JP2002206020A - Moisture-curable epoxy resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin composition capable of being cured with moisture at the normal temperature and a low temperature, having excellent preservation stability and capable of providing a cured product with excellent properties. SOLUTION: This epoxy resin composition comprises an epoxy resin and a latent curing agent having a ketimine group and an oxazolidine group in the molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a moisture-curable epoxy resin composition which is moisture-curable at normal and low temperatures, has excellent storage stability, and can be used as a one-pack type.

[0002]

2. Description of the Related Art Conventionally, epoxy resins have been widely used in the fields of paints, adhesives, civil engineering, construction, and the like. However, since most of them are of two-pack type, they have a drawback of poor workability during use. there were. As a method of one-part epoxy resin, JP-A-11-349663 uses a specific ketimine compound and a monofunctional oxazolidine compound as a curing agent for a one-part cold curing type epoxy resin, and stores the ketimine compound in comparison with a ketimine compound alone system. Improved stability and wet surface adhesion.

[0003]

However, in the above system using a ketimine compound and a monofunctional oxazolidine compound as a curing agent, the resin strength is greatly reduced by the oxazolidine compound, and the amount of the resin used is limited. There were enough cases.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems, and as a result, by using a compound having a ketimine group and an oxazolidine group in a molecule as a latent curing agent for an epoxy resin, The inventors have found that the above problem can be solved, and have completed the present invention. That is, the present invention is a moisture-curable epoxy resin composition comprising an epoxy resin (A) and a latent curing agent (B) represented by the following general formula (1). General formula

[0005]

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[Wherein R ¹ , R ² , R ⁴ and R ⁵ each independently represent a hydrogen atom, a linear or branched C 1-6
Or an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms, or R ¹ and R ² and / or R ⁴ and R ⁵ may combine to form a cycloalkyl ring having 5 to 7 carbon atoms. Where R ¹ and R ² and R
⁴ and R ⁵ are not simultaneously hydrogen atoms. R ³ is a linear or branched alkylene group having 2 to 10 carbon atoms; Z is an [amide group,
Even if the main chain and / or contains one or more selected from the group consisting of urethane groups, carbonate groups, ester groups, ether groups, sulfide groups, imino groups, urea groups, nitro groups, halogens, hydroxyl groups, and thiol groups. Good] (m + n) -valent organic group having 1 to 30 carbon atoms; m and n
Is a positive integer of 1 to 3. ]

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the epoxy resin (A) is not particularly limited as long as it has 2 to 10 epoxy groups in a molecule, and may be appropriately selected according to the use and purpose. However, preferably, it has 2 to 6 epoxy groups in the molecule and does not have active hydrogen, or has active hydrogen, when it has active hydrogen, Is 2000 or more. The epoxy equivalent (molecular weight per epoxy group) of (A) is preferably from 65 to 500, and more preferably from 90 to 300. When the epoxy equivalent is 500 or less, the crosslinked structure does not become loose, and the heat resistance of the cured product, and the physical properties such as mechanical strength are improved. On the other hand, when the epoxy equivalent is 65 or more, the toughness of the cured product is improved. is there.
As an example of (A), for example, Japanese Patent Application No. 11-256623
No. 1) to 7) below, for example, may be used.

1) Glycidyl ether (i) Diglycidyl ether of a dihydric phenol Diglycidyl ether of a dihydric phenol having 6 to 30 carbon atoms, for example, bisphenol F diglycidyl ether;
Bisphenol A diglycidyl ether, bishalogenated bisphenol A diglycidyl ether, tetrachlorobisphenol A diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, tetramethylbiphenyl diglycidyl ether,
Diglycidyl ether obtained from the reaction of 2 mol of bisphenol A with 3 mol of epichlorohydrin, etc .;

(Ii) trifunctional to hexafunctional or more,
Polyglycidyl ethers of polyhydric phenols having a carbon number of 6 to 50 or more and a molecular weight of 250 to 5000
Polyglycidyl ethers of polyhydric phenols of 3 to 6 or more, such as pyrogallol triglycidyl ether, dihydroxynaphthyl cresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, dinaphthyltriol triglycidyl ether, tetrakis ( 4-hydroxyphenyl)
Ethanetetraglycidyl ether, p-glycidylphenyldimethyltolyl bisphenol A glycidyl ether, trismethyl-tert-butyl-butylhydroxymethanetriglycidyl ether, glycidyl ether of phenol or cresol novolak resin, glycidyl ether of limonene phenol novolak resin, resorcinol and acetone The polyglycidyl ether of a polyphenol having a molecular weight of 400 to 5000 obtained by the condensation reaction is exemplified.

(Iii) Diglycidyl ether of a bifunctional aliphatic alcohol Diglycidyl ether of a diol having 2 to 100 carbon atoms and a molecular weight of 150 to 5000, for example, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol Diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol (molecular weight 150 to 400
0) Diglycidyl ether, polypropylene glycol (molecular weight: 180-5000) diglycidyl ether, polytetramethylene glycol (molecular weight: 200-500)
0) Diglycidyl ether, neopentyl glycol diglycidyl ether, alkylene oxide of bisphenol A [ethylene oxide or propylene oxide (1
(Iv) polyglycidyl ether of trifunctional to hexafunctional or higher aliphatic alcohols having 6 to 50 or more carbon atoms and a molecular weight of 290 to 1000.
Glycidyl ethers of trihydric to hexavalent or higher polyhydric alcohols such as 0, for example, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol hexaglycidyl ether, poly (n
= 2 to 5) glycerol polyglycidyl ether and the like.

2) Glycidyl ester Polyglycidyl ester of aromatic polycarboxylic acid having 6 to 20 or more carbon atoms and having 2 to 6 or more functional groups, and 6 to 20 or more carbon atoms, 2
Glycidyl esters of aliphatic or alicyclic polycarboxylic acids having a valence of from 6 to 6 or more. Specifically, the following are mentioned. (I) glycidyl ester of phthalic acid diglycidyl phthalate, diglycidyl isophthalate, diglycidyl terephthalate, and the like; (ii) polyglycidyl ester of aliphatic or alicyclic polycarboxylic acid glycidyl ester of (i) above Aromatic nucleus water additive, dimer acid diglycidyl ester, diglycidyl oxalate, diglycidyl malate, diglycidyl succinate, diglycidyl glutarate, diglycidyl adipate, diglycidyl pimerate, glycidyl (meth) acrylate (Co) polymers and the like.

3) Glycidylamine Glycidylamine, an aromatic amine having 6 to 20 or more carbon atoms and having a monovalent to 10-valent or more functional group, and glycidylamine of an aliphatic amine are exemplified. (I) Glycidylamines of aromatic amines N, N-diglycidylaniline, N, N-diglycidyltoluidine, N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane, N, N, N ′, N ′ -Tetraglycidyldiaminodiphenylsulfone, N, N,
N ', N'-tetraglycidyldiethyldiphenylmethane, N, N, O-triglycidylaminophenol and the like; (ii) glycidylamine of aliphatic amine N, N, N', N'-tetraglycidylhexamethylenediamine and the like Can be

4) Other chain aliphatic epoxides Epoxidized polybutadiene, epoxidized soybean oil and the like. 5) Other alicyclic epoxides having 6 to 50 or more carbon atoms and a molecular weight of 90 to 250
0, an alicyclic epoxide having 1 to 4 or more epoxy groups, for example, vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxydioxide Cyclopentyl ether, 3,4-epoxy-6-methylcyclohexylmethyl 3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, N, N,
N ', N'-tetraglycidylcyclohexylenediamine and bis (3,4-epoxy-6-methylcyclohexylmethyl) butylamine. It also includes a nuclear hydrogenated product of the phenolic epoxy compound. 6) A urethane-modified epoxy resin having a urethane bond in the structure, a reaction product of a polyether urethane oligomer and glycidol, and the like. 7) Acrylonitrile-butadiene rubber (NBR), butadiene-acrylonitrile copolymer having a carboxyl group (CTB) in a resin matrix
N), an epoxy resin in which amino group-terminated butadiene-acrylonitrile copolymer (ATBN), silicone rubber and the like are dispersed.

