoxy resin production method.

Examples of the catalyst (D) include an alkali metal compound, an organic phosphorus compound, a tertiary amine, a quaternary ammonium salt, a cyclic amine, and an imidazole.

Specific examples of the alkali metal compound include alkali metal hydroxides such as sodium hydroxide, lithium hydroxide, and potassium hydroxide; and alkali metals such as sodium carbonate, sodium bicarbonate, sodium chloride, lithium chloride, and potassium chloride. a salt; an alkali metal alkoxide such as sodium methoxide or sodium ethoxide; an alkali metal hydride such as an alkali metal phenoxide, sodium hydride or lithium hydride; an alkali metal salt of an organic acid such as sodium acetate or sodium stearate; .

Specific examples of the organophosphorus compound include, for example, triphenylphosphine, tri(o-tolyl)phosphine, tris(m-tolyl)phosphine, tris(p-tolyl)phosphine, and tris(2,4-dimethylphenyl)phosphine. , tris(2,5-dimethylphenyl)phosphine, tris(3,5-dimethylphenyl)phosphine, tris(p-tert-butylphenyl)phosphine, tris(p-methoxyphenyl)phosphine, tris(pair Third butoxyphenyl)phosphine, tris(p-n-octylphenyl)phosphine, tris(p-n-decylphenyl)phosphine, triallylphosphine, tributylphosphine, trimethylphosphine, triphenylphosphine, triiso Butylphosphine, tris(t-butyl)phosphine, tri-n-octylphosphine, tricyclohexylphosphine, tri-n-propylphosphine, di-t-butylmethylphosphine, tri-n-butylphosphine, cyclohexyldi-tert-butylphosphine, diethylbenzene Phosphine, di-n-butylphenylphosphine, di-t-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, diphenylpropanphosphine, isopropyldiphenylphosphine, cyclohexyldiphenylphosphine, bromination Tetramethylammonium, tetramethylammonium iodide, tetramethylammonium hydroxide, trimethylcyclohexyl chloride, trimethylcyclohexyl bromide, trimethylbenzylhydrazine chloride, trimethylbenzylphosphonium bromide, Tetraphenylphosphonium bromide, triphenylformam bromide, triphenylformamidine iodide, triphenylacetamidine chloride, triphenylacetam bromide, iodination Triphenylacetamidine, triphenylbenzylhydrazine chloride, triphenylbenzylhydrazine bromide, and the like.

Specific examples of the tertiary amines include, for example, triethylamine, tri-n-propylamine, tri-n-butylamine, triethanolamine, and N,N-dimethylbenzylamine.

Specific examples of the quaternary ammonium salt include, for example, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium hydroxide, triethylammonium 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, phenyltrimethylammonium chloride, and the like.

Specific examples of the cyclic amines include, for example, 1,8-diazabicyclo(5,4,0)-7-undecene and 1,5-diazabicyclo(4,3,0)- 5-decene and the like.

Specific examples of the imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole.

The catalyst (D) exemplified above may be used alone or in combination of two or more.

When the catalyst (D) is used, the amount of the epoxy group-containing compound (A) to be used is usually 10,000 ppm by weight or less, and preferably 10 to 5,000 ppm by weight.

 [Reaction solvent (E)]  

The reaction solvent (E) can also be used in the reaction step of producing the epoxy compound of the present invention. The reaction solvent (E) is removed before the raw material can be dissolved, and the rest is not particularly limited, and is usually an organic solvent.

The organic solvent may be, for example, an aromatic solvent, a ketone solvent, a guanamine solvent, or a glycol ether solvent.

Specific examples of the aromatic solvent include benzene, toluene, xylene, and the like.

Specific examples of the ketone-based solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, 2-octanone, cyclopentanone, cyclohexanone, and acetamidine.

Specific examples of the guanamine-based solvent include, for example, 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-based 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, and Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol 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 above-mentioned reaction solvent (E) may be used alone or in combination of two or more. Further, when a highly viscous product is generated during the reaction, the reaction solvent (E) may be further added to continue the reaction.

