JP2884149B2 - Epoxy resin curing agent and one-pack type epoxy resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an epoxy resin curing agent and a one-pack type epoxy resin composition using the same.
More specifically, the present invention relates to a one-pack type epoxy resin composition which is moisture-curable at room temperature, has a high curing rate, and has excellent storage stability.

[0002]

2. Description of the Related Art Conventionally, epoxy resins have been widely used in the fields of paints, adhesives, civil engineering, and construction because of their excellent characteristics. However, since most of them are two-packs, there is a drawback that workability is poor at the time of use. For one-pack, use a latent curing agent such as dicyandiamide as the curing agent, use a catalyst that generates an active group by ultraviolet rays to cure the epoxy resin, or use an acid anhydride-based curing agent However, these required heating or a device for irradiating ultraviolet rays.

As a one-part cold curing system for solving the above-mentioned disadvantages, a method is known in which ketimine is used as a curing agent, an amine is generated by external moisture, and an epoxy resin is cured. In addition, there were inconveniences such as a low curing speed, poor storage stability, and the fact that the cured product became hard, so that the blending amount had to be limited.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made to solve these problems, and a one-pack type epoxy resin composition excellent in fast-curing property, storage stability and workability, and a composition for the same. It is an object of the present invention to provide an epoxy resin curing agent.

As a result of intensive studies, the present inventors have completed an epoxy resin curing agent and a one-pack type epoxy resin composition which can solve the above problems. That is, the present invention has one kind of main chain selected from the group consisting of polyether, polyvinyl, polyester, polyamide, polycarbonate and novolak, and has at least a heterocyclic group represented by the following general formula (1) in a side chain. An epoxy resin curing agent comprising two heterocyclic-containing compounds, and a one-pack type epoxy resin composition comprising the epoxy resin curing agent and a polyepoxy compound.

[0006]

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In the formula, R ¹ and R ² may be the same or different, and represent a hydrogen atom, a linear or branched alkyl or alkenyl group having 1 to 6 carbon atoms, or Represents an aryl group having 6 to 8 carbon atoms, or represents a cycloalkyl ring having 5 to 7 carbon atoms together with the carbon atom to which R ¹ and R ² are bonded. R ³ is
Represents an alkylene group having 1 to 10 carbon atoms.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the epoxy resin curing agent of the present invention, R ¹ and R ² of the heterocyclic group represented by the above general formula (1) contained in the above heterocyclic-containing compound are as follows:
Specifically, for example, a hydrogen atom, a methyl group, an ethyl group,
Propyl group, isopropyl group, butyl group, isobutyl group, secondary butyl group, tertiary butyl group, pentyl group, isopentyl group, neopentyl group, tertiary pentyl group, hexyl group, isohexyl group, vinyl group, allyl group, propenyl group, Examples include a phenyl group and a benzyl group. Examples of the cycloalkyl ring in which R ¹ , R ^2, and the carbon atom to which R ¹ and R ² are bonded are a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and the like. Among these, from the viewpoint of curing speed, at least one of R ¹ and R ² are a hydrogen atom, or, preferably a linear or branched alkyl group having 1 to 3 carbon atoms, R ¹ and It is particularly preferred that at least one of R ² is a hydrogen atom, a methyl group or an ethyl group. As R ³ , specifically,
For example, methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, ethylethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group and the like are exemplified. Of these,
Ethylene, propylene, tetramethylene and pentamethylene groups are preferred from the viewpoint of curing speed.

In the epoxy resin curing agent of the present invention, the heterocyclic-containing compound has at least two heterocyclic groups represented by the general formula (1) in a side chain. When the number of the heterocyclic groups represented by the general formula (1) is less than 2, curing of the epoxy resin is insufficient, so that the range is limited to the above range. Preferably, it is 3 to 7.

The epoxy resin curing agent of the present invention preferably has no active hydrogen or has active hydrogen and an active hydrogen equivalent of 4000 or more. Here, the active hydrogen is a hydrogen atom bonded to an oxygen, nitrogen or sulfur atom having a high electronegativity, and the active hydrogen equivalent is a molecular weight per equivalent of active hydrogen. Examples of the group having active hydrogen include, for example, a hydroxyl group, an amino group, an imino group, a thiol group and the like.

Among the above-mentioned heterocyclic-containing compounds, polyether, polyvinyl, polyester, polyamide, polycarbonate and those having a novolak main chain have, for example, the structures represented by the following general formulas (2) to (9), respectively. Heterocycle-containing compounds are exemplified.

[0012]

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Hereinafter, these will be described in detail. The heterocyclic-containing compound having the structure represented by the general formula (2) has a polyether main chain. In the general formula (2), a is an integer of 2 to 200. From the viewpoint of the viscosity of the epoxy resin curing agent and the hardness of the cured epoxy resin, a is preferably 2 to 100. A ¹ is-
It represents an alkylene group substituted or unsubstituted with an XZ group, an arylene group, an arylalkylene group, a haloalkylene group, or a residue obtained by ring-opening polymerization of glycidyl ether. In the present specification, -XZ group is -X
A group represented by -Z (wherein, X represents a divalent organic group).
Z represents a heterocyclic group represented by the general formula (1). )
Represents

Examples of the above X include, for example, one or more groups selected from the group consisting of an ether group, a carbonate group, an ester group, an imino group, an amide group, a urethane group, a urea group and a sulfide group. illustrated etc. may also be a hydrocarbon group, and specific examples, -CH ₂ -, -
CH ₂ CH ₂ —, —CH ₂ OCH ₂ CH ₂ —, —CHO
_{C (= O) OCH 2 -} , - CH 2 NHCH 2 CH 2 -,
_{-CH 2 NHC (= O) NH} (CH 2) 6 NHC (=
O) O- and _{-CH 2 S (CH 2) 2} C (= O) O (C
H ₂ ) _2- and the like.

In formula (2), at least two of a ¹ A ¹ groups represent an alkylene group substituted with a -XZ group. From the viewpoint of the hardness of the cured product, 3-7 out of a number of A ¹ is, preferably represents an alkylene group substituted with -X-Z group.

Specific examples of A ^{1 in} the general formula (2) include methylene, ethylene, trimethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, heptamethylene. Group in which a hydrogen atom of an alkylene group exemplified by an octamethylene group or the like is substituted with an -XZ group; a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group , An alkylene group such as a hexamethylene group, a heptamethylene group and an octamethylene group; an arylene group such as a phenylene group, a tolylene group and a naphthylene group; an arylalkylene group such as a phenylethylene group and a tolylethylene group; a chloroethylene group, a dichloroethylene group; Halo such as bromoethylene group and chloromethylethylene group Cylene group: butyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, cresyl glycidyl ether, p-sec-butylphenyl glycidyl ether, glycidyl methacrylate, diglycidyl ether, (poly) ethylene glycol diglycidyl ether And (poly) propylene glycol diglycidyl ether, butanediol diglycidyl ether, diglycidyl aniline, trimethylolpropane triglycidyl ether, glyceryl triglycidyl ether and the like, and the residue obtained by ring-opening polymerization.