In addition to 1) to 7), any polyepoxide having two or more glycidyl groups capable of reacting with active hydrogen can be used. Of these, glycidyl ether and glycidylamine are preferable, and diglycidyl ether of dihydric phenols and diglycidyl ether of aliphatic alcohol are particularly preferable. These polyepoxides can be used in combination of two or more.

In the general formula (1), R ¹ , R ² ,
R ⁴ and R ⁵ are each independently a hydrogen atom, a linear or branched alkyl or alkenyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and 7 to 20 carbon atoms.
And an alkylaryl group having 7 to 20 carbon atoms. Specific examples include straight-chain or branched carbon atoms having 1 carbon atom.
Examples of the alkyl or alkenyl group of No. 6 to 6 include methyl group, ethyl group, propyl group, iso-propyl group, butyl group, iso-butyl group, sec-butyl group, t-butyl group, pentyl group, iso-pentyl group, neopentyl Groups, t-pentyl group, hexyl group, alkyl groups such as iso-hexyl group, and alkenyl groups such as vinyl group, allyl group, methallyl group, iso-propenyl group and propenyl group, and having 6 to 10 carbon atoms. Aryl groups include phenyl groups and naphthyl groups; aralkyl groups having 7 to 20 carbon atoms include benzyl groups and phenethyl groups;
Examples of the alkylaryl group of No. 20 include a nonylphenyl group.

A cycloalkyl ring (cyclopentyl ring, cyclohexyl ring, cycloheptyl ring and the like) which may be combined with R ¹ and R ² and R ⁴ and R ⁵ to form a carbon ring having 5 to 7 carbon atoms. Is mentioned. R ³ is a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group,
Isobutylene group, sec-butylene group, pentylene group,
Isopentylene group, neopentylene group, hexylene group,
It includes an isohexylene group and the like. The above R ¹ , R ² ,
When the number of carbon atoms of the alkyl group or alkenyl group of R ⁴ or R ⁵ exceeds 6, when the number of carbon atoms of the aryl group exceeds 10, or when the number of carbon atoms of the aralkyl group or the alkylaryl group exceeds 20, oxazolidine is used. There is a problem that the rate of hydrolysis of the group or ketimine group becomes slow. Also, R ³
When the number of carbon atoms exceeds 10, the balance between the stability of the heterocyclic group and the hydrolysis rate becomes poor.

At least one of R ¹ and R ^{2 in} the general formula (1) is preferably a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms from the viewpoint of the curing rate. More preferably, they are a hydrogen atom, a methyl group or an ethyl group. The same applies to R ⁴ and R ⁵ .

In (B), the sum (α) of carbon numbers of R ⁴ and R ⁵ is equal to or more than the sum (β) of carbon numbers of R ¹ and R ² ,
It is particularly preferable that the steric hindrance of the ketimine group represented by the general formula (5) to the Schiff base is larger than the steric hindrance of the oxazolidine group represented by the general formula (6) to the tertiary amine.

[0019]

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Since the Schiff base of the ketimine group has a higher basicity than the tertiary amine of the oxazolidine group, the storage stability is improved by the above-mentioned procedure. At this time, α
Is preferably 3, 4, 5, and β is any one of 2, 3, 4, and 5, and more preferably α ≧ β, and α is 4 or 5, and β is 2. Particularly preferred.

In the general formula (1), Z represents an amide group, a urethane group, a carbonate group, an ester group, an ether group,
The main chain and / or the side chain may contain at least one selected from the group consisting of a sulfide group, an imino group, a urea group, a nitro group, a halogen, a hydroxyl group, and a thiol group. ~ 30 organic groups. The valence of the organic group is preferably 2 to 4. The carbon number of the organic group is usually 1 to 30, preferably 1 to 16,
Particularly preferably, it is 1 to 10. If the carbon number of Z exceeds 30, the crosslinked structure formed by the reaction between the epoxy resin and the latent curing agent becomes loose, and the physical properties of the cured product are reduced. m and n are positive integers of 1 to 3, and when m and n exceed 3, the reaction rates of oxazolidination and ketimination decrease, and as a result, storage stability decreases. In order to further improve the storage stability, it is preferable that m ≧ n. R ¹ and R ² in m and R ⁴ and R ^{5 in} n may be the same or different, respectively. Examples of such organic groups include the following a) to d). a) (saturated or unsaturated) aliphatic group: an alkylene group such as a methylene group, an ethylene group, or a propylene group;
A residue obtained by removing a hydrogen atom of an aliphatic polyhydric alcohol having a functional group number of 2 to 6 or more (e.g., ethylene glycol, trimethylolpropane, pentaerythritol, and sorbitol); b) the following general formula (7): An alicyclic or heterocyclic-containing aliphatic group represented by the formula (10):

[0022]

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[0023]

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[0024]

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[0025]

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C) an aromatic ring-containing aliphatic group represented by the following general formulas (11) and (12):

[0027]

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[0028]

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D) alicyclic groups represented by the following formulas (13) to (14):

[0030]

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[0031]

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E) Heterocyclic group: piperazinylene group, isocyanurate group and the like. Of these, preferred are alicyclic groups, heterocyclic-containing aliphatic groups, and aromatic-ring-containing aliphatic groups, and more preferred are organic groups represented by formulas (7), (9) and (10). Particularly preferred is an organic group represented by the general formula (10).

The molecular weight per active hydrogen produced by the reaction of (B) with water is preferably from 30 to 500,
More preferably, it is 30 to 300. When the active hydrogen equivalent is 500 or less, the crosslinked structure is not loose, and the cured product has good chemical resistance and good physical properties such as mechanical strength.
When the active hydrogen equivalent is 30 or more, the cured product has good physical properties such as chemical resistance and mechanical strength.

The method for producing the latent curing agent (B) is not particularly limited, but for example, it can be produced by a method represented by the following reaction formula (15). That is, the polyamino compound (b1) is reacted with the monoepoxide (b2) to convert it into a secondary amino alcohol and a compound (b3) having at least one primary amino group, and then the (b3) and the carbonyl compound (b4) A dehydration condensation reaction is performed to convert the secondary amino alcohol in (b3) into an oxazolidine group and the primary amino group into a ketimine group to obtain (B).

[0035]

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In particular, when the ketimination and the oxazolidination are performed using different ketones, as shown in the reaction formula (16), a part of the primary amino groups in the polyamino compound (b1) is replaced with the carbonyl compound (b4). And then converted into a ketiminated polyamine (b5) by dehydration condensation to react with monoepoxide (b2) to give a ketiminated polyamino alcohol (b6), and finally (b6)
An oxazolidination reaction is carried out by dehydration condensation between the amino alcohol and (b4) to obtain (B).