 [Reaction conditions]  

Reaction of the above epoxy group-containing compound (A) with a piperidine ring-containing compound (B) or the above epoxy group-containing compound (A) and a piperidine ring-containing compound (B) and a phenol compound (C) The reaction can also be carried out under any conditions of normal pressure, pressure, and reduced pressure.

Further, the reaction temperature is usually 60 to 240 °C. When the reaction temperature is at least the above lower limit, the reaction proceeds easily, and if the reaction temperature is at most the above upper limit, the side reaction is difficult to proceed. From the viewpoint of obtaining a high-purity epoxy compound, it is preferably 80 to 220 ° C, more preferably 100 to 200 ° C, and particularly preferably 120 to 180 ° C.

The reaction time is not particularly limited, but is usually 0.5 to 24 hours, preferably 1 to 22 hours, more preferably 1.5 to 20 hours, and particularly preferably 2 to 10 hours. When the reaction time is at most the above upper limit, it is preferable in terms of improving production efficiency, and if it is at least the above lower limit, it is preferable from the viewpoint of being able to reduce unreacted components.

The above compound (B) is difficult to carry out the copolymerization reaction due to the structural relationship. However, if the reaction conditions are too severe due to the presence of a nitrogen atom, gelation may occur. By the above-mentioned preferred reaction conditions, even if the copolymerization of the above compounds (A) and (B) or the copolymerization of the above compounds (A), (B) and (C) is carried out, the unreacted components can be reduced and obtained. High purity epoxy compound.

 [Diluted solvent (F)]  

In the method for producing an epoxy compound of the present invention, the concentration of the solid portion may be adjusted by mixing the diluent solvent (F) after completion of the reaction. The diluent solvent (F) is removed before it can dissolve the epoxy compound, and any of them can be used, and is usually an organic solvent. Specific examples of the organic solvent can be used in the same manner as those exemplified for the above reaction solvent (E).

In the present invention, the terms "solvent" and "solvent" are referred to as "solvent" when the epoxy compound is reacted, and the user is referred to as "solvent" after completion of the reaction. Different types can also be used.

 [Composition containing an epoxy compound]  

The composition containing an epoxy compound of the present invention contains at least the above epoxy compound of the present invention and a hardener. Further, in the composition containing an epoxy compound of the present invention, other epoxy compounds, a curing accelerator, other components, and the like may be appropriately blended as needed.

 [hardener]  

The curing agent used in the composition containing an epoxy compound of the present invention is a substance which contributes to a crosslinking reaction between epoxy groups of an epoxy compound and/or a chain length extension reaction. In addition, in the present invention, a "hardening accelerator" is also known as a curing agent in the case of a substance which contributes to a crosslinking reaction and/or a chain length elongation reaction between epoxy groups of an epoxy compound.

The content of the curing agent in the composition containing the epoxy compound of the present invention is preferably 0.1 to 1000 parts by weight, more preferably 0.1 to 100 parts by weight, even more preferably 0.1 to 100 parts by weight based on 100 parts by weight of the epoxy compound of the present invention. 80 parts by weight, preferably 0.1 to 60 parts by weight.

Further, in the case of the epoxy compound-containing composition of the present invention, when the epoxy compound other than the epoxy compound of the present invention is contained, the curing agent content is preferably 0.1 part by weight based on 100 parts by weight of the total epoxy compound component. ~1000 parts by weight, more preferably 0.1 to 100 parts by weight, particularly preferably 0.1 to 80 parts by weight, most preferably 0.1 to 60 parts by weight.

The more desirable content of the hardener is the type of the hardener, which are as follows.

In the present invention, the "solid portion" means a component other than a solvent, and includes not only a solid epoxy compound but also a semi-solid, viscous liquid. Moreover, the "total epoxy compound component" means the total of the epoxy compound of this invention and the other epoxy compound mentioned later.