The heterocyclic-containing compound having the structure represented by the general formula (3) has a polyvinyl main chain. In the general formula (3), b is an integer of 2 to 200.
From the viewpoint of the viscosity of the epoxy resin curing agent and the hardness of the cured epoxy resin, b is preferably 2 to 100.
Q ¹ represents a hydrogen atom, an alkyl group, an aryl group, a haloalkyl group, a haloaryl group, an alkoxycarbonyl group, an acetoxy group, or a —XZ group. At least two of the b Q ^{1 in} the general formula (3) represent a —XZ group. From the viewpoint of the hardness of the cured product, 3-7 of b pieces of Q ¹ is, preferably represents an -X-Z group.

Specific examples of Q ^{1 in} the general formula (3) include a hydrogen atom, an alkyl group such as a methyl group and an ethyl group; an aryl group such as a phenyl group and a tolyl group; a chloromethyl group and a chloroethyl group. Haloalkyl group; chloromethylphenyl group, chloroethylphenyl group, 2,4,6-
Haloaryl groups such as trichlorophenyl group and 2,4,6-tribromophenyl group; alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group and butoxycarbonyl group; acetoxy group and -XZ group.

The heterocyclic-containing compound having the structure represented by the general formula (4) has a polyester main chain. In the general formula (4), c is an integer of 2 to 200. From the viewpoint of the viscosity of the epoxy resin curing agent and the hardness of the epoxy resin after curing, c is preferably 2 to 100. A ² and A ³ are the same or different and are each an alkylene group substituted or unsubstituted with an -XZ group,
Represents an arylene group, an aralkylene group, or a haloalkylene group substituted or unsubstituted with an -XZ group. At least two of c A ² and c A ^{3 in} the general formula (4) are selected from an alkylene group substituted with an -XZ group and an arylene group substituted with an -XZ group. Represents at least one selected from the group consisting of: From the viewpoint of the hardness of the cured product, 3 to 7 represent at least one selected from the group consisting of an alkylene group substituted with an -XZ group and an arylene group substituted with a -XZ group. Is preferred.

In the general formula (4), the above A ² and the above A
Specific examples of ³ include a hydrogen atom of an alkylene group such as a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, and an octamethylene group. A group in which a hydrogen atom of an aryl group such as a phenylene group or a tolylene group is substituted with an -XZ group; a methylene group, an ethylene group, a trimethylene group,
Propylene group, tetramethylene group, ethylethylene group,
Alkylene groups such as pentamethylene, hexamethylene, heptamethylene and octamethylene; phenyl,
Arylene group such as tolylene group; aralkylene group such as benzylidene group, ethylenephenylene group; chloroethylene group, dichloroethylene group, bromoethylene group, chloromethylethylene group, 1,2-dichlorobutylene group, 1-chlorobutylene group, etc. And a haloalkylene group.

The heterocyclic-containing compound having the structure represented by the general formula (5) has a polyester main chain. In the general formula (5), d is an integer of 2 to 200. From the viewpoint of the viscosity of the epoxy resin curing agent and the hardness of the epoxy resin after curing, d is preferably 2 to 100. A ⁴ is an alkylene group substituted or unsubstituted with an -XZ group, an arylene group substituted or unsubstituted with an -XZ group, an aralkylene group,
Or, it represents a haloalkylene group. At least two of d A ^{4 in} the general formula (5) are at least selected from the group consisting of an alkylene group substituted with an -XZ group and an arylene group substituted with an -XZ group. Represents one type. From the viewpoint of the hardness of the cured product, three to seven represent at least one selected from the group consisting of an alkylene group substituted with an -XZ group and an arylene group substituted with a -XZ group. preferable.

[0022] Specific examples of the A ⁴ in the general formula (5), such as those exemplified as specific examples of the A ² and the A ³ and the like.

The heterocyclic-containing compound having the structure represented by the general formula (6) has a polyamide main chain. In the general formula (6), e is an integer of 2 to 200.
From the viewpoint of the viscosity of the epoxy resin curing agent and the hardness of the epoxy resin after curing, e is preferably 2 to 100.
A ⁵ and A ⁶ are the same or different and are each an alkylene group substituted or unsubstituted with an -XZ group, -X
Represents an arylene group, an aralkylene group, or a haloalkylene group substituted or unsubstituted with a -Z group. At least two of e A ⁵ and e A ^{6 in} the general formula (6) are a group consisting of an alkylene group substituted with an -XZ group and an arylene group substituted with a -XZ group. Represents at least one selected from the group consisting of: From the viewpoint of the hardness of the cured product, 3 to 7 represent at least one selected from the group consisting of an alkylene group substituted with an -XZ group and an arylene group substituted with a -XZ group. Is preferred.

Specific examples of A ⁵ and A ^{6 in} the general formula (6) include those exemplified as the specific examples of A ² and A ³ above.

The heterocyclic-containing compound having the structure represented by the general formula (7) has a polyamide main chain. In the general formula (7), f is an integer of 2 to 200.
F is preferably from 2 to 100 in view of the viscosity of the epoxy resin curing agent and the hardness of the epoxy resin after curing.
A ⁷ is, -X-Z substituted or unsubstituted alkylene group with a group, -X-Z substituted or unsubstituted arylene group with a group, aralkylene group, or a haloalkylene group. At least two of the f A ^{7 in} the general formula (7) are at least two selected from the group consisting of an alkylene group substituted with an -XZ group and an arylene group substituted with an -XZ group. Represents one type. From the viewpoint of the hardness of the cured product, three to seven represent at least one selected from the group consisting of an alkylene group substituted with an -XZ group and an arylene group substituted with a -XZ group. preferable.

Specific examples of A ^{7 in} the general formula (7) include:
Like those exemplified as the specific examples of the A ⁴ can be cited.

The heterocyclic-containing compound having the structure represented by the general formula (8) has a polycarbonate main chain. In the general formula (8), g is an integer of 2 to 200. From the viewpoint of the viscosity of the epoxy resin curing agent and the hardness of the epoxy resin after curing, g is preferably 2 to 100. A ⁸ represents an alkylene group substituted or unsubstituted with an -XZ group, an arylene group substituted or unsubstituted with an -XZ group, an aralkylene group, or a haloalkylene group. At least two of the g A ^{8 in} the general formula (8) are at least selected from the group consisting of an alkylene group substituted with an -XZ group and an arylene group substituted with an -XZ group. Represents one type. From the viewpoint of the hardness of the cured product, three to seven represent at least one selected from the group consisting of an alkylene group substituted with an -XZ group and an arylene group substituted with a -XZ group. preferable.

Specific examples of A ^{8 in} the general formula (8) include:
Like those exemplified as the specific examples of the A ⁴ can be cited.