[0037]

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In the above production method, the polyamino compound (b1) is not particularly limited as long as it is an aliphatic amine having two or more primary amino groups, and for example, the following (b1-1) to (b1-3) And the like. (B1-1) Aliphatic polyamines having 2 to 18 carbon atoms: aliphatic polyamines, for example, alkylene diamine having 2 to 6 carbon atoms [ethylenediamine, 1,2-propylenediamine, trimethylenediamine, tetramethylenediamine,
Hexamethylenediamine, etc.], polyalkylene (C2-6) polyamines [diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.]; (C 1-4) or hydroxyalkyl (C 2
To 4) substituted [dialkyl (C1 to 3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, methyliminobispropylamine, etc.]; alicyclic or heterocyclic-containing aliphatic polyamine;
For example, norbornane diamine and the like; aromatic ring-containing aliphatic amines (8 to 15 carbon atoms) such as xylylenediamine, tetrachloro-p-xylylenediamine and the like; (b1-2) alicyclic polyamine having 4 to 15 carbon atoms; For example, 1,3-diaminocyclohexane, isophoronediamine, mensendiamine, 4,4′-methylenedicyclohexanediamine (hydrogenated methylenedianiline) and the like; (b1-3) a heterocyclic polyamine having 4 to 15 carbon atoms, for example, 1,4-diaminoethylpiperazine and the like; preferably, aliphatic polyamines, alicyclic group-containing polyamines, and aromatic ring-containing aliphatic amines; more preferably, alkyl (C2 to C6) polyamine alkyl ( C1-C4 or hydroxyalkyl (C2-C4) substituted, norbornanedia Emissions, is a xylylenediamine.

Examples of the monoepoxide (b2) include hydrocarbon oxides having 2 to 24 carbon atoms (ethylene oxide, propylene oxide, 1-butene oxide,
-Butene oxide, α-olefin oxide having 5 to 24 carbon atoms, styrene oxide, etc., glycidyl ether of a hydrocarbon having 3 to 10 carbon atoms (n-butyl glycidyl ether, allyl glycidyl ether, 2-ethyl-hexyl glycidyl ether, 2-methyloctyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, p-sec-butylphenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, etc.), glycidyl esters of monocarboxylic acids having 3 to 30 carbon atoms (glycidyl) Acrylate, glycidyl methacrylate and the like), epihalohydrin such as epichlorohydrin and epibromohydrin, and hydroxyl-containing oxides such as glycidol. Preferred are hydrocarbon oxides having 2 to 24 carbon atoms and glycidyl ethers of hydrocarbons having 3 to 10 carbon atoms.

The reaction between the polyamino compound (b1) and the monoepoxide (b2) is usually performed at 40 ° C. to 120 ° C., and if necessary, in the presence of a solvent and / or a catalyst. The ratio of (b1) to (b2) is preferably such that the primary amino group in (b1) and the epoxy group in (b2) are in a molar ratio of 1.0: 0.3 to 1.5, preferably Is 1.0:
0.5 to 1.0. As the solvent, aliphatic alcohols such as methanol, ethanol, isopropanol and n-butanol, alkylbenzenes such as toluene and xylene, hexane, heptane and the like can be used. Examples of the catalyst include carboxylic acids such as acetic acid and propionic acid, mineral acids such as hydrochloric acid and sulfuric acid, Lewis acids (for example, boron trifluoride / diethyl ether, zinc chloride, etc.), and the amount used is (b1) To 0.01 to 5.0 parts by weight, preferably 0.05 to 3.0 parts by weight. The polyamino alcohol (b) obtained by reacting under the above conditions
3) has at least one primary amino group and at least one secondary amino alcohol.

As the carbonyl compound (b4), aldehydes having 1 to 8 carbon atoms (b4-1) or 1-carbon atoms
To 8 ketones (b4-2). Specific examples of (b4-1) include formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, benzaldehyde,
Acrolein, crotonaldehyde and the like can be mentioned. Preferred among these are acetaldehyde, propionaldehyde and benzaldehyde. Specific examples of (b4-2) include acetone, methyl ethyl ketone, methyl isobutyl ketone, 3-pentanone,
2-hexanone, 3,3-dimethyl-2-butanone, cyclopentanone, cyclohexanone, acetophenone,
Benzophenone and the like. Among these, acetone, methyl ethyl ketone and methyl isobutyl ketone are preferred.

The dehydration-condensation reaction between (b3) and (b4)
One or more kinds of carbonyl compounds (b4) can be used, and the reaction can be performed in the presence of a catalyst if necessary. The equivalent ratio of the raw materials is preferably the amine equivalent of (b3) (the value obtained by dividing the molecular weight by the sum of the primary amine and the secondary amino alcohol): (b4) = 1: 1 to 10, more preferably 1: 1. 1 to 5. In the dehydration condensation reaction, water may be separated in the pit under reflux conditions using a water-insoluble solvent, or the reaction may be carried out in the presence of a dehydrating agent in the system. As the water-insoluble solvent, the same ones as described above can be used. When operating under reflux conditions, the reaction temperature is preferably from 20 to 150
° C, more preferably 50 to 100 ° C. When the temperature is higher than 20 ° C., the reaction proceeds. When the temperature is lower than 150 ° C., side reactions such as polymerization hardly occur. If necessary, the reaction may be performed under reduced pressure.

The conversion of (b1) and (b4) into a ketiminated polyamine (b5) by dehydration condensation can be carried out in the same manner as in the dehydration / condensation reaction of (b3) and (b4). The ratio is preferably the primary amine equivalent of (b1) (the molecular weight divided by the sum of the primary amines): (b
4) = 1: 0.2-5, more preferably 1: 0.3-
It is one.

The addition reaction of (b5) and (b2) and (b5)
6) and the dehydration condensation reaction of (b4)
The reaction of 1) and (b2) and the reaction of (b3) and (b4) can be performed under the same conditions.

As the catalyst for the dehydration reaction, an acid catalyst is used, if necessary, and is preferably boron trifluoride / diethyl ether, p-toluenesulfonic acid, sulfuric acid, etc., and the amount used is (b3) 100 parts by weight. To 0.1 to 5.
0 parts by weight, preferably 0.5 to 3.0 parts by weight.

As the dehydrating agent that can be used, generally, a neutral or alkaline dehydrating agent can be used, and specifically, synthetic zeolite, calcium chloride, sodium sulfate, potassium carbonate, metallic sodium, calcium oxide, barium oxide, water Potassium oxide and the like, and more preferably, synthetic zeolite and potassium carbonate. Also, two or more of these may be used in combination. The reaction temperature in the dehydration-condensation reaction varies depending on the dehydrating agent.
To 100 ° C, more preferably 30 to 80 ° C. If it is too low, the reaction will not proceed, and if it is too high, the water absorbed by the dehydrating agent tends to be released again. The amount of the dehydrating agent used is usually 1 to 5 times, preferably 1.5 to 3 times the theoretically generated water amount based on the water absorbing capacity of the dehydrating agent.

The weight average molecular weight of (B) is preferably 1
80 to 2000, more preferably 200 to 10
00. The viscosity at 25 ° C is preferably 5 to 2000
0 mPa · s, more preferably 10 to 1000
0, particularly preferably 10 to 3000. The latent amino group equivalent (molecular weight per ketimine group or oxazolidine group) is preferably from 40 to 300,
It is more preferably 50 to 200, and particularly preferably 6
0 to 150. When it is 40 or more, synthesis is easy, and when it is 300 or less, the mechanical strength and chemical resistance of the cured product are good.

