WO2018047799A1 - Epoxy compound, method for producing epoxy compound, epoxy compound-containing composition, coating material and cured product - Google Patents

Abstract

The present invention relates to an epoxy compound which comprises a divalent group represented by formula (1) and a divalent group represented by formula (2), and which has an epoxy equivalent weight of from 200 g/equivalent to 200,000 g/equivalent (inclusive). (In formulae (1) and (2), R¹-R⁴ and X are as defined in the description.)

Description

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

The present invention relates to an epoxy compound capable of forming a coating film excellent in light resistance, hardness and elution resistance, and a method for producing the same. Moreover, this invention relates to the epoxy compound containing composition, coating material, and hardened | cured material which are obtained using this epoxy compound.

Epoxy compounds are widely used in the fields of paint, civil engineering, adhesion, electrical materials, etc., because they are excellent in heat resistance, adhesion, flexibility, electrical properties, and the like. Patent Document 1 describes a reaction product of an epoxy resin having a high halogen content and a hindered amine compound. Patent Documents 2 to 4 disclose a composition of an epoxy resin and a hindered amine compound.

Japanese Laid-Open Patent Publication No. 8-165437 Japanese Unexamined Patent Publication No. 2009-108301 Japanese Unexamined Patent Publication No. 2016-113564 Japanese Laid-Open Patent Publication No. 9-176284

However, according to the study of the present invention, the coating film using the epoxy compound described in Patent Document 1 has insufficient light resistance. In addition, coating films using the compositions described in Patent Documents 2 to 4 have low hardness and have problems such as bleeding out.

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 which can form the coating film excellent in light resistance, hardness, and elution resistance, and its manufacturing method. Moreover, this invention is providing the epoxy compound containing composition obtained by using this epoxy compound, a coating material, and hardened | cured material.

As a result of intensive investigations to solve the above problems, the present inventors have found that an epoxy compound having a piperidine ring and having an epoxy equivalent of 200 g / equivalent or more and 200,000 g / equivalent or less has the above problem. We have found that it can be solved, and have completed the invention. That is, the gist of the present invention resides in the following [1] to [13].

[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 hydrocarbon group having 1 to 50 carbon atoms which may have a substituent.)
[2] The epoxy compound according to [1], wherein the total amount of total chlorine and total bromine is 3% by weight or less.
[3] The epoxy compound according to [1] or [2], including 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] The X is a group having a structure represented by any of the following formulas (3) to (8), and each aromatic ring or cycloalkylene group in the following formulas (3) to (8) is The epoxy compound according to any one of [1] to [4], each of which may be substituted with an alkyl group.

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

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

(In Formula (7), R ⁹ and R ¹⁰ may be the same or different and each represents 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] A paint comprising the epoxy compound according to any one of [1] to [5].
[7] In any one of [1] to [5], including a step of reacting a piperidine ring-containing compound with an epoxy group-containing compound having a total amount of total chlorine and total bromine of 5% by weight or less. The manufacturing method of the epoxy compound of description.
[8] Any one of [1] to [5], including a step of 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 as described in one.
[9] An epoxy compound-containing composition comprising the epoxy compound according to any one of [1] to [5] and a curing agent.
[10] The epoxy compound-containing composition according to [9], comprising 0.1 to 1000 parts by weight of the curing agent with respect to 100 parts by weight of the epoxy compound.
[11] The curing agent is composed of polyfunctional phenols, polyisocyanate compounds, amine compounds, acid anhydride compounds, imidazole compounds, amide compounds, mercaptan compounds, cationic polymerization initiators, and organic phosphines. The epoxy compound-containing composition according to [9] or [10], which is at least one selected from the group.
[12] A paint comprising the epoxy compound-containing composition according to any one of [9] to [11].
[13] A cured product obtained by curing the epoxy compound-containing composition according to any one of [9] to [11].

According to the present invention, an epoxy compound capable of forming a coating film excellent in light resistance, hardness and elution resistance and a method for producing the same are provided. Moreover, according to this invention, the epoxy compound containing composition obtained by using this epoxy compound, a coating material, and hardened | cured material 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 “˜” is used to express a numerical value or a physical property value before and after it, the value before and after that value 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 has an epoxy equivalent of 200 g / equivalent or more and 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), the coating film using the epoxy compound of the present invention has light resistance, hardness and elution resistance. Excellent in properties. When the epoxy equivalent is 200 g / equivalent or more and 200,000 g / equivalent or less, both 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. More preferably, R ¹ to R ⁴ are the same and are methyl groups.