The heterocyclic-containing compound having the structure represented by the general formula (9) has a novolak main chain. In the general formula (9), h is an integer of 2 to 200.
From the viewpoint of the viscosity of the epoxy resin curing agent and the hardness of the epoxy resin after curing, h is preferably 2 to 100.
Ar represents an aryl group. Q ² represents a hydrogen atom, an epoxy group, or a —XZ group. At least two of h Q ^{2 in} the general formula (9) represent a —XZ group. From the viewpoint of the hardness of the cured product, three to seven represent at least one selected from the group consisting of an alkylene group substituted with an -XZ group and an arylene group substituted with a -XZ group. preferable.

Specific examples of the Ar group in the general formula (9) include a substituted phenylene group which is a residue of a phenol novolak resin, and a substituted tolylene group which is a residue of a cresol novolak resin.

In the heterocycle-containing compounds having the structures represented by the general formulas (2) to (9), the ratio of the group having the -XZ group to the other group, the type of the other group, the X group By changing the values of a to h, the viscosity of the epoxy resin curing agent of the present invention, the compatibility with the polyepoxy compound, the hardness of the epoxy resin cured by the epoxy resin curing agent of the present invention, the flexibility, Physical properties such as weather resistance and chemical resistance can be controlled.

The number average molecular weight of the heterocyclic-containing compound having a structure represented by any of formulas (2) to (9) is preferably from 400 to 20,000, and more preferably from 600 to 20,000.
000 is more preferable. General formulas (2) to (9)
In a heterocyclic-containing compound having a structure represented by any of the above, the viscosity (25
C) is preferably 200 to 200,000 cP, more preferably 400 to 50,000 cP. In the heterocyclic-containing compound having a structure represented by any of the general formulas (2) to (9), the molecular weight per equivalent of the heterocyclic group represented by the general formula (1) is preferably 150 to 2,000, and more preferably 150 to 2,000. ~
More preferably, it is 500.

Examples of the heterocyclic-containing compound having a structure represented by any of the general formulas (2) to (9) include, for example, the following compounds belonging to the heterocyclic-containing compound having a structure represented by the general formula (2). Examples include compounds represented by the general formulas (10) to (12).

[0034]

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Hereinafter, these compounds will be described in detail. The compound represented by the general formula (10) has a polyether main chain. In the formula (10), a is the same as above. Q ³ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a haloalkyl group, a haloaryl group, or -X-
Represents a Z group. The group J represents any of the groups represented by the following general formulas (13) and (14).

[0036]

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In the formula (13), R ⁵ is a hydrogen atom, an alkyl group such as a methyl group, an ethyl group or a butyl group; a formyl group,
An acyl group such as an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, a pivaloyl group, a hexanoyl group, an octanoyl group, a lauroyl group, a benzoyl group, a toluoyl group, a cinnamoyl group, or the following general formula (15) Represents the group shown.

[0038]

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In the formula, R ⁷ represents an alkyl group, an aryl group or an aralkyl group, specifically, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group Tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, myristyl group, palmityl group,
Alkyl groups such as stearyl group; aryl groups such as phenyl group and tolyl group; aralkyl groups such as benzyl group and phenethyl group.

In the formula (14), R ⁶ represents a hydrogen atom, an alkyl group, an acyl group or a group represented by the above formula (15), and specific examples include those exemplified for the above R ⁵ . .

[0041] Specific examples of the Q ³ are, for example, a hydrogen atom, a methyl group, an ethyl group, butyl group, an alkyl group such as 2-ethylhexyl group, aryl groups such as phenyl and tolyl groups; chloromethyl group, chloroethyl A chloromethylphenyl group, a chloroethylphenyl group, a 2,4,6-trichlorophenyl group, a 2,4,6
A haloaryl group such as a tribromophenyl group; -XZ
And the like.

The compound represented by the general formula (11) has a polyether main chain. In the general formula (11), a is the same as described above. Q ⁴ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a haloalkyl group, a haloaryl group or a —XZ group.

[0043] Specific examples of the Q ⁴ are, like those exemplified as specific examples of the Q ³ and the like.

The compound represented by the general formula (12) has a polyether main chain. In the general formula (12), a is the same as described above. m is equal to the valence of R ⁴ and is an integer of 1 to 8. R ⁴ is a 1 to 8 valent group obtained by removing a hydrogen atom of a hydroxyl group from a 1 to 8 valent alcohol or phenol, or a 1 to 8 valent group obtained by removing a hydrogen atom of an amino group from 1 to 6 (poly) amines. Represents a group. The J group is the same as described above. Q ⁵ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a haloalkyl group, a haloaryl group, or -X-
Represents a Z group. At least two of a × m Q ^{5 in} the formula (12) represent a —XZ group. From the viewpoint of the hardness of the cured product, it is preferable that 3 to 7 represent -XZ groups.

[0045] Specific examples of the Q ⁵ is like those exemplified as specific examples of the Q ³ and the like.

[0046] In the above R ^4, 1 to 8-valent alcohol minus the hydroxyl hydrogen atoms corresponds to R ^4, specific examples of the phenols, for example, methanol, ethanol, 1-propanol, 2-propanol , 1-butanol, 2-butanol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, 2-ethyl-1-hexanol, 1-nonyl alcohol, 2-nonyl alcohol, 1-decanol, 2-decanol, 1- Undecanol, 2-undecanol,
Phenol, cresol, xylenol, naphthanol, benzyl alcohol, 2-phenylethanol, ethylene glycol, propylene glycol, 1,3-propanediol, catechol, resorcinol, hydroquinone, biphenyl-4,4-diol, bisphenol A, bisphenol B, bisphenol AD, bisphenol F, glycerin, pyrogallol, 1,2,4-
Benzenetriol, phloroglucinol, pentaerythritol, ribose, arabinose, xylose, lyxose, ribulose, xylulose, fructose,
Glucose, galactose, maltose, lactose,
Sucrose and the like.

[0047] In the above R ^4, Examples 1 to 6-valent (poly) amines minus the hydrogen atom of the amino group corresponds to R ^4, for example, methylamine, ethylamine, butylamine, dimethylamine Aliphatic amines such as aniline, diethylamine and dibutylamine; aromatic amines such as aniline, methylaniline, toluidine, dibenzylamine, diaminodiphenylmethane, metaphenylenediamine, diaminodimethylphenylmethane, diaminodiethylphenylmethane, xylylenediamine; (Poly) alkylene polyamines such as ethyleneamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine.

The epoxy resin curing agent of the present invention comprises the above-mentioned heterocyclic compound containing a heterocyclic group represented by the above general formula (1) in a side chain, as described in detail above. In general, a compound having at least one secondary amine bonded to a hydroxyalkyl group in a molecule and a compound having an aldehyde group in the molecule or a compound having a ketone group in the molecule are subjected to a dehydration condensation reaction. Can be obtained by

Examples of the compound having at least one secondary amine bonded to the hydroxyalkyl group in the molecule include, for example, polyepichlorohydrin obtained by homopolymerizing epichlorohydrin or a compound obtained by polymerizing epichlorohydrin in the presence of ethylene glycol; epichlorohydrin; A reaction between a copolymer of ethylene oxide or a copolymer of epichlorohydrin and propylene oxide, or a mixture thereof, with an alkanolamine having a primary hydroxyl group in an equimolar, 80 ° C, solvent such as dimethylformamide. Or a compound obtained by reacting these raw materials with an excessive amount of the alkanolamine at 80 ° C.

