JP2022034534A - Epoxy resin composition - Google Patents

Abstract

To provide an epoxy resin composition that prevents its volume from decreasing when it is cured and gives a cured product having excellent adhesion to a wet surface and excellent mechanical strength.SOLUTION: An epoxy resin composition contains a polyepoxide (A), a polyamine having 2-50 active hydrogen atoms directly binding N atoms (B), an expanding agent (C), water (D) and a silane coupling agent (E). The expanding agent (C) contains calcium oxide. The silane coupling agent (E) is a compound having at least one alkoxy group binding a silicon atom, and at least one functional group selected from the group consisting of an amino group, a mercapto group and an epoxy group. The molar ratio between calcium oxides in the expanding agent (C) and alkoxy groups binding silicon atoms in the silane coupling agent (E), (CaO/alkoxy group), is 1-40.SELECTED DRAWING: None

Description

The present invention relates to an epoxy resin composition.

Epoxy resins are used in a wide range of applications such as civil engineering, casting materials, and adhesives due to their excellent chemical and physical properties.
For example, in the field of civil engineering and construction, it is used as an adhesive for post-installed anchors, and is used when drilling holes in concrete structures to fix anchor bolts and the like. Since it is constructed on-site, there are cases where the adhesive is used when the adhesive surface is wet due to rainfall or the like. However, when water is present at the interface between the epoxy resin and the adherend, there is a problem that wetting of the epoxy resin to the surface of the adherend is hindered and the adhesive force is significantly reduced.
As a technique for improving the adhesive strength to a wet surface, a method of blending cement with an epoxy resin mixture composed of a liquid epoxy resin and an amine curing agent to improve the adhesiveness to a water-wet surface (Patent Document 1), an epoxy resin, and the like. A method of adding an aromatic alcohol to an epoxy curing agent and an inorganic filler (Patent Document 2) and a method of adding a silane coupling agent (Patent Document 3) are known.
However, the method of adding cement or aromatic alcohol has a problem that the adhesive force with the adherend is not sufficient. Further, in the method of adding a silane coupling agent, there is a problem that the adhesive force is not sufficiently developed when a gap is formed between the adhesive and the adherend due to shrinkage during curing.

Japanese Unexamined Patent Publication No. 57-12024 Japanese Patent Application Laid-Open No. 2002-338662 Japanese Unexamined Patent Publication No. 2014-19631

The present invention provides an epoxy resin composition capable of suppressing volume shrinkage during curing of the epoxy resin composition, having excellent adhesion to a wet surface, and being able to obtain a cured product having excellent mechanical strength. The purpose is.

The present inventors have arrived at the present invention as a result of studies for achieving the above object.
That is, the present invention contains a polyepoxide (A), a polyamine (B) having 2 to 50 active hydrogens directly linked to N atoms, a swelling agent (C), water (D), and a silane coupling agent (E). In an epoxy resin composition, the swelling agent (C) contains calcium oxide, and the silane coupling agent (E) is composed of at least one alkoxy group bonded to a silicon atom, and an amino group, a mercapto group, and an epoxy group. It is a compound having at least one functional group selected from the above group, and has an epoxy group bonded to a calcium oxide in the swelling agent (C) and a silicon atom in the silane coupling agent (E). Epoxy resin composition having a molar ratio (CaO / alkoxy group) of 1 to 40; a cured product obtained by curing the epoxy resin composition.

The epoxy resin composition of the present invention has the following effects.
(1) Since the composition has extremely small volume shrinkage during curing or moderately expands during curing, it is excellent in suppressing volume shrinkage. These can be evaluated by the volume change rate (%) before and after curing, which will be described later.
(2) Excellent adhesion to wet surfaces.
(3) The effect of deterioration of physical properties due to the formulation of silane coupling is small, and a cured product having excellent mechanical strength is provided.