In addition, the epoxy compound of the present invention is a divalent group represented by the above formula (1) from the viewpoint of handling properties during production of the epoxy compound and control of physical properties such as corrosion resistance and weather resistance when formed into a coating film. It is preferable to include 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 formula (2), X may have a substituent and has 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 aliphatic hydrocarbon group or aromatic hydrocarbon group. The cyclic aliphatic hydrocarbon group and the aromatic hydrocarbon group are collectively referred to as a hydrocarbon group having a cyclic structure. X is preferably a hydrocarbon group containing a cyclic structure.
The epoxy compound of this invention is excellent in chemical resistance, adhesiveness, and a softness | flexibility by having the bivalent group represented by the said Formula (2).

In addition, the epoxy compound of the present invention is a divalent group represented by the above formula (2) from the viewpoint of handling properties during production of the epoxy compound and control of physical properties such as corrosion resistance and weather resistance when formed into a coating film. It is preferable to include two or more different groups.

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 Formula (3), R ⁵ and R ⁶ may be the same or different, and represent a hydrogen atom or an alkyl group.)

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

(In Formula (7), R ⁹ and R ¹⁰ may be the same or different and each represents 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, 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, 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.

[Epoxy equivalent]
The epoxy equivalent of the epoxy compound of the present invention is 200 g / equivalent or more, preferably 250 g / equivalent or more, more preferably 300 g / equivalent or more. Thereby, the flexibility can be further improved.
In addition, the epoxy equivalent of the epoxy compound of the present invention is 200,000 g / equivalent or less, preferably 100,000 g / equivalent or less, and preferably 50,000 g / equivalent or less from the viewpoint of compatibility with other materials. More preferably.
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.

[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 with respect to the epoxy compound from the viewpoint of improving the light resistance and weather resistance of the coating film using the epoxy compound of the present invention. % By weight or less, more preferably 2% by weight or less, still more preferably 1% by weight or less. The lower limit is preferably 0% by weight, but may actually be 0.0001% by weight.
In addition, the chlorine and bromine in the epoxy compound of this invention mean what is contained with a partial form of a structure.

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, but for example, the total of the total chlorine amount and the total bromine amount as the epoxy group-containing compound (A) described later is The method of using the epoxy compound which is 5 weight% or less, Preferably it is 4 weight% or less is mentioned.

[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 particularly preferably 100,000 or less from the viewpoint of compatibility with other materials.
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.

[Method for producing epoxy compound]
The epoxy compound of this invention can be manufactured by copolymerizing the epoxy group containing compound (A) mentioned later as a raw material of an epoxy compound, and a piperidine ring containing compound (B).
Moreover, the epoxy compound of the present invention may be produced by copolymerizing 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 for the epoxy compound. it can.
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. In the epoxy group-containing compound (A) used in the present invention, the total amount of total chlorine and total bromine is 5% by weight or less, and a divalent group represented by the above formula (2) is introduced.

As the epoxy group-containing compound (A) used in the present invention, 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-tert -Butyl bisphenol A diglycidyl ether, tetramethylbisphe Bisphenol-based diglycidyl ethers such as Biol diglycidyl ether; Biphenol-based diglycidyl ethers such as biphenol diglycidyl ether, tetramethylbiphenol diglycidyl ether, dimethylbiphenol diglycidyl ether, and tetra-tert-butylbiphenol diglycidyl ether Benzenediol diglycidyl ethers such as hydroquinone diglycidyl ether, dihydroanthracene diglycidyl ether, methyl hydroquinone diglycidyl ether, dibutyl hydroquinone diglycidyl ether, resorcin diglycidyl ether, methyl resorcin diglycidyl ether; dihydroanthrahydroquinone diglycidyl ether Dihydroxy diphenyl ether diglycidyl ester Aromatic diglycidyl ethers such as tellurium, thiodiphenol diglycidyl ether, dihydroxynaphthalenediglycidyl ether; bisphenol diglycidyl ethers, biphenol diglycidyl ethers, benzenediol diglycidyl ethers and aromatics An epoxy compound in which hydrogen is added to the aromatic ring of diglycidyl ether selected from diglycidyl ethers; adipic acid, succinic acid, phthalic acid, tetrahydrophthalic acid, methylhexahydrophthalic acid, terephthalic acid, isophthalic acid, orthophthalic acid, Epoxy resins produced from various carboxylic acids such as biphenyl dicarboxylic acid and dimer acid and 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-decane (Poly) alkyle consisting only of a chain structure such as diol diglycidyl ether and 2,2-dimethyl-1,3-propanediol diglycidyl ether Glycol diglycidyl ether, alkylene glycol diglycidyl ethers having a cyclic structure such as 1,4-cyclohexanedimethanol diglycidyl ether.