Examples of the compound having an aldehyde group in the molecule include formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, benzaldehyde, acrolein, glyoxal and the like. Examples of the compound having a ketone group in the molecule include acetone, methyl ethyl ketone, methyl isobutyl ketone, 3-pentanone, 2-hexanone, 3,3-dimethyl-2-butanone, cyclopentanone, cyclohexanone, acetophenone, benzophenone and the like. Is exemplified.

In the above heterocyclic compound containing a heterocyclic group represented by the above general formula (1) in the side chain, the heterocyclic group represented by the above general formula (1) can be easily converted in the presence of moisture. Hydrolysis produces a compound having a secondary amine bonded to a hydroxyalkyl group and the corresponding aldehyde or ketone, which acts as a curing agent for the epoxy resin. Therefore, the heterocyclic-containing compound containing the heterocyclic group represented by the general formula (1) in the side chain is stable even in a system mixed with an epoxy resin, unless water is mixed in from the outside,
It becomes very useful as a curing agent for one-part type epoxy resin compositions. The heterocyclic-containing compound having a heterocyclic group represented by the general formula (1) in a side chain thereof is hydrolyzed by changing the type of the compound having an aldehyde group or the compound having a ketone group in the molecule. Speed can be controlled.

The one-pack type epoxy resin composition of the present invention has one kind of main chain selected from the group consisting of polyether, polyvinyl, polyester, polyamide, polycarbonate and novolak as described in detail above. An epoxy resin curing agent comprising a heterocyclic-containing compound having at least two heterocyclic groups represented by the above general formula (1) in a chain; and a polyepoxy compound. The mixing amount of the epoxy resin curing agent with respect to the polyepoxy compound is such that the ratio of the heterocyclic group equivalent of the heterocyclic group-containing compound represented by the general formula (1) to the epoxy equivalent of the polyepoxy compound is 0. It is preferable to mix them so as to be 5 to 1.5. By blending within this range, the number of active hydrogens in the secondary amine generated by hydrolysis of the heterocyclic group represented by the general formula (1) per one epoxy group of the polyepoxy compound is reduced. The number may be 0.7 to 1.3, preferably 0.9 to 1.1. When the ratio is less than 0.7 or exceeds 1.3, the curability is reduced, and the water resistance and mechanical strength of the cured product are reduced.

Examples of the polyepoxy compound to be added to the one-pack type epoxy resin composition of the present invention include bisphenol A, halogenated bisphenol A, bisphenol B, bisphenol AD, bisphenol F, resorcinol, hydroquinone, pyrocatechol, ,
Polyepoxy compounds obtained by adding epichlorohydrin to polyhydric phenols such as 4'-dihydroxybiphenyl and 1,5-hydroxynaphthalene and hydrogenated products thereof; novolak type, glycidyl ester type, glycidylamine type and heterocyclic type Polyepoxy compounds; glycidyl ethers of polyoxyethylene and polyoxypropylene; urethane-modified polyepoxy compounds having urethane bonds in the structure; acrylonitrile in the resin matrix
Butadiene rubber (NBR), terminal carboxybutadiene nitrile rubber (CTBN), polyepoxy compound dispersed with silicone rubber, etc., linear aliphatic epoxide type compound such as propylene oxide, butene oxide, 3,4
Alicyclic epoxide type compounds such as -epoxy-6-methylcyclohexylmethyl carboxylate, etc., and any other epoxy resin having a glycidyl group capable of reacting with active hydrogen of an amine. In the present invention, among these, glycidyl ester type, glycidyl ether type, glycidylamine type, linear aliphatic epoxide type and alicyclic epoxide type are preferable.
Two or more of these polyepoxy compounds may be used in combination.

In order to improve the storage stability of the one-pack type epoxy resin composition of the present invention, the polyepoxy compound together with the epoxy resin curing agent has no active hydrogen, or When having active hydrogen, those having an active hydrogen equivalent of 4000 or more are preferable. The active hydrogen equivalent in the one-pack type epoxy resin composition of the present invention is usually at least 2,000, preferably at least 20,000, more preferably at least 40,000. When the active hydrogen equivalent is less than 2,000, the storage stability of the one-pack type epoxy resin composition is insufficient.

In the case of having active hydrogen, the group having no active hydrogen is deactivated by deactivating the group having active hydrogen to a group which does not react with the epoxy resin, or an active hydrogen equivalent is required. Within the range. The inactivation of the active hydrogen group can be performed by monoisocyanate compounds (ethyl isocyanate, n-butyl isocyanate, phenyl isocyanate, etc.), acid anhydrides (acetic anhydride, succinic anhydride), acid halides (benzoyl chloride, etc.) or alkyl halides (Methyl chloride, methyl bromide, ethyl chloride, etc.).

The one-pack type epoxy resin composition of the present invention includes:
Further, a dehydrating agent, a filler, a plasticizer, a coloring inhibitor, a leveling agent, an antioxidant, a pigment, a dispersant, a reactive diluent, a solvent and the like may be blended. The dehydrating agent is for preventing water mixed in the one-pack type epoxy resin composition of the present invention for any reason from reacting with the heterocyclic group represented by the general formula (1). This is for improving the storage stability of the one-pack type epoxy resin composition. Examples of the dehydrating agent include a silane coupling agent, a monoisocyanate compound, and a carbodiimide compound.

The filler is composed of a finely pulverized solid. Its main purposes are to improve strength, elastic modulus, etc., to improve durability such as weather resistance, conductivity, heat conductivity, and the like. The objective is to improve the physical properties such as conductivity, improve the moldability such as fluidity and shrinkage, and to improve the economic aspects such as increasing the amount and saving resources. As the filler, for example, calcium carbonate, carbon black,
Clay, talc, titanium oxide, quicklime, kaolin, zeolite, diatomaceous earth, vinyl chloride paste resin, vinylidene chloride resin balloon and the like can be used, and they can be used alone or in combination.

The one-pack type epoxy resin composition of the present invention includes:
In order to increase the curing speed, a catalyst may be added as needed. Examples of the catalyst for the hydrolysis reaction of the heterocyclic group represented by the general formula (1) include formic acid, acetic acid, propionic acid, dibutyltin dilaurate and the like. Examples of the catalyst for the reaction between the secondary amine generated by the hydrolysis of the heterocyclic group represented by the general formula (1) and the epoxy group include tertiary amines and triphenylphosphine. Of these, tertiary amines are preferred, and specifically, for example, N, N-dimethylpropylamine,
Aliphatic tertiary amines such as N, N, N ', N'-tetramethylhexamethylenediamine;N-methylpyrrolidine;
Alicyclic tertiary amines such as N, N'-dimethylpiperazine; aromatic tertiary amines such as benzyldimethylamine and dimethylaminomethylphenol;

The use of the one-pack type epoxy resin composition of the present invention is not limited at all. Examples thereof include an adhesive, a sealing agent, an anticorrosive coating agent, a primer, a waterproofing agent for concrete, and a coating agent for a coated floor. Examples of such applications include concrete repair injectants, printed circuit board laminates, semiconductor sealants, and insulating agents.