As a specific example of (B), those in which each symbol in the general formula (1) is shown in Table 1 can be mentioned.

[0049]

[Table 1]

The epoxy resin composition of the present invention comprises the epoxy resin (A) and the latent curing agent (B). The epoxy resin composition has the following general formula for the purpose of further improving low-temperature curability, improving the curing speed, and reducing the viscosity. It may contain the hetero ring-containing compound (C) represented by (2). General formula

[0051]

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[In the formula (2), w is an integer of 1 to 10,
Q ¹ , U ¹ and V ¹ are each independently an oxygen or sulfur atom; R ⁶ is a residue or a hydrogen atom of the cyclic ether group-containing compound (D); R ⁷ is a hydrocarbon group having 2 to 10 carbon atoms . ]

In the formula (C), w is 1 to 10,
Preferably 2 to 8 integer, Q ^1, U ¹ and V ¹ was, respectively oxygen or sulfur atom. Preferably, Q1 is a sulfur atom, ^one of U ¹ and V ¹ is a sulfur atom and the other is an oxygen atom. R ⁷ is a hydrocarbon group having 2 to 10 carbon atoms, a trivalent hydrocarbon _{group> CH (CH 2) m- (} m is an integer from 1 to 9)
For example,> CHCH ₂ —,> CHC
H ₂ CH ₂ —,> CHCH ₂ CH ₂ CH ₂ —,> CHCH ₂ C
H ₂ CH ₂ CH ₂ CH ₂ — and the like; tetravalent hydrocarbon group> CH (C
H ₂ ) a group represented by mCH <(m is an integer of 0 to 8), for example,> CHCH <,> CHCH ₂ CH <,> CH
CH ₂ CH ₂ CH <,> CHCH ₂ CH ₂ CH ₂ CH ₂ CH <
And the like, preferably a trivalent hydrocarbon group,
Particularly preferred are> CHCH ₂ — and> CHCH ₂ CH ₂ —. R ⁶ is a hydrogen atom or a residue of the cyclic ether group-containing compound (D), and R ⁷ is a residue constituting a ring other than the oxygen atom in the epoxy group. (D) is the general formula (1)
7). General formula

[0054]

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The cyclic ether group is not particularly limited as long as it has one oxygen atom in the ring, and examples thereof include compounds having 1 to 10 cyclic ether groups in the molecule. Examples of the cyclic ether group-containing compound (D) include an epoxy group-containing compound (D1) and an oxetane compound (D
2) and the like, and preferably an epoxy group-containing compound (D1). The epoxy group-containing compound (D1) includes:
Monoepoxide (d11) and two epoxy groups in the molecule
Polyepoxide (D11). The monoepoxide (d11) is not particularly limited as long as it has one epoxy group in the molecule, and can be appropriately selected depending on the use and purpose. An example of this is (b)
The same as in 2) can be mentioned.

The polyepoxide (D11) is not particularly limited as long as it has two or more epoxy groups in the molecule, and can be appropriately selected depending on the application and purpose.
Examples of the polyepoxide (D11) include the same as those of the above-mentioned epoxy resin (A), and preferred examples are also the same.

As the oxetane compound (D2), an aliphatic oxetane compound having 6 to 20 carbon atoms (3-ethyl-
3-hydroxymethyloxetane, etc.), having 7 to 30 carbon atoms
Aromatic oxetane compounds (benzyloxetane, xylylenebisoxetane, etc.), aliphatic carboxylic acid oxetane compounds having 6 to 30 carbon atoms (adipate bisoxetane, etc.), and aromatic carboxylic acid oxetane compounds having 8 to 30 carbon atoms (Such as terephthalate bisoxetane), an alicyclic carboxylic acid oxetane compound having 8 to 30 carbon atoms (such as bisoxetane cyclohexanedicarboxylate), and an aromatic isocyanate oxetane compound.

Heterocycle-containing compound (C) in the present invention
Is not particularly limited, for example, 0.5 to 0.5 to the cyclic ether group-containing compound (D) and its epoxy group
It is obtained by reacting 10 times equivalent of carbon disulfide in a solvent in the presence of a catalyst. The solvent is not particularly limited as long as it does not inhibit the reaction and dissolves the raw materials and products.
Usually, an aprotic solvent is used. For example, ethers (tetrahydrofuran, dioxane, diethyl cellosolve, dioxolan, trioxane, dibutyl cellosolve, diethyl carbitol, dibutyl carbitol, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, etc.), esters (methyl acetate) , Ethyl acetate, n-butyl acetate, etc.), and other polar solvents (acetonitrile, dimethylformamide,
N-methylpyrrolidone, dimethylsulfoxide, etc.) and the like, preferably tetrahydrofuran, acetone,
Ethyl acetate and the like. The catalyst is a halide of an alkali metal or an alkaline earth metal, and examples thereof include lithium chloride, lithium bromide, lithium iodide, potassium chloride, and calcium bromide, and lithium bromide is preferred. The amount of the catalyst was 0.001 to the epoxy group of (D).
１．０1.0 equivalent. Preferably it is 0.01 to 0.1 times equivalent. The reaction temperature is generally 0-100 ° C, preferably 20-70 ° C. The heterocyclic compound (C1) using the epoxy group-containing compound (D1) as the cyclic ether group-containing compound (D) is represented by the following general formula (3):
This is indicated by (4). General formula

[0059]

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[0060]

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[Wherein, w is an integer of 1 to 10. U ² , V ²
Is one of S and the other is O, more preferably U ² is O and V ² is S. R ⁸ is polyepoxide (D11)
Or it is a residue of monoepoxide (d11). R ⁹ is the residue of an alicyclic epoxide. The weight average molecular weight of the hetero ring-containing compound (C) is preferably from 120 to 12,000, and more preferably from 20 to 12,000.
0 to 8,000. The heterocycle equivalent is preferably 12
0 to 1,200, more preferably 200 to 800
It is. The viscosity at 25 ° C is usually 5 to 20,000 mP
a · s, preferably 10 to 10,000 mPa · s
s, more preferably 5,000 mPa · s or less,
Particularly preferably, it is 10 to 1,000 mPa. Specific examples of the heterocyclic-containing compound (C) obtained as described above include those in which each symbol in the general formula (2) is described in Table 2.

[0062]

[Table 2]

In the moisture-curable epoxy resin composition of the present invention, the ratio of (A) to (B) is such that the number of active hydrogens in (B) produced by the reaction with moisture or water is:
(A) is preferably 0.5 to 1 to one epoxy group.
The number is 2.0, and more preferably 0.7 to 1.3. When the number is 0.5 or more, or 2.0 or less, it is preferable that the curability does not decrease and the water resistance and mechanical strength of the cured product do not decrease. When using (C),
The number of heterocyclic groups in (C) is preferably 0.01 to 0.5, and more preferably 0.05 to 0.2, per one epoxy group in (A). This number is 0.01
When the number is equal to or more than 0.5 or less than 0.5, the curability is not reduced and the water resistance and mechanical strength of the cured product are preferably not reduced. More preferably, the amount of (C) added is from 0.1 to 100 parts by mass, more preferably from 0.5 to 100 parts by mass, per 100 parts by mass of (A) in the moisture-curable epoxy resin composition. It is 50 parts by mass, particularly preferably 1 to 20 parts by mass. If the addition amount is 0.1 part by mass or more, the curing promoting effect and the viscosity reducing effect are sufficient, and if it is less than 100 parts by mass, the cured product has good physical properties such as water resistance, chemical resistance, and mechanical strength. It is.