Also, examples of the trifunctional or higher functional epoxy group-containing compound include the following. 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- Droxy-3,5-dimethylphenyl) -1-methylethyl] phenyl] ethylidene] bis (2-methylphenol) type epoxy resin, 2,6-bis (4-hydroxy-3,5-dimethylbenzyl) -4- Trifunctional epoxy resins such as methylphenol type 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 Tetrafunctional epoxy resins such as (4-hydroxyphenyl) -p-xylene type epoxy resin; 2,4,6-tris [(4-hydroxyphenyl Pentafunctional epoxy resins such as methyl] -1,3-benzenediol type epoxy resins; epoxy compounds produced from various amine compounds such as diaminodiphenylmethane, aminophenol, xylenediamine, and epihalohydrin; aliphatic polyols; Epoxy compounds produced from epihalohydrins, phenol novolac epoxy resins, cresol novolac epoxy resins, bisphenol A novolac epoxy resins, naphthol novolac epoxy resins, phenol aralkyl epoxy resins, biphenyl aralkyl epoxy resins, phenol modified xylene epoxy Obtained by condensation reaction of resins and various phenols with various aldehydes such as hydroxybenzaldehyde, crotonaldehyde, and glyoxal. Polyhydric phenolic resins which, polyfunctional epoxy resins of epoxy resin or the like using a co-condensed 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) used in the present invention is not particularly limited as long as it introduces a divalent group represented by the above formula (1), but preferably contains neither chlorine nor bromine. For example, examples of the compound having one NH group in the molecule include 2,2,6,6-tetramethyl-4-piperidyl methacrylate. 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] and the like. 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) 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 in the production process and controlling the physical properties of the resulting epoxy compound.

The phenolic compound (C) used in the present invention must contain neither chlorine nor bromine. For example, compounds having two hydroxyl groups bonded to an aromatic ring include bisphenol A, bisphenol F, bisphenol E, bisphenol Z, bisphenol S, bisphenol AD, bisphenol acetophenone, bisphenol trimethylcyclohexane, bisphenol fluorene, tetramethyl bisphenol A, tetra Bisphenols such as methyl bisphenol F, tetra-tert-butyl bisphenol A, tetramethyl bisphenol S; biphenols such as biphenol, tetramethyl biphenol, dimethyl biphenol, tetra-tert-butyl biphenol; hydroquinone, methyl hydroquinone, dibutyl hydroquinone, resorcin Benzene diols such as methylresorcin (where “benzene” “Alls” is 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 diphenol; dihydroxynaphthalenes such as dihydroxynaphthalene; and dihydroxystilbenes 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-trimethyl) Phenol), 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-methyl Trifunctional phenolic compounds such as til] phenyl] ethylidene] bis (2-methylphenol), 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, Tetrafunctional phenolic compounds such as 2-tetrakis (p-hydroxyphenyl) ethane, 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-based novolak resins such as bisphenol A novolac resin; various phenol resins such as naphthol novolak resin, phenol aralkyl resin, terpene phenol resin, dicyclopentadiene phenol resin, phenol biphenylene resin, phenol-modified xylene resin, and various of these Polyhydric phenol resins obtained by condensation reaction of various phenols with various aldehydes such as hydroxybenzaldehyde, crotonaldehyde, glyoxal, etc., co-condensation resin of heavy oil or pitches with phenols and formaldehyde, etc. Examples include polyfunctional phenolic compounds.