When the one-pack type epoxy resin composition of the present invention is used in the above applications, the curing reaction can be promoted by adding an appropriate amount of water before the application. The amount of water to be added is such that the equivalent ratio of the heterocyclic group to the water molecule in the composition is 0.1.
It is preferable to mix them so as to be 5 to 2.0.

[0061]

The present invention will be further described below with reference to examples, but the present invention is not limited to these examples. In addition,
In the following, “part” indicates “part by weight”.

Example 1 83.4 g of ethylene glycol and 3.88 g of boron trifluoride-diethyl ether complex were placed in a reaction vessel, and epichlorohydrin 5 was maintained at a reaction temperature of 15 to 25 ° C.
After dropwise adding 00 g at a constant rate over 10 to 14 hours, the temperature was kept at that temperature for 2 hours. 100 in the reaction vessel
g of calcium oxide was added and neutralized at 80 ° C. for 2 hours. The salt produced by the neutralization and the excess calcium oxide were removed by filtration to obtain an intermediate product A. Intermediate product A has a structure in which epichlorohydrin is polymerized at both ends of ethylene glycol, has a number average molecular weight of 413 and a viscosity of 1530 cP.
(25 ° C.) as a pale yellow transparent viscous liquid. 580 g of the intermediate product A, 450 g of dimethylformamide, and 360 g of 2-hydroxyethylamine were added to the reaction vessel and reacted at 80 ° C. for 2 hours. After distilling off dimethylformamide and excess 2-hydroxyethylamine under reduced pressure, 640 g potassium carbonate and 800 g
And reacted at 60 ° C. for 48 hours. Further, 205 g of acetic anhydride was added and reacted at 25 ° C. for 5 hours. After completion of the reaction, salts were removed by filtration, and then excess acetone was distilled off under reduced pressure to obtain compound A containing heterocycle.
The heterocyclic-containing compound A (hereinafter, referred to as “compound A”) was a brown viscous liquid having a heterocyclic group equivalent of 170, an active hydrogen equivalent of 45000, a number average molecular weight of 690, and a viscosity of 5,200 cP (25 ° C.).

Example 2 500 g of epichlorohydrin and 500 g of toluene were placed in a reaction vessel, and while maintaining the temperature at 15 to 25 ° C., 7.59 g of boron trifluoride diethyl etherate was dropped into the reaction vessel. The oligomerization reaction was performed for 3 hours. The reaction was stopped with a 10% aqueous sodium hydroxide solution and washed with water until neutral. Under reduced pressure, unreacted epichlorohydrin with toluene was distilled off. The product was subjected to GPC analysis (Toyo Soda HLC-802) in chloroform solvent.
(Type, solvent) to obtain fraction A, which is the fraction corresponding to the peak with the longest flow time, and fraction B, which is a mixture of the other fractions. Fraction A is a viscous, colorless and transparent liquid mainly composed of a cyclic tetramer of epichlorohydrin, having a number average molecular weight of 366 and a viscosity of 13,000 c.
P (25 ° C.). Fraction B was considered to consist of a linear oligomer of epichlorohydrin, and was a viscous, colorless, transparent liquid having a number average molecular weight of 602 and a viscosity of 4,800 cP (25 ° C.). 463 g of fraction B, 480 g of dimethylformamide, and 306 g of 2-hydroxyethylamine were placed in a reaction vessel and reacted at 80 ° C. for 2 hours. After distilling off dimethylformamide and excess 2-hydroxyethylamine under reduced pressure, 690 g was added to the reaction vessel.
Of potassium carbonate and 900 g of acetone at 60 ° C.
The reaction was performed for 8 hours. Further, 220 g of acetic anhydride was added and reacted at 25 ° C. for 5 hours. After completion of the reaction, salts were removed by filtration, and then excess acetone was distilled off under reduced pressure to obtain a heterocyclic-containing compound B. Heterocycle-containing compound B
(Hereinafter referred to as “Compound B”) has a heterocyclic group equivalent of 157,
It was a brown viscous liquid having an active hydrogen equivalent of 48000, a number average molecular weight of 1020, and a viscosity of 4600 cP (25 ° C.).

Example 3 458 g of the fraction A described in Example 2, 480 g of dimethylformamide and 400 g of 2-hydroxyethylamine were placed in a reaction vessel and reacted at 80 ° C. for 2 hours.
After distilling off dimethylformamide and excess 2-hydroxyethylamine under reduced pressure, 690 g of potassium carbonate and 900 g of acetone were added to the reaction vessel and reacted at 60 ° C. for 48 hours. Further, 200 g of acetic anhydride was added, and 25
The reaction was performed at 5 ° C. for 5 hours. After completion of the reaction, salts were removed by filtration, and then excess acetone was distilled off under reduced pressure to obtain compound C containing heterocycle. Heterocycle-containing compound C (hereinafter referred to as “compound C”) has a heterocyclic group equivalent of 158, an active hydrogen equivalent of 51,000, a number average molecular weight of 630, and a viscosity of 8900 cP.
(25 ° C.) brown viscous liquid.

Example 4 580 g of the intermediate product A described in Example 1, 450 g of dimethylformamide, and one end of 1,4-dichlorobutane were aminated with aqueous ammonia, and then neutralized with an aqueous sodium hydroxide solution. 550 g of 4-hydroxybutylamine obtained by hydrolysis under alkaline conditions
Was added to a reaction vessel and reacted at 80 ° C. for 2 hours. After distilling off dimethylformamide and excess 4-hydroxyethylamine under reduced pressure, 640 g of potassium carbonate and 800 g of acetone were added to the reaction vessel and reacted at 60 ° C. for 48 hours. Further, 220 g of acetic anhydride was added and reacted at 25 ° C. for 5 hours. After completion of the reaction, salts were removed by filtration, and then excess acetone was distilled off under reduced pressure to obtain heterocycle-containing compound D. Heterocycle-containing compound D (hereinafter referred to as “compound D”) has a heterocyclic group equivalent of 186 and an active hydrogen equivalent of 4
9000, number average molecular weight 633, viscosity 5000 cP (2
(5 ° C.).