The epoxy resin composition of the present invention comprises a polyepoxide (A), a polyamine (B) having 2 to 50 active hydrogens directly linked to N atoms, a swelling agent (C), water (D), and a silane coupling agent (E). In the epoxy resin composition containing, the swelling agent (C) contains calcium oxide, and the silane coupling agent (E) has at least one alkoxy group bonded to a silicon atom, an amino group, a mercapto group and the like. It is a compound having at least one functional group selected from the group consisting of epoxy groups, and is bonded to calcium oxide in the swelling agent (C) and silicon atoms in the silane coupling agent (E). It is an epoxy resin composition having a molar ratio (CaO / alkoxy group) with an alkoxy group of 1 to 40.

[Polyepoxide (A)]
The polyepoxide (A) in the present invention has two or more epoxy groups in the molecule and does not have an alkoxy group bonded to a silicon atom, and has physical properties (mechanical strength, etc.) and epoxy of the cured product. From the viewpoint of handleability of the resin composition, the number of epoxy groups is preferably 2 to 10, and more preferably 2 to 6.
One type of polyepoxide (A) may be used, or two or more types may be used in combination.

(A) Number average molecular weight [hereinafter abbreviated as Mn. The measurement is based on the gel permeation chromatography (GPC) method under the conditions described below. ] Is preferably 100 to 10,000, more preferably 160 to 3,000, from the viewpoint of the physical properties of the cured product (mechanical strength and the like) and the handleability of the epoxy resin composition.
The epoxy equivalent (molecular weight per epoxy group) of (A) is preferably 50 to 1,000 from the viewpoint of physical properties (mechanical strength, etc.) of the cured product and handleability of the epoxy resin composition. It is preferably 80 to 500.

Examples of (A) include the following (A1) to (A4), and a mixture of two or more thereof.

(A1) Polyglycidyl ether (A11) Diglycidyl ether of dihydric phenol [carbon number (hereinafter abbreviated as C) 6 to 30] Bisphenol (bisphenol-F, -A, -B, -AD or S, etc.) Diglycidyl ether , Halogenized bisphenol A (tetrachlorobisphenol A, etc.) diglycidyl ether, monocyclic dihydric phenol (catechol, resorcinol, hydroquinone, etc.) diglycidyl ether, condensed polycyclic dihydric phenol [1,5-dihydroxynaphthalene, dihydroxybiphenyl, Octachloro-4,4'-dihydroxybiphenyl, 9,9'-bis (4-hydroxyphenyl) fluorene, etc.] Diglycidyl ether, diglycidyl ether, etc. obtained from the reaction of 2 mol of bisphenol A and 3 mol of epichlorohydrin;

(A12) Polyglycidyl ether of polyvalent (trivalent to hexavalent or higher) phenol Polyglycidyl ether of polyhydric phenol (C6 or more and Mn 5,000 or less), for example, trihydric phenol [pyrogalol, dihydroxynaphthylcresol, tris (Pyrogallol, dihydroxynaphthylcresol, tris) Hydroxyphenyl) methane, dinaphthylliol, p-glycidylphenyldimethyltril bisphenol A, etc.] Triglycidyl ether, tetravalent phenol [tetrakis (4-hydroxyphenyl) ethane, 4,4'-oxybis (1,4-phenylethyl) Tetracresol, bis (dihydroxynaphthalene), etc.] Tetraglycidyl ether, phenol or polyglycidyl ether of cresol novolak resin (Mn400-5,000), polyglycidyl ether of limonenephenol novolak resin (Mn400-5,000), phenol and glioxal , Polyphenol (Mn400-5,000) polyglycidyl ether obtained by condensation reaction with glutaaldehyde, or formaldehyde, and polyphenol (Mn400-5,000) polyglycidyl ether obtained by condensation reaction between resorcin and acetone;