Of 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) and the piperidine ring-containing compound (B) used for the production of the epoxy compound of the present invention, or the epoxy group-containing compound (A) and the piperidine ring used for the production of the epoxy compound of the present invention The compounding ratio of the containing compound (B) and the phenol compound (C) is preferably a compounding ratio at which the theoretical epoxy equivalent of the resulting epoxy compound is 200,000 g / equivalent or less, and a compounding ratio of 150,000 g / equivalent or less. The ratio is more preferably 100,000 g / equivalent or less, particularly preferably in view of ensuring compatibility with other materials.

On the other hand, the lower 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. .

The compounding ratio of the epoxy group-containing compound (A) and the piperidine ring-containing compound (B) is, for example, 1 to 100 parts by weight of the piperidine ring-containing compound (B) with respect to 100 parts by weight of the epoxy group-containing compound (A). can do.
Moreover, as a compounding ratio of an epoxy group-containing compound (A), a piperidine ring-containing compound (B), and a phenol compound (C), for example, a piperidine ring-containing compound (100 parts by weight with respect to 100 parts by weight of the epoxy group-containing compound (A)) B) 1 to 100 parts by weight, phenol compound (C) 1 to 100 parts by weight.

Here, the theoretical epoxy equivalent means that the epoxy group-containing compound (A), piperidine ring-containing compound (B), and phenol compound (C) all have an epoxy group, NH group and / or OH group of 1: 1. It means the epoxy equivalent of the reaction product when reacted.
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)]
In the reaction step for producing the epoxy compound of the present invention, a catalyst (D) may be used. 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, tricyclohe Silphosphine, tri-n-propylphosphine, di-tert-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 black Id, trimethylbenzylphosphonium bromide, tetraphenylphosphonium bromide, triphenylmethylphosphonium bromide, triphenylmethylphosphonium iodide, triphenylethylphosphonium chloride, triphenylethylphosphonium bromide, triphenylethylphosphonium iodide, triphenylbenzylphosphonium chloride, And triphenylbenzylphosphonium bromide.

Specific examples of 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 Ride, and phenyl trimethylammonium chloride and the like.

Specific examples of the 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 the catalyst (D) is used, the amount used is preferably 10,000 ppm by weight or less, for example, 10 to 5000 ppm by weight, based on the amount of the epoxy group-containing compound (A) used.

[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.
Specific examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, 2-octanone, cyclopentanone, cyclohexanone, acetylacetone and the like.
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 glycol ether solvents 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 thereof 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 between the epoxy group-containing compound (A) and the piperidine ring-containing compound (B), or the reaction between the epoxy group-containing compound (A), the piperidine ring-containing compound (B) and the phenol compound (C) is carried out at normal pressure. , Pressurization, and reduced pressure.

The reaction temperature is usually 60 to 240 ° C. If the reaction temperature is not less than the lower limit, the reaction is likely to proceed, and if the reaction temperature is not more than the upper limit, the side reaction is unlikely to proceed. The temperature is preferably 80 to 220 ° C, more preferably 100 to 200 ° C, and still more preferably 120 to 180 ° C, from the viewpoint of obtaining a high-purity epoxy compound.

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 further preferably 2 to 10 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 of reducing unreacted components.

The compound (B) is less likely to undergo a copolymerization reaction due to its structure, and on the other hand, due to the presence of nitrogen atoms, there is a concern that the reaction may be gelled if the reaction conditions are made more severe. By the preferred reaction conditions described above, unreacted components are reduced even when copolymerization of the compounds (A) and (B) or copolymerization of the compounds (A), (B) and (C). A pure epoxy compound can be obtained.

[Diluted solvent (F)]
In the method for producing an epoxy compound of the present invention, the solid content concentration may be adjusted by mixing the diluting solvent (F) after completion of the reaction. The dilution solvent (F) may be any solvent as long as it can dissolve the epoxy compound, but 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 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 0.1 to 100 parts by weight with respect to 100 parts by weight of the epoxy compound of the present invention. More preferably 0.1 to 80 parts by weight, particularly preferably 0.1 to 60 parts by weight.