Example 5 Polyethylene glycol (PEG200, average molecular weight 2
00, manufactured by Sanyo Chemical Co., Ltd.) 200 g, epichlorohydrin 5
Then, while maintaining the temperature at 15 to 25 ° C., 7.59 g of boron trifluoride diethyl ether complex was dropped into the reaction vessel, and the reaction was carried out at 15 to 25 ° C. for 5 hours. After that, methylene dichloride was distilled off under reduced pressure, and 1100 g of 2
A 0% aqueous potassium hydroxide solution was added, and a hydrolysis reaction was performed at 100 ° C. for 5 hours. After completion of the reaction, the precipitate was separated by filtration to obtain an intermediate product B. The intermediate product B has a structure in which the chlorine group of a compound in which epichlorohydrin is added to both ends of polyethylene glycol at an average of 2.2 mol each is substituted with a hydroxyl group, the number average molecular weight is 660, and the viscosity is 3400 cp (25
C) as a pale yellow transparent viscous liquid. 525 g of diethanolamine, 400 g of acetone and potassium carbonate 32
0 g was added to the reaction vessel and reacted at 60 ° C. for 48 hours.
After the completion of the reaction, potassium carbonate was removed by filtration, and then excess acetone was distilled off under reduced pressure to obtain an intermediate product C.
330 g of intermediate B, 300 g of intermediate C, 225 g of dimethyl carbonate and 5 g of sodium methylate
After reacting at 140 ° C. for 10 hours, generated methanol and unreacted substances were distilled off under reduced pressure to obtain heterocyclic-containing compound E. Heterocycle-containing compound E (hereinafter referred to as “compound E”) has a heterocyclic group equivalent of 171 and an active hydrogen equivalent of 5100.
0, number average molecular weight 860, viscosity 7600 cP (25 ° C.)
Was a brown viscous liquid.

Example 6 615 g of styrene octamer, 320 g of methyl monochloromethyl ether, 500 g of toluene, 5 g of aluminum chloride
g was placed in a reaction vessel and reacted at 100 ° C. for 5 hours. After completion of the reaction, the precipitate was separated by filtration and toluene was distilled off. 50
Put 0 g of 2-hydroxyethylamine into the reaction vessel,
The reaction was performed at 80 ° C. for 2 hours. After distilling off excess 2-hydroxyethylamine under reduced pressure, 800 g of potassium carbonate and 900 g of acetone were added to the reaction vessel, and 48
Allowed to react for hours. Further, 200 g of acetic anhydride was added and 2 g
The reaction was performed at 5 ° C. for 5 hours. After completion of the reaction, salts were removed by filtration, and then excess acetone and acetic anhydride were distilled off under reduced pressure to obtain a heterocyclic-containing compound F. Heterocycle-containing compound F
(Hereinafter referred to as “Compound F”) has a heterocyclic group equivalent of 290,
It was a brown viscous liquid having an active hydrogen equivalent of 48,000, a number average molecular weight of 17000, and a viscosity of 3200 cP (25 ° C.).

Example 7 180 g of glycerin, 5% formaldehyde aqueous solution 60
0 g and 500 g of 40% sulfuric acid were put into a reaction vessel, and an acetalization reaction was performed at 70 ° C. for 5 hours under dehydration conditions. This was neutralized with an alkali, water was distilled off, and the salt was filtered off. 200 g of carbon tetrachloride and 5 g of triphenylphosphine were added to the filtrate, and the mixture was refluxed for 5 hours. 100 g of 5% sulfuric acid was added thereto, and a hydrolysis reaction was performed at 80 ° C. for 2 hours. This was neutralized with an alkali, water was distilled off, and the salt was filtered off. 300 g of terephthalic acid and 0.1 g of p-toluenesulfonic acid were added to the filtrate.
1 g was added, and an esterification reaction was performed under dehydration conditions. 200 g of 2-aminoethanol to this polyester
After adding and reacting at 100 ° C for 5 hours, excess 2-aminoethanol was distilled off. 300 g of potassium carbonate and 200 g of acetone were added thereto and reacted at 60 ° C. for 48 hours. After completion of the reaction, salts were removed by filtration, and then excess acetone was distilled off under reduced pressure to obtain a heterocyclic compound G. Heterocycle-containing compound G (hereinafter, referred to as “compound G”)
Has a heterocyclic group equivalent of 380, an active hydrogen equivalent of 120,000,
It was a brown viscous liquid having a number average molecular weight of 1700 and a viscosity of 4000 cP (25 ° C.).

Example 8 100 g of 4-pentene-5-olide, 500 carbon tetrachloride
g and 200 g of bromine were placed in a reaction vessel and reacted at room temperature for 10 hours, after which carbon tetrachloride and unreacted bromine were distilled off under reduced pressure. This was transferred to another reaction vessel, replaced with nitrogen, 2 g of a 10% benzene solution of diethylammonium chloride was added, and a polymerization reaction was performed at 50 ° C. for 20 hours. In addition, 20
0 g of chloroform was added for dilution, and the mixture was poured into diethyl ether, whereby a fibrous polymer was precipitated. This is filtered,
It was dried under reduced pressure. 20 amino-2-ethanol in a reaction vessel
After adding 0 g and reacting at 100 ° C. for 5 hours, excess 2-aminoethanol was distilled off. 300 g of potassium carbonate and 200 g of acetone were added thereto and reacted at 60 ° C. for 48 hours. After completion of the reaction, salts were removed by filtration, and then excess acetone was distilled off under reduced pressure to obtain a heterocycle-containing compound H. Heterocycle-containing compound H (hereinafter referred to as "compound H")
Has a heterocyclic group equivalent of 270, an active hydrogen equivalent of 150,000,
It was a brown viscous liquid having a number average molecular weight of 1100 and a viscosity of 1200 cP (25 ° C.).

Example 9 160 g of terephthalic acid, 81 g of methyl monochloromethyl ether, 200 g of toluene and 2 g of aluminum chloride were placed in a reaction vessel and reacted at 100 ° C. for 5 hours. After completion of the reaction, the precipitate was separated by filtration and toluene was distilled off. This is 2
After adding 200 g of -aminoethanol and reacting at 100 ° C for 5 hours, excess 2-aminoethanol was distilled off.
68 g of ethylenediamine was added to the reaction vessel, and a polyamide reaction was performed under dehydration conditions. 300 g of potassium carbonate and 200 g of acetone were added thereto and reacted at 60 ° C. for 48 hours. After completion of the reaction, salts were removed by filtration, and then excess acetone was distilled off under reduced pressure to obtain a heterocyclic compound I.
I got Heterocycle-containing compound I (hereinafter referred to as “compound I”) has a heterocyclic group equivalent of 210 and an active hydrogen equivalent of 8000.
0, number average molecular weight 1700, viscosity 3700 cP (25
C) brown viscous liquid.

Example 10 97 g of 4-pentene-5-lactam, 500 carbon tetrachloride
g and 200 g of bromine were placed in a reaction vessel and reacted at room temperature for 10 hours, and unreacted bromine was distilled off under reduced pressure. To this, 10 g of ε-aminocaproic acid was added, and 250 ° C.
And kept at this temperature for 5 hours. 2- in the reaction vessel
200 g of aminoethanol, dimethylformamide 2
After adding 100 g and reacting at 100 ° C. for 5 hours, excess 2 g was added.
-Aminoethanol and dimethylformamide were distilled off. 300 g of potassium carbonate and 200 g of acetone were added thereto and reacted at 60 ° C. for 48 hours. After completion of the reaction, salts were removed by filtration, and then excess acetone was distilled off under reduced pressure to obtain a heterocyclic-containing compound J. Heterocycle-containing compound J (hereinafter referred to as “compound J”) has a heterocyclic group equivalent of 22.
0, an active hydrogen equivalent of 93,000, a number average molecular weight of 980, and a viscosity of 4,200 cP (25 ° C.).