(A13) Diglycidyl ether aliphatic diol (C2 or more and Mn 5,000 or less) [Dihydric alcohol [for example, ethylene glycol, propylene glycol, tetramethylene glycol, neopentyl glycol, 1,6-hexanediol (hereinafter) EG, PG, TMG, NPG, 1,6-HD, respectively), polyalkylene glycol [for example, polyethylene glycol (hereinafter abbreviated as PEG; molecular weight 106 or more and Mn 4,000 or less), polypropylene glycol (hereinafter abbreviated as PPG), respectively. Diglycidyl ether having a molecular weight of 134 or more and Mn 5,000 or less), polytetramethylene glycol (hereinafter abbreviated as PTMG; molecular weight 162 or more and Mn 5,000 or less)], etc.;

(A14) Aliphatic poly (trivalent to hexavalent or higher) all (C6 or higher and Mn 10,000 or lower) polyglycidyl ether aliphatic polyol [polyhydric (3 to 6-valent) alcohol [trimethylolpropane, glycerin, Pentaerythritol, sorbitol (hereinafter abbreviated as TMP, GR, PE, SO, respectively), etc.], intramolecular or intermolecular dehydrations of polyhydric alcohols [poly (n = 2-5) GR], and alkylenes of these polyhydric alcohols. Oxide [hereinafter abbreviated as AO. C2-6, for example, ethylene oxide, 1,2-propylene oxide (hereinafter abbreviated as EO and PO, respectively)] adducts, etc.] polyglycidyl ether and the like;

(A15) Polyglycidyl ether of alicyclic-containing poly (divalent to tetravalent or higher) all C3 or more and Mn 5,000 or less, for example, 1,2-cyclopropanediol, 2,2,4,4-tetra Methyl-1,3-cyclobutanediol, 1,4-cyclohexanediol, hydrogenated bisphenol A, 1,2,3-cyclopropanetriol, 1,3,5-cyclohexanetriol, sucrose and their AOs (1-20 mol) ) Polyglycidyl ether such as additives;

(A16) Aromatic ring-containing polyhydric (divalent to tetravalent or higher) alcohol polyglycidyl ether C8 or higher and Mn 5,000 or lower, AO (1 to 20 mol) adduct of bisphenol A, m- or p. -Xylylene glycol, benzenediethanol, 1,2-diphenylethane-1,2-diol, 1,1,2,2-tetraphenylethane-1,2-diol and their AO (1-20 mol) addition Polyglycidyl ether for things, etc .;

(A2) Polyglycidyl ester (A21) Glycidyl ester of aromatic polyvalent (divalent to 6-valent or higher) carboxylic acid Polyglycidyl ester of aromatic polyvalent carboxylic acid (C6-C20 or higher), for example, aromatic Dicarboxylic acid (ortho-, iso- or terephthalic acid, etc.) diglycidyl ester, aromatic tricarboxylic acid (trimeric acid, etc.) triglycidyl ester;
(A22) Polyglycidyl ester of aliphatic or alicyclic-containing polyvalent carboxylic acid (C6 to C20 or higher) For example, aliphatic dicarboxylic acid (oxalic acid, maleic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, etc.) Diglycidyl ester, aliphatic tricarboxylic acid (tricarbaryl acid, etc.) Triglycidyl ester, (co) polymer of glycidyl (meth) acrylate (polymerization degree 2 to 10), alicyclic-containing polyvalent carboxylic acid (dimeric acid, etc.) Polyglycidyl ester of the above (A21) nuclear hydrogenated product;