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 preferably 0 with respect to 100 weight part of all the epoxy compound components. 0.1 to 1000 parts by weight, more preferably 0.1 to 100 parts by weight, still more preferably 0.1 to 80 parts by weight, and particularly preferably 0.1 to 60 parts by weight.
More preferable content of the curing agent is as described below according to the kind of the curing agent.

In the present invention, “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, as the curing agent, polyfunctional phenols, polyisocyanate compounds, amine compounds, acid anhydride compounds, imidazole compounds, amide compounds, mercaptan compounds, cationic polymerization initiation It is preferable to use at least one member selected from the group consisting of an agent and organic phosphines.

Examples of polyfunctional phenols include bisphenol A, bisphenol F, bisphenol S, bisphenol B, bisphenol AD, bisphenol Z, tetrabromobisphenol A, and the like; 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, these polyfunctional phenols and monofunctional phenols such as phenol, cresol and alkylphenol and novolaks and resols which are polycondensates of aldehydes can be mentioned.

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.
Further, a polyisocyanate compound obtained by reacting these polyisocyanate compounds with a compound having at least two active hydrogen atoms such as an amino group, a hydroxyl group, a carboxyl group and water, or 3 to 3 of the above polyisocyanate compounds. A pentamer 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.

Examples of mercaptan compounds include butyl mercaptan, dodecyl mercaptan, hexyl mercaptan, pentaerythritol tetrakis (3-mercaptopropionate), 1,1 ′-[isopropylidenebis (p-phenyleneoxy) bis [3-mercaptopropane -2-ol] and the like.

Cationic polymerization initiators generate cations by heat or active energy ray irradiation, and include aromatic onium salts. Specifically, anionic components 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, phosphorus, etc. And a compound comprising an aromatic cation component containing the above atoms. 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 / ethyltriphenyl. Examples include borate, 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) The amino group or the acid anhydride group of the acid anhydride compound) is preferably used so as to be 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 relative to the number of hydroxyl groups in the epoxy compound-containing composition is in the range of 1: 0.01 to 1: 1.5 in an equivalent ratio. It is preferable to use it.

When an imidazole compound is used as the curing agent, it is preferably used in the range of 0.5 to 10 parts by weight with respect to 100 parts by weight of the total epoxy compound component as a solid content in the epoxy compound-containing composition.
When an amide compound is used as the curing agent, it is preferably used in a range of 0.1 to 20% by weight with respect to the total amount of all the epoxy compound components and the amide compound as a solid content in the epoxy compound-containing composition. .

When a mercaptan-based compound is used as the curing agent, it is preferably used in the range of 1 to 100 parts by weight with respect to 100 parts by weight of the total epoxy compound component as a solid content in the epoxy compound-containing composition.
When a cationic polymerization initiator is used as the curing agent, it is preferably used in the range of 0.01 to 15 parts by weight with respect to 100 parts by weight of the total epoxy compound component as a solid content in the epoxy compound-containing composition.
When organic phosphines are used as the curing agent, 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, organic acid dihydrazide, boron halide amine complex 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 resin such as tetrabromobisphenol A type epoxy resin, other polyfunctional phenol type epoxy resin, epoxy resin hydrogenated to the aromatic ring of the above aromatic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy 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, 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.

[paint]
The coating material of this invention contains the epoxy compound of this invention, or the epoxy compound containing composition of this invention.

In addition to the epoxy compound of the present invention or the epoxy compound-containing composition of the present invention, the paint of the present invention may be added with various additives that are added to the solvent and the usual paint, if necessary. It is obtained by mixing by the method.

As a solvent, 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.
Examples of the additive include various stabilizers such as ultraviolet absorbers, antioxidants, weathering stabilizers and heat resistance inhibitors, colorants such as dyes, organic pigments and inorganic pigments, and conductivity imparting such as carbon black and ferrite. Agents, pigment dispersants, leveling agents, antifoaming agents, thickeners, preservatives, fungicides, rust inhibitors and wetting agents.

[Cured product]
The cured product of the present invention 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 curing the epoxy compound-containing composition of the present invention to obtain a cured product is different depending on the blending component and blending amount in the epoxy compound-containing composition, and the shape of the blend, Usually, heating conditions of 50 to 200 ° C. for 5 seconds to 180 minutes can be mentioned. This heating is performed in a two-stage process of primary heating at 50 to 160 ° C. for 5 seconds to 30 minutes and secondary heating at 90 to 280 ° 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 a 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. .