Example 11 180 g of glycerin, 5% aqueous formaldehyde solution 60
0 g and 500 g of 40% sulfuric acid were put into a reaction vessel, and an acetalization reaction was performed at 70 ° C. for 5 hours under dehydration conditions. This was neutralized with an alkali, water was distilled off, and the salt was filtered off. 200 g of carbon tetrachloride and 5 g of triphenylphosphine were added to the filtrate, and the mixture was refluxed for 5 hours. 100 g of 5% sulfuric acid was added thereto, and a hydrolysis reaction was performed at 80 ° C. for 2 hours. This was neutralized with an alkali, water was distilled off, and the salt was filtered off. 180 g of dimethyl carbonate was added to the filtrate and reacted at 140 ° C. for 5 hours. After distilling off excess dimethyl carbonate and methanol under reduced pressure, 200 g of 2-aminoethanol was added to the reaction vessel, and the mixture was reacted at 100 ° C. for 5 hours. Then, excess 2-aminoethanol was distilled off. 300 g of potassium carbonate and 200 g of acetone were added thereto, and
Allowed to react for hours. After the reaction, remove salts by filtration,
Then, excess acetone was distilled off under reduced pressure to obtain a heterocyclic compound-containing compound K. Heterocycle-containing compound K (hereinafter “Compound K”)
Is equivalent to a heterocyclic group equivalent of 210 and an active hydrogen equivalent of 120.
000, number average molecular weight 1600, viscosity 1400 cP (2
(5 ° C.).

Example 12 Phenol novolak resin (Shaunol BRG-55)
5, 200 g of epichlorohydrin, 200 g of toluene and 200 g of toluene were placed in a reaction vessel, and the atmosphere was replaced with nitrogen.
4 g was slowly charged so that the liquid temperature did not exceed 40 ° C. After aging at 40 ° C. for 2 hours, 200 g of water was added for liquid separation, and the toluene layer was taken out and placed in another reaction vessel.
After 200 g of 2-aminoethanol was added thereto and reacted at 100 ° C. for 5 hours, excess 2-aminoethanol was distilled off. 300 g of potassium carbonate and 200 g of acetone were added thereto and reacted at 60 ° C. for 48 hours. Further, 200 g of acetic anhydride was added and reacted at 25 ° C. for 5 hours. After completion of the reaction, salts were removed by filtration, and then excess acetone was distilled off under reduced pressure to obtain a heterocyclic-containing compound L. The heterocycle-containing compound L (hereinafter, referred to as “compound L”) was a brown solid having a heterocyclic group equivalent of 290, an active hydrogen equivalent of 100,000, a number average molecular weight of 1,700, and a viscosity of 400 cP (150 ° C.).

Reference Example 1 60 g of ethylenediamine and 40 of methyl isobutyl ketone
0 g was placed in a reaction vessel equipped with a reflux pipe equipped with a water separator, the inside of the vessel was replaced with nitrogen, and then reacted at 120 to 130 ° C. for 12 hours. Water generated with the progress of the reaction was removed one after another to smooth the progress of the reaction. After completion of the reaction, excess methyl isobutyl ketone was distilled off under reduced pressure to obtain ketimine A.

Examples 13 to 24, Comparative Example 1 The compounds A to L obtained in Examples 1 to 12 and the ketimine A obtained in Reference Example 1 were used as epoxy resin curing agents. A one-pack type epoxy resin composition was prepared with an appropriate formulation, and the following items were evaluated. Epicoat 828 (made by Yuka Shell Epoxy) was used as the polyepoxy compound. The results are shown in Tables 1 to 3. Comparative Example 1 is listed in each table for convenience of reference. PGE in Table 3 is
Represents phenylglycidyl ether.

Evaluation 1. Storage stability: The compositions of the compositions shown in Tables 1 to 3 were placed in an airtight container purged with nitrogen, and the composition was observed for 6 months when left at 40 ° C. in an atmosphere. 2. Mechanical properties: 25% of the compositions shown in Tables 1-3
After cultivating at 65 ° C. and 65% for 4 weeks and curing, the tensile strength and elongation were measured. 3. Adhesion: A composition having the composition shown in Tables 1 to 3 was applied between a concrete plate and a steel attachment for a Kenken-type adhesion tester, cultivated at 25 ° C. and 65% for 4 weeks, and cured. The adhesive strength was measured with a single-axis Kenken-type adhesive strength tester, and the state of the adhesive surface layer at that time was observed. 4. Coating strength: A composition having the composition shown in Tables 1 to 3 was applied to a steel plate to a thickness of 50 μm, and was cultivated at 25 ° C. and 65% for 4 weeks and cured, and then stipulated in JIS A 5400. A flex resistance test and a pencil hardness test were performed in accordance with the above methods. 5. Curing speed: A composition having the composition shown in Tables 1 to 3 was applied to a steel plate to a thickness of 50 μm, and kept at 25 ° C. and 65%, and
Days, 2 days, 3 days, 7 days after pencil hardness (JIS A
5400).

[0077]

[Table 1]

[0078]

[Table 2]

[0079]

[Table 3]

The one-pack type epoxy resin compositions of the present invention of Examples 1 to 12 all show good storage stability and are faster than the one-pack type epoxy resin compositions using ketimine A as a curing agent. The cure speed was indicated.

[0081]

Since the epoxy resin curing agent of the present invention has the above-mentioned constitution, the one-pack type epoxy resin composition of the present invention using the same can be cured by moisture at normal temperature, and has high storage stability and high speed. Excellent curability and workability. The one-pack type epoxy resin composition of the present invention is useful as a one-pack type paint, coating agent, adhesive and sealing agent for substrates such as concrete, wood, metal and glass.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification symbol FI H01B3 / 40 H01B3 / 40G (56) References JP-A-5-9267JP, A) JP-A-4-221370 (JP, A) JP-A-56-47473 (JP, A) JP-A-5-117252 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08G 59/40 C08G 59/50-59 / 60 C09J 163/00-163/10 C09K 3/10 C09D 163/00-163/10 H01B 3/40

Claims (17)