(A3) Glycidylamine of polyamine (C6 to C20 or more and having 2 to 10 or more active hydrogens directly linked to nitrogen atom) Polyglycidylamine of (A31) aromatic amine For example, N, N -Diglycidylaniline, N, N-diglycidyltoluidine, N, N, N', N'-tetraglycidyldiaminodiphenylmethane, N, N, N', N'-tetraglycidyldiaminodiphenylsulfone, N, N, N' , N'-tetraglycidyldiaminoethylphenylmethane, N, N, O-triglycidylaminophenol;
(A32) Polyglycidylamines of aliphatic amines For example, N, N, N', N'-tetraglycidylxylylenediamine, N, N, N', N'-tetraglycidyl hexamethylenediamine;
(A33) Polyglycidylamine of alicyclic-containing or heterocyclic-containing amine (C6 to C20 or more and having 2 to 10 or more active hydrogens directly linked to nitrogen atoms) Polyglycidyl amine of alicyclic Glysidylamines (eg, hydrogenated products of N, N, N', N'-tetraglycidylxylylene diamine), polyglycidylamines of heterocyclic-containing amines (eg, trisglycidylmelamine);

(A4) Other polyepoxides (A41) Aliphatic poly (divalent to hexavalent or higher) Epoxides C6 or higher and Mn2,500 or lower, such as epoxidized polybutadiene and epoxidized soybean oil;
(A42) Alicyclic poly (divalent to tetravalent or higher) Epoxyd C6 or more and Mn2,500 or less, for example, vinylcyclohexenedioxide, limonendioxide, dicyclopentadiendioxide, bis (2,3-) Epoxycyclopentyl) ether, ethylene glycol bisepoxydicyclopentyl ether, 3,4-epoxy-6-methylcyclohexylmethyl-3', 4'-epoxy-6'-methylcyclohexanecarboxylate, bis (3,4-epoxy-6) -Methylcyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) butylamine.

Of these (A), (A1) and (A2) are preferable, and (A11) and (A12) are particularly preferable, from the viewpoint of the physical properties (mechanical strength, etc.) of the cured product. Preferred are glycidyl ether of bisphenol F, diglycidyl ether of bisphenol A, polyglycidyl ether of phenol novolac resin and polyglycidyl ether of cresol novolak resin.

[Polyamine (B)]
The polyamine (B) in the present invention has 2 to 50, preferably 2 to 10, and more preferably 3 to 8 active hydrogens directly linked to N atoms. If the number is less than 2, the physical properties (mechanical strength, etc.) of the cured product will be inferior, and if the number exceeds 50, the handling property of the epoxy resin composition will be poor.
One type of polyamine (B) may be used, or two or more types may be used in combination.

The Mn of (B) is preferably 30 to 25,000, more preferably 45 to 1,600, from the viewpoint of the physical properties (mechanical strength and the like) of the cured product and the handleability of the epoxy resin composition.

The active hydrogen equivalent (molecular weight per active hydrogen) of (B) is preferably 15 to 500, more preferably 20 to 200 from the viewpoint of physical properties (mechanical strength, etc.) and industrial aspects of the cured product.

Examples of (B) include the following (B1) to (B9), and a mixture of two or more thereof.

(B1) aliphatic poly (2 to 7 valent) amines C2 or more and Mn500 or less, for example, C2 to 10 alkylenediamines (ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.), polyalkylenes. (C2-10) Poly (trivalent to hexavalent or higher) amines [diethylenetriamine, iminobispropylamine, bis (hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.], and them. Alkyl (C1-4) or hydroxyalkyl (C2-4) substituents such as dialkyl (C1-3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2,5-hexa Methylenediamine, Methyliminobispropylamine, N, N'-di-n-butyl-1,6-hexanediamine;

(B2) Alicyclic-containing poly (2-trivalent) amines C4-15, such as 1,3-diaminocyclohexane, 1,3-bisaminomethylcyclohexane, isophoronediamine, mensendiamine, 4,4'-methylene Dicyclohexanediamine (hydrogenated methylenedianiline);

(B3) Heterocycle-containing poly (2-trivalent) amines C4-15, such as piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4-bis (2-amino-2-methyl) Propyl) piperazine;

(B4) Aromatic ring-containing polyamines C8 to 15, for example, xylylenediamine, tetrachlor-p-xylylenediamine;