The moisture-curable epoxy resin composition of the present invention can further contain a basic compound (E) if necessary for the purpose of further promoting curing. Examples of the basic compound (E) include a tertiary amine compound (E1), an alkali compound (E2) such as sodium methylate, sodium hydroxide, sodium hydroxide, and lithium carbonate; and a Lewis base compound (E1) such as triethylphosphine and triphenylphosphine.
3) and the like. Preferred of these are 3
Secondary amine compound (E1).

The (E1) is not particularly limited as long as it is a compound having a tertiary amino group in the molecule, and examples thereof include the following. (I) an aliphatic amine having 3 to 20 carbon atoms and an amino group having 1 to 4 trimethylamine, triethylamine, tetraethylmethylenediamine, tetramethylpropane-1,3-diamine, tetramethylhexane-1,6-diamine, pentamethyldiethylenetriamine, Pentamethyldipropylenetriamine, bis (2-dimethylaminoethyl) ether, ethylene glycol (3-dimethyl) aminopropyl ether, dimethylaminoethanol, dimethylaminoethoxyethanol, N, N, N'-trimethylaminoethyl-ethanolamine, (Ii) an aromatic amine having 9 to 20 carbon atoms and an amino group having 1 to 4 dimethylbenzylamine, N, N-dimethylaminomethylphenol (DMP-10: registered trademark, ROHM & HA) Etc.), tris (N, N-dimethylaminomethyl) phenol (DMP-30: registered trademark, manufactured by Rohm & Haas), and (iii) a heterocycle having 4 to 20 carbon atoms and 1 to 6 amino groups. Compounds 1,2-dimethylimidazole, dimethylpiperazine,
N-methyl-N '-(2-dimethylamino) -ethylpiperazine, N-methylmorpholine, N- (N', N'-
Dimethylaminoethyl) morpholine, N-methyl-N '
-(2-hydroxyethyl) morpholine, 1,8-diazabicyclo (5,4,0) -undecene-7 (DBU:
Registered trademark, manufactured by San Apro), 1,5-diazabicyclo (4,3,0) -nonene-5 (DBN: registered trademark, manufactured by San Apro), 6-dibutylamino-1,8-diazabicyclo (5,4, 0) -undecene-7 (DBA-DB
U: registered trademark, manufactured by San Apro Co., Ltd.), triethylenediamine, hexamethylenetetramine and the like.

(E1) The type and the amount of addition may be appropriately selected according to the curing speed and the pot life to be obtained. Usually, the amount is preferably 0.1 to 100 parts by mass of (A). About 01 to 50 parts by mass are added. Also, (E
The same applies to the amounts of (2) and (E3).

The moisture-curable epoxy resin composition of the present invention further comprises a compatibilizer, a dehydrating agent, a flexibility-imparting agent, an adhesion-imparting agent, a curing accelerating catalyst, a filler, a deodorant, a coloring inhibitor, One or more selected from the group consisting of leveling agents, antioxidants, pigments, dispersants, reactive diluents, solvents, water retention agents, and wetting agents may be blended. The blending amount is the total weight 1
The amount is 50 parts by weight or less, preferably 30 parts by weight or less, particularly preferably 20 parts by weight or less based on 00 parts by weight.

The compatibilizer is used to improve the compatibility of each component in the storage and curing process when the moisture-curable epoxy resin of the present invention is used as a one-pack type, and to prevent phase separation and the like. Since the latent curing agent (B) in the epoxy resin composition of the present invention has a ketimine group and an oxazolidine group and has high solubility in the epoxy resin, the compatibility between the latent curing agent during storage and the epoxy resin is good. However, when these amino compounds are formed by hydrolysis, they have very high hydrophilicity, so that the compatibility with the epoxy resin is deteriorated, the phases are separated, and poor curing or deterioration in physical properties may be caused. Examples of the compatibilizer include surfactants such as a cationic surfactant, an anionic surfactant, an amphoteric surfactant, and a nonionic surfactant, and phenols having an SP value of 10 to 20 (phenol, cresol, resorcinol). etc),
Examples thereof include alcohols (eg, methanol and ethanol) and carboxylic acids (eg, salicylic acid and propionic acid). Preferred are nonionic surfactants which do not react with the resin composition and do not impair storage stability.

Specific examples of the nonionic surfactant include, for example, an aliphatic alcohol (C8 to C24) alkylene oxide (C2 to C8) adduct (degree of polymerization = 1 to 1)
00) [lauryl alcohol ethylene oxide addition (polymerization degree = 20), oleyl alcohol ethylene oxide addition (polymerization degree = 10), Macko alcohol ethylene oxide addition (polymerization degree = 35), etc.], polyoxyalkylene (carbon number) 2-8, degree of polymerization = 1-100)
Higher fatty acid (C8-24) ester [polyethylene glycol monostearate (degree of polymerization = 20), polyethylene glycol distearate (degree of polymerization = 30)
Etc.], polyhydric (divalent to 10-valent or higher) alcohol fatty acid (C8 to C24) ester [glyceryl monostearate, ethylene glycol monostearate, sorbitan laurate (mono / di) ester, sorbitan palmitic acid (Mono / di) ester, sorbitan stearic acid (mono / di) ester, sorbitan oleic acid (mono / di) ester, sorbitan coconut oil (mono / di)
Esters, etc.], polyoxyalkylenes (C 2-8,
Higher fatty acid (C8-C24) ester of polyhydric (divalent to divalent or higher) alcohol [polyoxyethylene (degree of polymerization = 10) sorbitan lauric acid (mono / di) ester , Polyoxyethylene (degree of polymerization = 20) sorbitan palmitic acid (mono / di)
Ester, polyoxyethylene (degree of polymerization = 15) sorbitan stearic acid (mono / di) ester, polyoxyethylene (degree of polymerization = 10) sorbitan oleic acid (mono /
Di) ester, polyoxyethylene (degree of polymerization = 25) lauric acid (mono / di) ester, polyoxyethylene (degree of polymerization = 50) stearic acid (mono / di) ester,
Polyoxyethylene (polymerization degree = 18) oleic acid (mono / di) ester, sorbitan, polyoxyethylene (polymerization degree = 50) dioleic acid methyl glucoside, etc., fatty acid alkanolamide [1: 1 coconut oil fatty acid diethanolamide, 1: 1 lauric acid diethanolamide, etc.], polyoxyalkylene (2-8 carbon atoms, degree of polymerization =
1 to 100) alkyl (C1 to C22) phenyl ether (polyoxyethylene (degree of polymerization = 20) nonylphenyl ether and the like), polyoxyalkylene (C2 to C2)
8, degree of polymerization = 1-100) alkyl (8-24 carbon atoms)
Amino ether and alkyl (C24-C) dialkyl (C1-C6) amine oxide [lauryl dimethyl amine oxide etc.], polydimethylsiloxane polyoxyethylene adduct, polyoxyethylene / polyoxypropylene block polymer (weight average) Molecular weight = 300
To 10,000).