In the composition containing an epoxy compound of the present invention, a polyfunctional phenol, a polyisocyanate compound, an amine compound, an acid anhydride compound, an imidazole compound, a guanamine compound, or a thiol compound is preferably used as the curing agent. At least one of the group consisting of a cationic polymerization initiator and an organic phosphine.

Examples of the polyfunctional phenols include bisphenol A, bisphenol F, bisphenol S, bisphenol B, bisphenol AD, bisphenol Z, and bisphenols such as tetrabromobisphenol A; 4, 4'-linked Biphenols such as phenol, 3,3',5,5'-tetramethyl-4,4'-biphenol; catechol, resorcinol, hydroquinone, dihydroxynaphthalene; and these compounds a hydrogen atom bonded to an aromatic ring, such as a halogen group, an alkyl group, an aryl group, an ether group, an ester group, or a non-blocking substituent such as an organic substituent containing a hetero element such as sulfur, phosphorus or ruthenium. Replacement, etc.

Further, for example, such polyfunctional phenols, or monofunctional phenols such as phenol, cresol or alkylphenol, phenolic compounds such as polycondensates of aldehydes, and resoles may be used.

Examples of the polyisocyanate-based compound include, for example, toluene diisocyanate, methylcyclohexane diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, and hexamethylene diene. Polyisocyanate compounds such as isocyanate, benzoyl diisocyanate, hydrogenated terephthalic diisocyanate, dimer acid diisocyanate, trimethylhexamethylene diisocyanate, and isocyanuric acid triisocyanate.

Further, for example, the polyisocyanate compound or a polyisocyanate compound obtained by reacting a compound having at least two active hydrogen atoms such as an amine group, a hydroxyl group, a carboxyl group or water, or the polyisocyanate compound may be used. Three to five-mers and so on.

Examples of the amine compound are: aliphatic primary, secondary, tertiary amines; aromatic primary, secondary, tertiary amines; cyclic amines, guanidines, urea derivatives, etc., specifically, for example, three extensions Ethylenetetramine, diaminodiphenylmethane, diaminodiphenyl ether, m-xylylenediamine, dicyandiamide, 1,8-diazabicyclo(5,4,0)-7-undecene, 1,5-diazabicyclo(4,3,0)-5-pinene, dimethylurea, guanidine urea, and the like.

Examples of the acid anhydride-based compound include phthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, maleic anhydride, and a condensate of an unsaturated compound.

Examples of the imidazole-based compound include 1-isobutyl-2-methylimidazole, 2-methylimidazole, 1-benzyl-2-methylimidazole, 2-ethyl-4-methylimidazole, and 2 - phenylimidazole, benzimidazole, and the like. Further, the imidazole-based compound can also function as a curing accelerator described later, but is classified as a curing agent in the present invention.

Examples of the amide-based compound include dicyandiamide and a derivative thereof, and a polyamide resin.

Examples of the thiol-based compound include, for example, butanol, dodecyl mercaptan, hexyl mercaptan, pentaerythritol tetrakis(3-mercaptopropionate), 1,1'-[isopropylidene double (pair) Phenoxy) bis[3-mercaptopropan-2-ol] and the like.

The cationic polymerization initiator is a person which generates a cation by irradiation with heat or an active energy ray, and may be, for example, an aromatic sulfonium salt or the like. Specifically, for example, an anionic component such as SbF ^6- , BF ^4- , AsF ^6- , PF ^6- , CF ₃ SO ₃ ^2- , B(C ₆ F ₅ ) ^4- , and iodine, sulfur, nitrogen, and phosphorus may be contained. A compound composed of an aromatic cation component of an atom. Particularly preferred are diaryl iodonium salts and triarylsulfonium salts.