(B5) Polyamide Polyamine Polyamide obtained by condensation of a polyamine having a molecular weight of 200 or more and Mn 1,000 or less, for example, a dicarboxylic acid (dimeric acid or the like) and an excess [2 equivalents or more per equivalent of a carboxyl group such as (B1) or the like]. Polyamine;

(B6) Polyetherpolyamine A hydrogenated product of a cyanoethylated product having a molecular weight of 100 or more and Mn 1,000 or less, for example, a polyether polyol [the polyalkylene glycol or the like];

(B7) Epoxy-added polyamine A reaction product having a molecular weight of 100 or more and Mn 1,000 or less, for example, 1 mol of an epoxy compound and 1 to 30 mol of the above (B1) [epoxy compound [the polyepoxide (A) and a monoepoxide (butyl glycidyl ether)). , Phenylglycidyl ether, etc.), etc.] 1 mol and 1 to 30 mol of the aliphatic polyamine (B1) reaction product (molecular weight 100 or more and Mn 1,000 or less), etc.];

(B8) Cyanoethylated polyamines having a molecular weight of 100 or more and Mn 500 or less, for example, acrylonitrile and the above (B1).
Reaction product (biscyanoethyldiethylenetriamine, etc.);

(B9) Other polyamine (B91) hydrazine compounds (those having a molecular weight of 32 or more and Mn 500 or less, such as hydrazine and monoalkyl hydrazine)
(B92) Dihydrazid compound [Molecular weight 74 or more and Mn 1,000 or less, for example, acid (succinic acid, adipic acid, isophthalic acid, terephthalic acid, etc.) dihydrazide]
(B93) A guanidine compound (molecular weight 59 or more and Mn 500 or less, for example, butyl guanidine, 1-cyanoguanidine).

Of the above (B), (B1) to (B5) are preferable from the viewpoint of physical properties (mechanical strength, etc.) of the cured product, and (B1), (B4) and (B5) are more preferable. Yes, and particularly preferred are (B1) and (B4).

[Leavening agent (C)]
The leavening agent (C) in the present invention expands by reacting with water and contains calcium oxide.

The shape of (C) is preferably powder from the viewpoint of handleability of the epoxy resin composition.
The volume average particle size of (C) is preferably 0.1 to 800 μm, more preferably 0.5 to 250 μm, from the viewpoint of the viscosity and workability of the epoxy resin composition.

Examples of (C) include the product names "Pacific HyperExpan (for structure)", "Pacific Hyperexpan M (for structure / heat hydration suppression type)", "Pacific expand (for structure)", and "Pacific". "Expan (for products)", all manufactured by Pacific Material Co., Ltd., product names "Denka Power CSA Type S", "Denka Power CSA Type R", "Denka Power CSA Type T", "Denka CSA # 10", "Denka CSA # 20", both manufactured by Denki Kagaku Kogyo Co., Ltd., etc., are commercially available and available.

[Water (D)]
Examples of the water (D) in the present invention include ion-exchanged water, ultrapure water, distilled water, tap water, city water, industrial water and a mixture of two or more of these, and the physical properties (mechanical strength, etc.) of the cured product. ) And industrially, ion-exchanged water, ultrapure water and distilled water are preferable, and ion-exchanged water is more preferable.

[Silane coupling agent (E)]
The silane coupling agent (E) in the present invention has at least one alkoxy group bonded to a silicon atom and at least one functional group selected from the group consisting of an amino group, a mercapto group and an epoxy group. It is a compound.
The silane coupling agent (E) reacts with (A) or (B) in the epoxy resin composition by having at least one functional group selected from the group consisting of an amino group, a mercapto group and an epoxy group. It is possible to impart adhesiveness to the wet surface of the epoxy resin composition.
Further, the alkoxy group bonded to silicon in the silane coupling agent (E) is hydrolyzed by water (D) in the epoxy resin composition or water adhering to the adhesive surface in a wet state to generate alcohol. This alcohol acts as a plasticizer in the cured product of the epoxy resin composition and has a problem of lowering the mechanical strength. However, in the present invention, by containing calcium oxide as the swelling agent (C), It is presumed that the produced alcohol reacts with calcium oxide to obtain an epoxy resin composition capable of obtaining a cured product having excellent adhesiveness to a wet surface without impairing the mechanical strength.