[Use of epoxy compounds]
By using the epoxy compound of the present invention, a coating film excellent in light resistance, hardness and elution resistance can be formed. 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). In particular, the paint is often used outdoors, and the epoxy compound and the epoxy compound-containing composition of the present invention are preferably used.

Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to the following examples. 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, and solvents used in the following examples and comparative examples are as follows.

[Epoxy group-containing compound (A)]
A-1: Bisphenol A diglycidyl ether (manufactured by Mitsubishi Chemical Corporation, jER (registered trademark) 828US, epoxy equivalent: 186 g / equivalent, total chlorine amount: 0.16% by weight)

[Piperidine ring-containing compound (B)]
B-1: Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (Tinvin 770DF manufactured by BASF)

[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 (Tokyo Chemical Industry Co., Ltd.)

[Evaluation methods]
Evaluation methods in the following examples and comparative examples are as follows.

[Epoxy equivalent]
With respect to the epoxy compounds obtained in Examples 1 to 5 and Comparative Examples 1 and 2, the epoxy equivalent (g / equivalent) was measured based on JIS K 7236.

[Total chlorine and total bromine]
For the epoxy compounds obtained in Examples 1 to 5 and Comparative Examples 1 and 2, samples were collected 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 —H ₂ O ₂ aqueous solution. Chlorine content and bromine content (% by weight) in the absorbing solution were measured by ion chromatography.
Equipment: Quartz tube tubular furnace (Mitsubishi Chemical Corporation, AQF-100 type)
Ion chromatograph (Dionex, ICS-1000)

[Weight average molecular weight (Mw)]
The weight average molecular weight of the epoxy compounds obtained in Examples 1 to 5 and Comparative Examples 1 and 2 was measured by gel permeation chromatography (GPC). The apparatus and measurement conditions used for the GPC measurement are as follows.
Device: GPC
Model: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TSKGEL HM-H + H4000 + H4000 + H3000 + H2000 (manufactured by Tosoh Corporation)
Detector: UV-8020 (manufactured by Tosoh Corporation), 254 nm
Eluent: THF (0.5 mL / min, 40 ° C.)
Sample: 1% tetrahydrofuran solution (10μ injection)
Calibration curve: Standard polystyrene (manufactured by Tosoh Corporation)

[Light resistance]
20 parts by weight of cyclohexanone and 2-ethyl-4-methylimidazole (jER Cure (registered trademark) EMI24 manufactured by Mitsubishi Chemical Corporation) with respect to 100 parts by weight of the epoxy compound solutions obtained in Examples 1 to 5 and Comparative Examples 1 and 2 0.2 parts by weight was mixed and applied onto a steel sheet described in JIS K5600-1-4 using a 150 μm film applicator and heated at 150 ° C. for 90 minutes to prepare a coating film. 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 used as an evaluation index of light resistance.

・ Weather meter device: Atlas Weather Meter Ci4000 (Toyo Seiki Seisakusho Co., Ltd.)
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 Industries Co., Ltd.)

[Coating hardness]
Using the epoxy compound solutions or epoxy compounds obtained in Examples 1 to 5 and Comparative Examples 1 and 2, a coating film was produced on the steel sheet by the same method as in the light resistance evaluation. The obtained coating film was measured for pencil hardness using a pencil hardness tester (manufactured by Otsugi Equipment Co., Ltd.) based on JIS K5600-5-4 and used as an evaluation index of coating film hardness.

[Elution resistance]
Using the epoxy compound solutions or epoxy compounds obtained in Examples 1 to 5 and Comparative Examples 1 and 2, a coating film was produced on the steel sheet by the same method as in the light resistance evaluation.
100 g of tetrahydrofuran is put into a 200 ml sample bottle, and a test piece obtained by cutting the obtained coating plate into 4 cm × 4 cm is immersed in the sample bottle, left at room temperature for 12 hours or more, then taken out from tetrahydrofuran and heated at 100 ° C. for 2 hours. After time drying, the weight was measured and the gel fraction (%) was calculated by the following formula. The gel fraction (%) was used as an evaluation index for dissolution resistance.
Gel fraction (%) = [{(weight of specimen after drying at 100 ° C. for 2 hours) − (weight of specimen before treatment)} / (weight of specimen before treatment)] × 100
The higher the gel fraction (%) value, the better the elution resistance of the coating film.