Examples of the organic phosphines include, for example, tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine, etc.; the onium salt system can be exemplified by tetraphenylphosphonium tetraphenylborate or tetraphenylphosphonium. ‧ Ethyl triphenyl borate, tetrabutyl hydrazine, tetrabutyl borate, etc.; tetraphenyl borate can be exemplified by: 2-ethyl-4-methylimidazole ‧ tetraphenyl borate, N- base Porphyrin ‧ tetraphenyl borate and the like.

When a hardener is a polyfunctional phenol, an amine compound, or an acid anhydride compound, a functional group in the hardener (polyfunctional phenolic) with respect to the total epoxy group in the composition containing the epoxy compound The equivalent ratio of the hydroxyl group, the amine group of the amine compound or the acid anhydride group of the acid anhydride compound is preferably in the range of 0.8 to 1.5.

When a polyisocyanate compound is used as the curing agent, the number of isocyanate groups in the polyisocyanate compound is preferably in the range of 1:0.01 to 1:1.5, based on the number of hydroxyl groups in the composition containing the epoxy compound. .

When the curing agent is an imidazole-based compound, the solid content in the composition containing the epoxy compound is preferably in the range of 0.5 to 10 parts by weight based on 100 parts by weight of the total epoxy compound component.

When the sulphonate-based compound is used as the curing agent, the solid content in the composition containing the epoxy compound is preferably in the range of 0.1 to 20% by weight based on the total amount of the total epoxy compound component and the guanamine-based compound. .

When the thiol compound is used as the curing agent, the solid content in the composition containing the epoxy compound is preferably in the range of 1 to 100 parts by weight based on 100 parts by weight of the total epoxy compound component.

When the curing agent is a cationic polymerization initiator, the solid content in the composition containing the epoxy compound is preferably in the range of 0.01 to 15 parts by weight based on 100 parts by weight of the total epoxy compound component.

When the organic phosphine is used as the curing agent, the solid content in the composition containing the epoxy compound is preferably in the range of 0.1 to 20% by weight based on the total amount of the total epoxy compound component and the organic phosphine.

In the composition containing an epoxy compound of the present invention, in addition to the above-exemplified curing agent, for example, an organic acid diterpene, a boron halide amine complex or the like may be used as a curing agent. These hardeners 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 epoxide of the present invention (also referred to as "another epoxy compound" in the present specification) may be used.

Examples of the other epoxy compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, phenol novolak type epoxy resin, and cresol novolac. Type epoxy resin, bisphenol A phenolic epoxy resin, tetrabromobisphenol A epoxy resin, other polyfunctional phenolic epoxy resin and other epoxy propylene ether type epoxy resin; in the above aromatic epoxy resin Aromatic ring with hydrogen-added epoxy resin, glycidyl ester epoxy resin, glycidylamine epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, etc. Oxygen compound. The other epoxy compounds listed above may be used alone or in combination of two or more.

When the composition containing the epoxy compound of the present invention contains the epoxy compound of the present invention and other epoxy compounds, in the composition containing the epoxy compound, among the total epoxy compound components belonging to the solid portion, other epoxy The proportion of the compound is preferably 1% by weight or more, more preferably 5% by weight or more, and more preferably 99% by weight or less, more preferably 95% by weight or less. When the ratio of the other epoxy compound is at least the above lower limit value, the effect of improving the physical properties by blending other epoxy compounds can be sufficiently obtained. On the other hand, when the ratio of the other epoxy compound is at most 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]  

In the epoxy compound-containing composition of the present invention, when the coating film is formed or the like, the viscosity of the composition containing the epoxy compound is appropriately adjusted, and the solvent may be blended for dilution. In the epoxy compound-containing composition of the present invention, the solvent is used to ensure the handling property and workability at the time of molding the composition containing the epoxy compound, and the amount of use is not particularly limited. Further, as described above, in the present invention, the terms "solvent" and "solvent" are used in accordance with the form of use, and the same may be used independently or different materials may be used.

In the solvent which can be contained in the epoxy compound of the present invention, one or two or more kinds of organic solvents exemplified for the reaction solvent (E) to be used in the production of the epoxy compound of the present invention can be used.