As the nonionic surfactant used among them, a nonionic surfactant having an SP value close to that of the amino compound after hydrolysis is used to prevent phase separation due to hydrolysis of the latent curing agent. Is preferred. The SP value (χ ¹ ) of the surfactant and the SP value (χ ² ) of the amino compound formed by decomposing (B) with water are represented by the general formula χ2 +
More preferably, 2 ≧ ^{２ 1} ≧ χ 2-2 is satisfied. χ ¹
There without phase separation surface activity that it chi ² -2 or more, chi ¹
When χ ² +2 or less, the surfactant does not undergo phase separation during one-liquid formation. It can be appropriately selected according to (B) among the above activators.

The amount of the surfactant to be added depends on the amount of the resin composition 100
It is usually 0.01 to 20 parts by mass, preferably 0.05 to 10 parts by mass with respect to parts by mass. When the amount is 0.01 parts by mass or more, a surfactant effect is exhibited, and when the amount is 20 parts by mass or less, there is little influence on physical properties of a cured product.

The dehydrating agent prevents water mixed in the moisture-curable epoxy resin composition of the present invention for any reason from reacting with the latent curing agent (B) or the heterocyclic compound (C). This is for improving the liquid storage stability.
Examples of the dehydrating agent include silane coupling agents (vinyl trimethoxysilane and the like described later), monoisocyanate compounds (phenyl isocyanate and the like), zeolites (synthetic zeolites and the like described later), orthoesters (orthoglyte) Trimethyl acid), 2,2-dimethoxypropane and the like. Of these, vinyltrimethoxysilane and 2,2-dimethoxypropane are preferred. The amount is 20 parts by mass or less, preferably 10 parts by mass or less, based on 100 parts by mass of the resin composition.

Examples of the catalyst for the hydrolysis reaction of the latent curing agent (B) include organic acids (phosphate ester, p-toluenesulfonic acid, formic acid, acetic acid, propionic acid, etc.) and organic tin compounds (dibutyltin dilaurate, etc.). Is mentioned.
Examples of the catalyst for the reaction between the primary or secondary amine generated by the hydrolysis of (B) and the epoxy group include tertiary amines, phenols, and triphenylphosphine. As the tertiary amine, the same as (E1) can be mentioned. Of these, tertiary amines and phenols are preferred.
Aliphatic tertiary amines such as N-dimethylpropylamine, N, N, N ', N'-tetramethylhexamethylenediamine; heterocyclic tertiary amines such as N-methylpyrrolidine, N, N'-dimethylpiperazine Aromatic tertiary amines such as benzyldimethylamine and dimethylaminomethylphenol are particularly preferred.

The adhesiveness-imparting agent is used not only at the time of application under normal conditions, but also for particularly improving the adhesiveness at the time of application under water-containing concrete or high humidity. As the adhesion imparting agent, a silane coupling agent,
Examples thereof include a titanium coupling agent and an aluminum coupling agent, and preferably include a silane compound having a hydrolyzable silyl group. Examples of such a silane compound include vinylalkyl (1 to 4 carbon atoms) alkoxy (1 to 4 carbon atoms) silane [for example, vinyltrimethoxysilane,
Vinyltriethoxysilane, etc.), (meth) acryloyloxyalkyl (C1-4) alkoxy (C1
4) silane [for example, γ-methacryloxypropyltrimethoxysilane and the like], alkyl (1 to 4 carbon atoms) alkoxy (1 to 4 carbon) silane [for example, methyltrimethoxysilane, methyltriethoxysilane and the like], amino (molecule) 1 to 4) alkyl (2 to 15 carbon atoms) alkoxy (1 to 4 carbon atoms) silane [for example, γ- (2-aminoethyl) aminopropyltrimethoxysilane, aminopropyltrimethoxysilane, N-phenylamino Propylmethyldimethoxysilane, etc.), epoxy (1 to 4 per molecule)
Alkyl (C1-4) Alkoxy (C1-4)
4) silane [for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, etc.], mercapto (1 to 4 in the molecule) alkyl (1 to 4 carbon atoms) alkoxy (1 to 4 carbon atoms) To 4) silanes [for example, γ-mercaptopropyltrimethoxysilane and the like] and the like. Of these, preferred are vinylalkylalkoxysilane, (meth) acryloyloxyalkylalkoxysilane, and epoxyalkylalkoxysilane, and particularly preferred are vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxy. Propyltrimethoxysilane. The amount of these silane compounds used is 0.1 to 50 parts by mass, preferably 1 to 1 part by mass, based on the epoxy resin (A).
0 parts by mass. When the amount is 0.1 part by mass or more, adhesiveness (particularly, adhesion on a wet surface) is improved, and when the amount is 50 parts by mass or less, it reacts with moisture during use and does not hinder ring opening of the heterocyclic group. These silane compounds may be used in combination of two or more.

The filler is usually a finely pulverized solid, and the main purpose of the compounding is represented by performance such as strength and elastic modulus, durability such as weather resistance, conductivity, and heat conductivity. This is an improvement in physical properties, an improvement in molding processability such as fluidity and shrinkage, or an improvement in economic aspects such as an increase in amount and resource saving. Examples of the filler include inorganic fillers such as calcium carbonate, carbon black, clay, talc, titanium oxide, quicklime, kaolin, zeolite, and diatomaceous earth, and organic fillers such as vinyl chloride paste resin and vinylidene chloride resin balloon. And can be used alone or as a mixture. As the reactive diluent, in addition to ordinary low molecular weight epoxy compounds (phenyl glycidyl ether, butyl glycidyl ether, etc.), acrylate compounds (trimethylolpropane triacrylate, polyethylene glycol diacrylate, etc.), low molecular weight oxazolidine compounds (4, 4-dimethyl-1,3-oxazolidine) can also be used. These additives need to be sufficiently dehydrated before addition.

In order to improve the storage stability of the composition of the present invention, the epoxy resin (A), together with the latent curing agent (B) and the heterocyclic-containing compound (C) mixed if necessary, can be activated hydrogen. Or if it has active hydrogen, the active hydrogen equivalent is 2
Those having a molecular weight of 000 or more are preferred. The active hydrogen equivalent of the entire moisture-curable epoxy resin composition of the present invention during storage is preferably 4,000 or more, more preferably 20,000 or more, and particularly preferably 40,000 or more. When the active hydrogen equivalent is 4000 or more, the storage stability of the moisture-curable epoxy resin composition is good. If it has active hydrogen, deactivate the group having active hydrogen to a group that does not react with the epoxy resin to make it have no active hydrogen, or make the active hydrogen equivalent within a required range. It can be. 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 composition of the present invention further comprises a deodorant (G)
May be included. Examples of the deodorant (G) include, but are not particularly limited to, activated carbon, zeolite, silica sol, and silica gel. Among these, zeolite is preferred. In addition, the amount added as a mass ratio,
(C): (G) = 1: 0.01 to 0.5, preferably
1: 0.05 to 0.3.

The composition of the present invention is produced by blending (A), (B) and, if necessary, (C) a surfactant, a dehydrating agent, a filler and other various additives according to a conventional method. Preferably, it is obtained as follows. That is, first, (A), if necessary (C), and further, if necessary, various solid additives such as fillers are charged into a high-viscosity mixing stirrer or the like in a predetermined amount, preferably 20 to 150. C., more preferably at a temperature of 50-100 C. and preferably at 7
00-1 mmHg, more preferably 400-1 mmHg
g under reduced pressure to obtain a mixture. Next, a predetermined amount of a latent curing agent (B), a dehydrating agent as needed, and various liquid additives are added to a high-viscosity mixing stirrer containing the mixture thus obtained. 760-5
The mixture is further stirred under reduced pressure at 00 mmHg to obtain the desired moisture-curable epoxy resin composition. The storage stability of the moisture-curable epoxy resin composition of the present invention thus obtained is particularly excellent, and is suitable as a one-pack type moisture-curable epoxy resin composition. Of course, it can also be used as a two-pack type in which (A), (B) and others are mixed at the time of use.