(57) [Claims] 1. A polymer having one main chain selected from the group consisting of polyether, polyvinyl, polyester, polyamide, polycarbonate and novolak, and having at least two heterocyclic groups represented by the following general formula (1) in the side chain. An epoxy resin curing agent comprising a heterocyclic-containing compound having at least one heterocyclic compound. Embedded image In the formula, R1 and R2 may be the same or different, and may be a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 6 carbon atoms, or 6 to 6 carbon atoms. 8 represents an aryl group or has 5 carbon atoms together with the carbon atom to which R1 and R2 are attached.
Represents 7 to 7 cycloalkyl rings. R3 has 1 to 1 carbon atoms
Represents an alkylene group of 0. 2. The heterocyclic-containing compound has no active hydrogen or has active hydrogen and has an active hydrogen equivalent of 4
The epoxy resin curing agent according to claim 1, which has a molecular weight of 000 or more. 3. The compound of the following general formula (2):
The epoxy resin curing agent according to claim 1, which is a compound having a structure represented by any one of (1) to (9). Embedded image In the formula (2), a represents an integer of 2 to 200. A1 is
—X—Z represents an alkylene group substituted or unsubstituted, an arylene group, an arylalkylene group, a haloalkylene group, or a residue obtained by ring-opening polymerization of glycidyl ether. X represents a divalent organic group. Z
Represents a heterocyclic group represented by the general formula (1). At least two of the A A1 in the formula (2) are -X-
Represents an alkylene group substituted with a Z group. In equation (3), b
Is an integer of 2 to 200. Q1 represents a hydrogen atom, an alkyl group, an aryl group, a haloalkyl group, a haloaryl group, an alkoxycarbonyl group, an acetoxy group, or-
Represents an XZ group. At least two of the b Q1s in the formula (3) represent a -XZ group. In the formula (4), c is 2
It is an integer of ~ 200. A2 and A3 are the same or different and are each an alkylene group substituted or unsubstituted with an -XZ group, an arylene group substituted or unsubstituted with an -XZ group, an aralkylene group, or , A haloalkylene group. C A2s in the formula (4)
And at least two of c3 A3s represent at least one selected from the group consisting of an alkylene group substituted with an -XZ group and an arylene group substituted with an -XZ group. In the formula (5), d is an integer of 2 to 200.
A4 represents an alkylene group substituted or unsubstituted with an -XZ group, an arylene group substituted or unsubstituted with an -XZ group, an aralkylene group, or a haloalkylene group. D A4s in the formula (5)
At least two of them represents at least one selected from the group consisting of an alkylene group substituted with an -XZ group and an arylene group substituted with an -XZ group. Equation (6)
Where e is an integer of 2 to 200. A5 and A6 are the same or different and are each an alkylene group substituted or unsubstituted with an -XZ group, an arylene group substituted or unsubstituted with an -XZ group, an aralkylene group, or Represents a haloalkylene group. At least two of e A5 and c A6 in the formula (6) are:
It represents at least one selected from the group consisting of an alkylene group substituted with an -XZ group and an arylene group substituted with an -XZ group. In the formula (7), f is an integer of 2 to 200. A7 represents an alkylene group substituted or unsubstituted by an -XZ group, an arylene group substituted or unsubstituted by an -XZ group, an aralkylene group, or a haloalkylene group. F in equation (7)
At least two of A7 represent at least one selected from the group consisting of an alkylene group substituted with a -XZ group and an arylene group substituted with a -XZ group.
In the formula (8), g is an integer of 2 to 200. A8 is
Represents an alkylene group substituted or unsubstituted with an -XZ group, an arylene group substituted or unsubstituted with an -XZ group, an aralkylene group, or a haloalkylene group. At least two of the g A8s in the formula (8) are at least one selected from the group consisting of an alkylene group substituted with an -XZ group and an arylene group substituted with an -XZ group. Represents In the equation (9), h is
It is an integer of 2 to 200. Ar represents an aryl group.
Q2 represents a hydrogen atom, an epoxy group, or a -XZ group. At least two of the h Q2s in equation (9) are:
Represents an -XZ group. 4. The divalent organic group X has at least one group selected from the group consisting of an ether group, a carbonate group, an ester group, an imino group, an amide group, a urethane group, a urea group and a sulfide group. 4. A hydrocarbon group which may be a hydrocarbon group.
The epoxy resin curing agent as described. 5. The heterocyclic-containing compound has a viscosity (25 ° C.) of 200 to 200,000 cP and a molecular weight per equivalent of the heterocyclic group represented by the general formula (1) of 150 to 2,000. The epoxy resin curing agent as described. 6. The epoxy resin curing agent according to claim 3, wherein the compound having a structure represented by the general formula (2) is a compound represented by any of the following general formulas (10) to (12). Embedded image In the formula (10), a is the same as described above. Q3 represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a haloalkyl group, a haloaryl group or a -XZ group. The group J represents any of the groups represented by the following general formulas (13) and (14). Embedded image In the formula (13), R5 represents a hydrogen atom, an alkyl group, an acyl group, or a group represented by the following general formula (15). Equation (1
In 4), R6 represents a hydrogen atom, an alkyl group, an acyl group, or a group represented by the following general formula (15). Embedded image In the formula (15), R7 represents an alkyl group, an aryl group or an aralkyl group. In the formula (11), a is the same as described above.
Q4 represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a haloalkyl group, a haloaryl group or a -XZ group. In the formula (12), a is the same as described above. R4 is 1
It represents a 1 to 8 valent group obtained by removing a hydrogen atom of a hydroxyl group from a ８ 8 valent alcohol or phenol or a 1 to 8 valent group obtained by removing a hydrogen atom of an amino group from 1 to 6 (poly) amines. m is equal to the valence of R4 and is an integer of 1 to 8. The J group is the same as described above. Q5 represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a haloalkyl group, a haloaryl group or a -XZ group. A × in equation (12)
At least two of the m Q5s represent a -XZ group. 7. A one-pack type epoxy resin composition comprising the epoxy resin curing agent according to claim 1 and a polyepoxy compound. 8. The method according to claim 7, wherein the ratio of the heterocyclic group equivalent represented by the general formula (1) of the heterocyclic-containing compound to the epoxy equivalent of the polyepoxy compound is 0.5 to 1.5. Liquid epoxy resin composition. 9. The polyepoxy compound is a glycidyl ether type, glycidyl ester type, glycidylamine type,
The one-pack type epoxy resin composition according to claim 7, which is one kind of polyepoxy compound selected from the group consisting of a linear aliphatic epoxide type and an alicyclic epoxide type. 10. The one-pack type epoxy resin composition according to claim 7, wherein the polyepoxy compound has no active hydrogen or has active hydrogen and has an active hydrogen equivalent of 4000 or more. 11. The one-pack type epoxy resin composition according to claim 7, wherein the one-pack type epoxy resin composition has an active hydrogen equivalent of 2000 or more. 12. An adhesive comprising the one-pack type epoxy resin composition according to claim 7 as a main component. 13. A sealing agent comprising the one-pack type epoxy resin composition according to claim 7 as a main component. 14. An anticorrosive coating agent or a coating agent for a coated floor, comprising the one-pack type epoxy resin composition according to claim 7 as a main component. 15. A primer comprising the one-pack type epoxy resin composition according to claim 7 as a main component. 16. A water-blocking agent for concrete or an injection for repairing concrete, comprising the one-pack type epoxy resin composition according to claim 7 as a main component. 17. An insulating agent comprising the one-pack type epoxy resin composition according to claim 7 as a main component.