 [Other ingredients]  

The composition containing an epoxy compound of the present invention may contain other components in addition to the above-exemplified components. Other components include, for example, a curing accelerator (except for the above-mentioned curing agent), a decane coupling agent, a flame retardant, an antioxidant, a photostabilizer, a plasticizer, a reactive diluent, a pigment, an inorganic filler, Organic fillers, etc. The other components listed above may be used in combination as appropriate in accordance with the physical properties required for the composition containing the epoxy compound.

 [paint]  

The coating of the present invention contains the epoxy compound of the present invention or the composition containing the epoxy compound of the present invention.

Further, in addition to the epoxy compound of the present invention or the epoxy compound-containing composition of the present invention, various methods known in the art, mixed solvents, and various additives usually added to the coating may be used as needed. .

In the solvent, one or two or more kinds of organic solvents exemplified in the reaction solvent (E) used in the production of the epoxy compound of the present invention can be used.

Examples of the above additives include various stabilizers such as ultraviolet absorbers, antioxidants, weather stabilizers, and heat inhibitors; colorants such as dyes, organic pigments, and inorganic pigments; and conductivity imparting agents such as carbon black and ferrite iron; and pigments; Dispersing agents, leveling agents, defoaming agents, tackifiers, preservatives, anti-fungal agents, rust inhibitors and wetting agents.

 [hardened material]  

The cured product of the present invention can be obtained by hardening the composition containing the epoxy compound of the present invention. Here, "hardening" means deliberately hardening an epoxy compound by heat and/or light, and the degree of hardening can be controlled according to desired physical properties and use.

When the composition containing the epoxy compound of the present invention is cured to be a cured product, the curing method of the composition containing the epoxy compound is based on the blending component, the blending amount, and the blend shape in the composition containing the epoxy compound. However, it is usually different, for example, heating conditions of 50 to 200 ° C and 5 seconds to 180 minutes. The heating system is preferably heated at a temperature of 50 to 160 ° C for 5 seconds to 30 minutes from the viewpoint of reducing the hardening failure, and is 90 to 280 ° C higher than the primary heating temperature by 40 to 120 ° C for 1 minute. Two-stage treatment of 150 minutes of secondary heating was carried out.

When the cured product is a semi-cured material, the curing reaction of the composition containing the epoxy compound may be carried out by heating or the like to the extent that the shape can be maintained. When the composition containing the epoxy compound contains a solvent, most of the solvent is removed by a method such as heating, depressurization, or air drying, but a solvent of 5% by weight or less may remain in the semi-cured material.

 [Use of epoxy compound]  

By using the epoxy compound of the present invention, a coating film excellent in light resistance, hardness, and dissolution resistance can be formed. Thereby, the epoxy compound of the present invention and the composition containing the epoxy compound blended therefor are suitable for use in coatings, electric and electronic materials, adhesives, fiber reinforced resins (FRP) and the like. In particular, the related coatings are often used outdoors, and the epoxy compound and the composition containing the epoxy compound of the present invention are suitably used.

 [Examples]  

Hereinafter, the present invention will be more specifically described based on the examples, but the present invention is not limited by the following examples. In addition, the various manufacturing conditions and evaluation result values in the following embodiments are intended to include the upper or lower preferred values of the embodiments of the present invention, and the preferred ranges may also be implemented by the above upper (or lower) values, and the following The range of values specified by the combination of the values of the examples or the examples.

 [raw materials, etc.]  

The materials, catalysts, 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) 828 US by Mitsubishi Chemical Corporation, epoxy equivalent: 186 g / equivalent, total chlorine: 0.6% by weight)

 [Compound (B) containing piperidine ring]  

B-1: bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (Tinuvin 770DF, manufactured by BASF)

 [phenolic compound (C)]  

C-1: bisphenol A (manufactured by 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 method]  

The evaluation methods of the following examples and comparative examples are as follows.