In the actual curing reaction when the composition of the present invention is used, the amino group generated by the reaction of water in the air with the ketimine group and oxazolidine group of (B) and (C) are used. In this case, the reaction proceeds by the reaction of the thiol group formed by reacting a part of the thiol group with the compound (A). That is, since the curing reaction proceeds only from the surface in contact with air, when the ratio of the area of contact with air to the volume is small, the curing speed becomes extremely slow. Conversely, if the ratio of surface area to volume is increased,
The curing speed is greatly increased to a practical level. Therefore, when the moisture-curable epoxy resin composition is used as a one-pack type, the pot life becomes tens to hundreds of times longer than the tens of minutes of the conventional two-pack type. The used moisture-curable epoxy resin composition can be used successively, and the time and quantity restrictions during construction are greatly reduced. The curing temperature of the composition of the present invention is usually -10C or more, preferably -5 to 100C, particularly preferably -5 to 40C. The humidity condition is preferably 20
~ 100% R.C. H. And particularly preferably 10 to 80
% R. H. It is. The curing time is a few minutes to 100 hours.

The use of the moisture-curable epoxy resin composition of the present invention is not limited at all, but includes heavy-duty anticorrosive paints, anticorrosive coating materials, household adhesives, structural adhesives, civil and architectural adhesives. Agents, electrodeposition coatings for automobiles, powder coatings, resins for low-pressure resin injection method, coated floor materials, laminates for printed circuit boards,
Examples of applications include sealing agents for semiconductors, insulating agents, sealing agents, paving materials, seismic reinforcement resins, and hot melt adhesives.

The application using the composition of the present invention can be carried out according to a conventional method. For example, when used as a primer for various adherends, coated floor materials, dustproof paint, etc., depending on the film thickness or the shape of the applied surface, it is possible to use the sinking method, mortar method, lining method, coating method, etc. It is possible to construct by either, from the cured form of the epoxy resin composition of the present invention,
The sinking method or the coating method is preferred. As a coating method of the coating method, a general method such as brush coating, spray coating, and various coater coatings can be used. The coating amount of the composition of the present invention is not particularly limited.
00 μm, 50 to 500 for base coat and top coat
μm is preferred. The composition of the present invention can be applied over several times. In addition, the coating applied on the epoxy resin composition of the present invention is not particularly limited, and a normal top coating can be used without any particular limitation.For example, alkyd resin, epoxy resin, chlorinated rubber, silicone alkyd resin, silicone Acrylic resin-based and fluororesin-based paints can be used.

The cured product obtained by curing the composition of the present invention is excellent in flexibility, adhesion to concrete on a wet surface,
Excellent adhesion to various adherends.

[0083]

The present invention will be further described with reference to the following examples.
The present invention is not limited to this. In the following, parts indicate parts by weight. 1) Production of latent curing agent (B1) In a 1 L four-necked flask equipped with a water separator and a stirrer, 104 parts of 2-aminoethylaminoethanol and p-
Toluenesulfonic acid (1 part) was charged and mixed by stirring. Next, 400 parts of methyl isobutyl ketone was dropped in under cooling for 30 minutes so that the temperature did not exceed 50 ° C. After the dropping was completed, the heat generation was stopped, and the mixture was heated under reflux at 100 to 110 ° C to remove generated water. . After confirming that a theoretical amount of water was generated, the mixture was cooled to 80 ° C., and 20 parts of KW-1000 (manufactured by Kyowa Chemical Industry Co., Ltd .; acid adsorbent) was charged and stirred for 1 hour.
Next, 10 parts of diatomaceous earth A was used as a filter aid under a nitrogen atmosphere.
The solution was filtered at 0 ° C., and 50 parts of a synthesis (manufactured by Union Showa: Zeolite Molecular Sieve 3A) was added to the obtained filtrate, and allowed to stand overnight. Next, the synthetic zeolite was removed by filtration, and excess methyl isobutyl ketone was removed under heating under reduced pressure to obtain a latent curing agent (B1). The obtained (B1) has a latent amino group equivalent (molecular weight per ketimine group or oxazolidine group) of 90 and a viscosity (20 ° C .; B-type viscometer) of 80 m.
It was a red-brown liquid liquid of Pa · s.

2) Production of Latent Curing Agent (B2) 136 parts of xylylenediamine was charged into a 1 L four-necked flask equipped with a water separator and a stirrer, and 120 parts of methyl isobutyl ketone was heated at 50 ° C. Do not exceed the temperature and put it in two portions under cooling. After the exotherm subsides, molecular sieve 3A (manufactured by Union Showa: synthetic zeolite) 1
After adding 00 parts, the mixture was stirred at 40 ° C. for 3 hours and further stirred at room temperature overnight. When the conversion of this reaction was monitored by measuring the consumption of methyl isobutyl ketone by GC (gas chromatography), the conversion after standing at room temperature overnight was 88%. The molecular sieve is removed by filtration,
The obtained amine intermediate A was placed in a 1-L glass autoclave, and propylene oxide (59 parts) was added dropwise at a rate not exceeding 40 ° C. After the completion of the dropwise addition, the reaction was carried out at 40 ° C. for 5 hours, then the temperature was raised to 80 ° C., and unreacted propylene oxide was reacted to obtain amine intermediate B. Next, 232 parts of acetone, 1 part of p-toluenesulfonic acid, and 100 parts of molecular sieve 3A (manufactured by Union Showa: synthetic zeolite) were added to 277 parts of the amine intermediate B, and 40 parts of the mixture were added.
Stirred at 12 ° C. for 12 hours. Next, 20 parts of KW-1000 (manufactured by Kyowa Chemical Industry Co., Ltd .; acid adsorbent) was charged, and the mixture was further stirred for 1 hour. Next, 10 parts of diatomaceous earth A was filtered at 40 ° C. under a nitrogen atmosphere as a filter aid, and 50 parts of molecular sieve 3A (manufactured by Union Showa: synthetic zeolite) was added to the obtained filtrate and allowed to stand overnight. Then remove the synthetic zeolite by filtration,
Excess acetone was removed under heating under reduced pressure to obtain a latent curing agent (B2). The obtained (B2) had a molecular weight of 105 and a viscosity (2) per ketimine group or oxazolidine group.
0 ° C .; B-type viscometer) It was a red-brown liquid liquid of 1500 mPa · s.

3) Production of Heterocycle-Containing Compound (C-2EH) In a glass reactor equipped with a stirrer, 76 parts of carbon disulfide, 5 parts of lithium bromide, and 120 parts of THF were charged and dissolved by stirring. Glycidyl ether 190
Part was kept at 20 ° C or lower, and then dropped at 40 ° C for 5 minutes.
Aged for hours. Under reduced pressure, THF and excess carbon disulfide were distilled off, followed by filtration. The obtained hetero ring-containing compound (C-2EH) was a yellow liquid having a viscosity of 43 mPa · s (25 ° C.) and a hetero ring group equivalent of 262.