[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 and 0.72 part by weight of tetramethylammonium chloride 50% aqueous solution (D-1) were placed in a 5 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 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, the coating film hardness and the elution resistance were evaluated by the above-mentioned methods, and the results were obtained. It is shown in Table 1.

(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 and 0.12 part by weight of a 50% aqueous solution of tetramethylammonium chloride (D-1) were 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 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, the coating film hardness and the elution resistance were evaluated by the above-mentioned methods, and the results were obtained. It is shown in Table 1.

(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 of 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, the coating film hardness and the elution resistance were evaluated by the above-mentioned methods, and the results were obtained. It is shown in Table 1.

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) (B-1) sebacate, 50% aqueous solution of tetramethylammonium chloride ( D-1) 0.105 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. This was dissolved in 320 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, the coating film hardness and the elution resistance were evaluated by the above-mentioned methods, and the results were obtained. It is shown in Table 1.

(Example 5)
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 and 0.4 part by weight of a tetramethylammonium chloride 50% aqueous solution (D-1) are 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, the coating film hardness and the elution resistance were evaluated by the above-mentioned methods, and the results were obtained. It is 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 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, the coating film hardness and the elution resistance were evaluated by the above-mentioned methods, and the results were obtained. It is 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 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), and further 28 parts by weight of bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (B-1) was added and dissolved. (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, the coating film hardness and the elution resistance were evaluated by the above-mentioned methods, and the results were obtained. It is shown in Table 1.

[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 / equivalent. The following coating films prepared using the epoxy compounds of Examples 1 to 5 showed high light resistance and high hardness and elution resistance.

On the other hand, the coating film produced using the epoxy compound of Comparative Example 1 having no structure of Formula (1) had insufficient light resistance.
Moreover, the coating film produced using the epoxy compound of Comparative Example 2 that does not have the structure of Formula (1) had insufficient elution resistance.

The epoxy compound of the present invention is considered to be capable of forming a coating film having good light resistance, hardness and elution resistance by having both groups of formula (1) and formula (2).

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application filed on September 6, 2016 (Japanese Patent Application No. 2016-173721), the contents of which are incorporated herein by reference.

The coating film using the epoxy compound of the present invention has excellent weather resistance, hardness and elution resistance. 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 (13)

1. 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 hydrocarbon group having 1 to 50 carbon atoms which may have a substituent.)
2. The epoxy compound according to claim 1, wherein the total amount of total chlorine and total bromine is 3% by weight or less.
3. The epoxy compound according to claim 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 claims 1 to 3, comprising two or more different groups as the divalent group represented by the formula (2).
5. X is a group having a structure represented by any of the following formulas (3) to (8), and each aromatic ring or cycloalkylene group in the following formulas (3) to (8) is an alkyl group. The epoxy compound according to any one of claims 1 to 4, which may be substituted with:
   

   

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

   

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

   

   

   

   (In Formula (7), R ⁹ and R ¹⁰ may be the same or different and each represents 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. A paint containing the epoxy compound according to any one of claims 1 to 5.
7. The epoxy compound according to any one of claims 1 to 5, comprising a step of reacting the piperidine ring-containing compound with an epoxy group-containing compound having a total amount of total chlorine and total bromine of 5% by weight or less. Production method.
8. The piperidine ring-containing compound, an epoxy group-containing compound in which the total of the total chlorine amount and the total bromine amount is 5% by weight or less, and a step of reacting the phenol compound, according to any one of claims 1 to 5. A method for producing an epoxy compound.
9. An epoxy compound-containing composition comprising the epoxy compound according to any one of claims 1 to 5 and a curing agent.
10. The epoxy compound-containing composition according to claim 9, comprising 0.1 to 1000 parts by weight of the curing agent with respect to 100 parts by weight of the epoxy compound.
11. 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 9 or 10, wherein the composition is at least one selected from the group consisting of:
12. A paint comprising the epoxy compound-containing composition according to any one of claims 9 to 11.
13. A cured product obtained by curing the epoxy compound-containing composition according to any one of claims 9 to 11.