 [epoxy equivalent]  

The epoxy compound obtained in each of Examples 1 to 5 and Comparative Examples 1 and 2 was measured for epoxy equivalent (g/eq.) in accordance with JIS K 7236.

 [Total chlorine and total bromine]  

For the epoxy compounds obtained in Examples 1 to 5 and Comparative Examples 1 and 2, the sample was taken on a magnetic plate, heated in a quartz tube tubular furnace, and the chlorine in the combustion gas was absorbed by a 0.1%-H ₂ O ₂ aqueous solution. Bromine. Chlorine and bromine (% by weight) in the absorption liquid were measured by an ion chromatography analyzer.

Device: Quartz tube tubular furnace (Mitsubishi Chemical Co., Ltd., AQF-100 type)

Ion Chromatography Analyzer (Dionex, ICS-1000)

 [Weight average molecular weight (Mw)]  

With respect to the epoxy compounds obtained in Examples 1 to 5 and Comparative Examples 1 and 2, the weight average molecular weight was measured by gel permeation chromatography (GPC). The apparatus and measurement conditions used in the GPC measurement are as follows.

Device: GPC

Model: HLC-8120GPC (made by Tosoh Corporation)

Pipe column: TSKGEL HM-H+H4000+H4000+H3000+H2000 (made by Tosoh Corporation)

Detector: UV-8020 (manufactured by Tosoh Corporation), 254nm

Eluent: THF (0.5mL / min, 40 ° C)

Sample: 1% tetrahydrofuran solution (10μ injection)

Checking line: Standard polystyrene (made by Tosoh Corporation)

 [light resistance]  

100 parts by weight of the epoxy compound solution obtained in Examples 1 to 5 and Comparative Examples 1 and 2, 20 parts by weight of cyclohexanone, and 2-ethyl-4-methylimidazole (jER Cure, manufactured by Mitsubishi Chemical Corporation) (registered trademark) EMI24) 0.2 parts by weight, coated on a steel plate described in JIS K5600-1-4 using a 150 μm coating film trickle, and heated at 150 ° C for 90 minutes to prepare a coating film. The obtained coating film was subjected to light irradiation for 167 hours by the following weatherproofer, and the yellowing degree (ΔYI) was measured by the following color difference meter, and the evaluation index of light resistance was used.

 ‧ weatherproof machine  

Device: ATLAS aging test machine Ci4000 (manufactured by Toyo Seiki Co., Ltd.)

Light source: 6500W water-cooled xenon arc lamp

Test conditions: Blackboard temperature 89 ° C

Room humidity 50%

Irradiation intensity 100W/m ² (300~400nm)

 ‧ Colorimeter: ZE6000 (made by Nippon Denshoku Industries Co., Ltd.)    [film hardness]  

Using the epoxy compound solution or the epoxy compound obtained in Examples 1 to 5 and Comparative Examples 1 and 2, a coating film was formed on the steel sheet in the same manner as in the above-mentioned light resistance evaluation. For the obtained coating film, the pencil hardness was measured using a pencil hardness tester (manufactured by Daisuke Kogyo Co., Ltd.) in accordance with JIS K5600-5-4, and an evaluation index of the hardness of the coating film was used.

 [resistance to dissolution]  

Using the epoxy compound solution or the epoxy compound obtained in Examples 1 to 5 and Comparative Examples 1 and 2, a coating film was formed on the steel sheet in the same manner as in the above-mentioned light resistance evaluation.

100 g of tetrahydrofuran was placed in a 200 ml sample vial, and a 4 cm × 4 cm test piece cut out from the obtained coated plate was immersed therein, and allowed to stand at room temperature for 12 hours or more, and then the test piece was taken out from tetrahydrofuran and allowed to stand at 100 ° C for 2 hours. After drying, the weight was measured, and the gel fraction (%) was calculated according to the following formula. The gel fraction (%) was used as an evaluation index for the dissolution resistance.