(Examples 1 to 5) 4) Production of moisture-curable epoxy resin composition Epicoat 8 previously dehydrated at 80 ° C. and 20 mmHg.
07 (manufactured by Yuka Shell Epoxy Co., Ltd .; bisphenol F type epoxy resin) and a heterocyclic-containing compound (C-2EH) in a ratio shown in Table 3, and after cooling to room temperature, as a latent curing agent and a dehydrating agent SZ-6300 (manufactured by Dow Corning Toray Silicone Co., Ltd .: vinyltrimethoxysilane), and if necessary, Narrow Acty N-95 (manufactured by Sanyo Kasei Kogyo Co., Ltd .: polyoxyalkylene alkyl ether) as a nonionic surfactant; As KBM-403
(Manufactured by Shin-Etsu Chemical Co., Ltd .: γ-glycoxypropyltrimethoxysilane) were added, and the mixture was again stirred under reduced pressure to produce a one-pack moisture-curable epoxy resin composition.

5) Table 3 shows the measurement results of the physical properties of the coating film and the storage stability of the moisture-curable epoxy resin composition at low and normal temperatures. (I) Viscosity: measured at 0 ° C. and 25 ° C. in a nitrogen atmosphere by a BL or BH type rotational viscometer. (Ii) Drying time to the touch: After applying the composition to a steel sheet specified by JIS A5400 using a 0.1 mm film applicator, the composition was dried at 0 ° C. and 30% R.F. H. And 25 ° C,
60% R.C. H. And the time until the surface resin of the coating film did not adhere to the finger was indicated. (Iii) Appearance: The state of the coating film surface was visually observed. Glossy, no swelling, no peeling, etc. were rated as ○, striped, but no swelling, peeling, etc. were rated Δ, and swelling, peeling, etc. were rated X. (Iv) Pencil hardness: A composition having the composition shown in Table 3 was prepared according to JISA
After being applied to a steel sheet specified in 5400 using a film applicator of 0.1 mm, the temperature was changed to 0 ° C. and 30% R.C. H.
Below and 25 ° C, 65% R.C. H. The pencil hardness of the surface of the cured coating film was measured according to JIS A5400.

(V) Adhesion (wet surface): A concrete plate soaked in water for 1 day was wiped lightly with a dry cloth.
Was applied at 0 ° C. and 30% R.C. H. Below and 25 ° C, 65% R.C. H. With respect to the cured product cultivated under the following conditions for 7 days, the adhesion was measured with a single-screw type Kenken-type adhesion tester, and the state of the adhesion surface layer was observed. 100%
も の indicates that the material was broken by the concrete, △ indicates that the material was partially broken, and × indicates that the concrete and the resin were separated at the interface. (Vi) Storage stability: A composition having the composition shown in Table 3 was placed in a sealed container purged with nitrogen, and allowed to stand in a 40 ° C. atmosphere for 3 months, and then visually observed for appearance and fluidity. The case where there was fluidity and there was no change in appearance was evaluated as ○, the case where there was fluidity but increased the viscosity was rated as Δ, and the case where gelation occurred was evaluated as ×.

When the one-pack type moisture-curable epoxy resin composition obtained in 4) was stored in a closed container and stored, all the examples showed good storage stability and cured physical properties.

[0090]

[Table 3]

(Comparative Examples 1-2) As in Examples 1-5,
A commercially available ketimine H (Epicure H-3, manufactured by Yuka Shell Epoxy) and, if necessary, oxazolidine M (ZOLDI
NEMS-PLUS, manufactured by Angus Co., Ltd.) with the formulation examples shown in Table 3, and the same tests were conducted. The results are shown in Table 3.

From the results of Examples 1 to 5 and Comparative Examples 1 and 2, the moisture-curable epoxy resin composition of the present invention can be cured and cured at low and normal temperatures at a lower temperature than conventional one-pack moisture-curable epoxy resin compositions. It was found that physical properties and storage stability were excellent.

[0093]

The moisture-curable epoxy resin composition of the present invention has the following effects. (1) Possibility of one-part type, which is a disadvantage of two-part type, in which there is a quantitative error in mixing the main agent and the curing agent, poor mixing, poor adhesion due to excess pot life, and pot life due to temperature changes in the workplace. Curing failure due to the variation of (2) The curing speed at normal temperature is high. In particular, since the composition to which (C) is added can be cured even at 0 ° C., it is possible to perform construction in winter, which was difficult in the past. (3) A cured product having excellent flexibility and wettability is provided. (4) Excellent storage stability.

Claims (9)

[Claims] 1. A moisture-curable epoxy resin composition comprising an epoxy resin (A) and a latent curing agent (B) represented by the following general formula (1). General formula [Wherein, R ¹ , R ² , R ⁴ and R ⁵ each independently represent a hydrogen atom, a linear or branched alkyl or alkenyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, An aralkyl group having 7 to 20 carbon atoms or an alkylaryl group having 7 to 20 carbon atoms, R ¹ and R ² and / or R
⁴ and R ⁵ may be bonded to form a cycloalkyl ring of 5-7 carbon atoms. However, R ¹ and R ² and R ⁴ and R ⁵ are not simultaneously hydrogen atoms. R ³ is a straight or branched carbon number 2
Z is an amide group, a urethane group,
It may contain at least one selected from the group consisting of a carbonate group, an ester group, an ether group, a sulfide group, an imino group, a urea group, a nitro group, a halogen, a hydroxyl group, and a thiol group] ( (m + n) valent organic group having 1 to 30 carbon atoms; m and n are positive integers of 1 to 3; ] 2. The moisture-curable epoxy resin composition according to claim 1, wherein the sum of carbon numbers of R ⁴ and R ⁵ is not smaller than the sum of carbon numbers of R ¹ and R ² . 3. The moisture-curable epoxy resin composition according to claim 1, further comprising a heterocyclic-containing compound (C) represented by the following general formula (2). General formula Wherein, w is an integer of 1 to 10, Q ^1, U ¹ and V ¹ was each independently represent an oxygen or sulfur atom; residue or a hydrogen atom of R ⁶ is a cyclic ether group-containing compound (D); R ⁷ Is carbon number 2
And 10 to 10 hydrocarbon groups. ] 4. The moisture-curable epoxy resin composition according to claim 2, wherein (C) is a heterocyclic-containing compound (C1) represented by the following general formula (3) or (4). General formula [Wherein, w is an integer of 1 to 10, one of U ² and V ² is S and the other is O; R ⁸ is a residue obtained by removing an epoxy group from polyepoxide (D11) or monoepoxide (d11);
⁹ is an alicyclic epoxide residue. ] 5. The viscosity at 25 ° C. of (C) is 1
The pressure is from 0 mPa · s to 1000 mPa · s.
The moisture-curable epoxy resin composition according to any one of the above. 6. The method according to claim 1, wherein the number of active hydrogens generated by decomposing with water in (B) is 0.5 to 2.0 per one epoxy group in (A). Or the moisture-curable epoxy resin composition. 7. The moisture-curable epoxy resin composition according to claim 1, further comprising a nonionic surfactant added to said composition. 8. SP value of the nonionic surfactant and (χ ^1), (B) is the SP value of the amino compound produced by hydrolysis (chi ²⁾ and the general formula ^{χ 2 + 2 ≧ χ 1 ≧} χ satisfies the ^2-2 7. moisture-curable epoxy resin composition. 9. An epoxy resin cured product obtained by curing the composition according to claim 1.