Gel fraction (%) = [{(weight of test piece after drying at 100 ° C for 2 hours) - (weight of test piece before treatment)} / (weight of test piece before treatment)] × 100

The higher the gel fraction (%) value, the more excellent the dissolution resistance of the coating film is.

 [Manufacture of epoxy compounds ‧ evaluation]    (Example 1)  

1200 parts by weight of bisphenol A diglycidyl ether (A-1) and 24.9 parts by weight of bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (B-1) 460 parts by weight of bisphenol A (C-1) and 0.72 parts by weight of a 50% aqueous solution of tetramethylammonium chloride (D-1), charged into a 5 L flask, and subjected to polymerization at 165 ° C for 6 hours under a nitrogen atmosphere. Upon reaction, the target epoxy compound is obtained. This was dissolved in 1685 parts by weight of methyl ethyl ketone (F-1) (solid content: 50% by weight). With respect to the obtained epoxy compound solution, the total of the epoxy equivalent, the total chlorine amount and the total bromine amount, the weight average molecular weight (Mw), the light resistance, the coating film hardness, and the dissolution resistance were evaluated in accordance with the above methods. The results are shown in Table 1. .

 (Example 2)  

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

 (Example 3)  

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

 (Example 4)  

175 parts by weight of bisphenol A diglycidyl ether (A-1) and 145 parts by weight of bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (B-1) And 0.105 parts by weight of a tetramethylammonium chloride 50% aqueous solution (D-1), which was placed in a 1 L flask, and subjected to a polymerization reaction at 165 ° C for 6 hours under a nitrogen atmosphere to obtain a target epoxy compound. This was dissolved in 320 parts by weight of methyl ethyl ketone (F-1) (solid content: 50% by weight). With respect to the obtained epoxy compound solution, the total of the epoxy equivalent, the total chlorine amount and the total bromine amount, the weight average molecular weight (Mw), the light resistance, the coating film hardness, and the dissolution resistance were evaluated in accordance with the above methods. The results are shown in Table 1. .

 (Example 5)  

200 parts by weight of bisphenol A diglycidyl ether (A-1) and 36 parts by weight of bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (B-1) And 125 parts by weight of tetrabromobisphenol A (C-2) and 0.4 parts by weight of a 50% aqueous solution (D-1) of tetramethylammonium chloride were placed in a 1 L flask and operated at 165 ° C under a nitrogen atmosphere. The target polymerization of the epoxy compound is obtained in an hour. This was dissolved in 361 parts by weight of methyl ethyl ketone (F-1) (solid content: 50% by weight). With respect to the obtained epoxy compound solution, the total of the epoxy equivalent, the total chlorine amount and the total bromine amount, the weight average molecular weight (Mw), the light resistance, the coating film hardness, and the dissolution resistance were evaluated in accordance with the above methods. The results are shown in Table 1. .

 (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 (D-1) of tetramethylammonium chloride were charged. In a 1 L flask, polymerization was carried out at 165 ° C for 6 hours under a nitrogen 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). With respect to the obtained epoxy compound solution, the total of the epoxy equivalent, the total chlorine amount and the total bromine amount, the weight average molecular weight (Mw), the light resistance, the coating film hardness, and the dissolution resistance were evaluated in accordance with the above methods. The results are shown in Table 1. .

 (Comparative Example 2)  

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 (D-1) of tetramethylammonium chloride were charged. In a 1 L flask, polymerization was carried out at 165 ° C for 6 hours under a nitrogen atmosphere to obtain an epoxy compound. This was dissolved in 280 parts by weight of methyl ethyl ketone (F-1), and further added with bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (B-1) 28 weight. Parts and dissolved (solid content of 50% by weight). With respect to the obtained epoxy compound solution, the total of the epoxy equivalent, the total chlorine amount and the total bromine amount, the weight average molecular weight (Mw), the light resistance, the coating film hardness, and the dissolution resistance were evaluated in accordance with the above methods. The results are shown in Table 1. .

 [Evaluation results]  

As is apparent from Table 1, Example 1 using a divalent group represented by the formula (1) and a divalent group represented by the formula (2) and having an epoxy equivalent of 200 g/eq or more and 200,000 g/eq or less is used. The epoxy compound of 5, the produced coating film exhibits high light resistance, and has high hardness and dissolution resistance.

On the other hand, the coating film produced by using the epoxy compound of Comparative Example 1 having no structure (1) was insufficient in light resistance.

Further, the coating film prepared by using the epoxy compound of Comparative Example 2 having no structure of the formula (1) was insufficient in dissolution resistance.

In the epoxy compound of the present invention, it is judged that by combining the groups represented by the formula (1) and the formula (2), a coating film having good light resistance, hardness, and dissolution resistance can be formed.

The present invention has been described with reference to the detailed and specific embodiments thereof, and various modifications and additional modifications can be made without departing from the spirit and scope of the invention. The present application is based on the Japanese Patent Application (Japanese Patent Application No. 2016-173721) filed on Sep.

 (industrial availability)  

The coating film using the epoxy compound of the present invention has excellent weather resistance, hardness, and dissolution resistance. Thereby, the epoxy compound of the present invention, the epoxy compound-containing composition containing the epoxy compound, and the cured product thereof are suitable for use in coatings, electric and electronic materials, adhesives, fiber reinforced resins (FRP), and the like. .

Claims (13)

An epoxy compound containing 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/eq or more and 200,000 g/eq or less; (In the formula (1), R ¹ to R ⁴ may be the same or different, and represent 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 hydrocarbon group having 1 to 50 carbon atoms which may have a substituent).  The epoxy compound according to claim 1, wherein the total chlorine amount and the total bromine amount are 3% by weight or less.    The epoxy compound according to claim 1 or 2, wherein the divalent group represented by the above formula (1) contains two or more kinds of different groups.    The epoxy compound according to any one of claims 1 to 3, wherein the divalent group represented by the above formula (2) contains two or more kinds of different groups.   The epoxy compound according to any one of claims 1 to 4, wherein the X system has a group having a structure represented by any one of the following formulas (3) to (8); and the following formula (3) to (8) Each aromatic ring or cycloalkyl group in the ) may also be substituted by an alkyl group; [Chemical 3] (In the formula (3), R ⁵ and R ⁶ may be the same or different and represent a hydrogen atom or an alkyl group; (In the formula (4), R ⁷ and R ⁸ may be the same or different and represent 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 a C 1 to 5 alkyl group; (In the formula (8), R ¹¹ and R ¹² may be the same or different and each represents a direct bond or a C 1 to 5 alkyl group).  A coating material comprising the epoxy compound according to any one of claims 1 to 5.    A method for producing an epoxy compound according to any one of claims 1 to 5, which comprises a compound containing a piperidine ring and a total chlorine amount and a total bromine amount of 5% by weight or less. A step of carrying out a reaction of a compound containing an epoxy group.    A method for producing an epoxy compound according to any one of claims 1 to 5, which comprises: a compound containing a piperidine ring, a total chlorine amount and a total bromine amount of 5% by weight or less A step of reacting a compound containing an epoxy group and a phenol compound.    A composition containing an epoxy compound, which comprises the epoxy compound according to any one of claims 1 to 5, and a curing agent.    The composition containing an epoxy compound according to claim 9, wherein the curing agent is contained in an amount of 0.1 to 1000 parts by weight based on 100 parts by weight of the epoxy compound.    The composition containing an epoxy compound according to claim 9 or 10, wherein the curing agent is a polyfunctional phenol, a polyisocyanate compound, an amine compound, an acid anhydride compound, an imidazole compound, a guanamine compound, or the like. At least one selected from the group consisting of a thiol compound, a cationic polymerization initiator, and an organic phosphine.    A coating material comprising the epoxy compound-containing composition according to any one of claims 9 to 11.    A cured product obtained by hardening a composition containing an epoxy compound according to any one of claims 9 to 11.