Examples of the silane coupling agent (E) include those having an amino group {aminoalkyl (preferably 2 to 10 carbon atoms) trialkoxy (preferably 1 to 10 carbon atoms of the alkoxy group) silane (specifically, 3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, etc.), N-substituted-aminoalkyl (preferably 2 to 10 carbon atoms) Trialkoxy (preferably alkoxy group having 1 to 10 carbon atoms) silane (specifically Specifically, N-phenyl-3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane. , N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3- (methylamino) propyltrimethoxysilane, 3- (methyl) (Amino) propyltriethoxysilane, etc.)}, those having a mercapto group {mercaptoalkyl (preferably 2 to 10 carbon atoms) trialkoxy (preferably 1 to 10 carbon atoms of an alkoxy group) silane (specifically, 3) -Mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropyltriethoxysilane, etc.)}, those having an epoxy group {glycidoxyalkyl (preferably carbon) Number 2 to 10) Trialkoxy (preferably alkoxy group having 1 to 10 carbon atoms) Silane (specifically, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glyceride) Sidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, etc.), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2 -(3,4-Epoxycyclohexyl) ethylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 5,6-epoxyhexyltrimethoxysilane, 5,6-epoxyhexylmethyldimethoxysilane, 5,6-Epoxyhexylmethyldiethoxysilane, 5,6-epoxyhexyltriethoxysilane, etc.} and the like.
Of these, the alkoxy group preferably has 1 to 5 carbon atoms, and more preferably the alkoxy group has 1 to 3 carbon atoms, from the viewpoint of reactivity with the leavening agent (C) and adhesiveness.
Further, from the viewpoint of the volume change rate, those having an amino group are preferable.

[Epoxy resin composition]
The epoxy resin composition of the present invention comprises the above (A), (B), (C), (D) and (E), and the calcium oxide in the leavening agent (C) and the silane coupling. The molar ratio (CaO / alkoxy group) with the alkoxy group bonded to the silicon atom in the agent (E) is 1 to 40. If the molar ratio (CaO / alkoxy group) is less than 1, the mechanical strength tends to be inferior, and if it exceeds 40, the adhesive strength tends to decrease.
The molar ratio (CaO / alkoxy group) is preferably 2 to 30, more preferably 4 to 15, from the viewpoint of mechanical strength and adhesiveness.

The contents of (A), (B), (C), (D) and (E) in the composition are those of (A), (B), (C), (D) and (E). Based on the total weight, each is as follows.
(A) is preferably 40 to 80% by weight, more preferably 45 to 70% by weight, and particularly preferably 50 to 65% by weight, from the viewpoint of handleability of the composition and physical properties (mechanical strength, etc.) of the cured product. Is.
(B) is preferably 10 to 50% by weight, more preferably 15 to 45% by weight, and particularly preferably 20 to 40% by weight, from the viewpoint of handleability of the composition and physical properties (mechanical strength, etc.) of the cured product. Is.
From the viewpoint of volume change rate and handleability, (C) is preferably 3 to 40% by weight, more preferably 5 to 30% by weight, and particularly preferably 7 to 20% by weight.
(D) is preferably 0.5 to 7% by weight, more preferably 1 to 6% by weight, and particularly preferably 1.5 to 5% by weight from the viewpoint of volume change rate and physical properties (mechanical strength, etc.). be.
(E) is preferably 0.5 to 5% by weight, more preferably 1 to 4% by weight, and particularly preferably 2 to 3% by weight from the viewpoint of adhesive strength (particularly, adhesive strength on a wet surface). Is.

The molar ratio of the epoxy group (A) to the active hydrogen (B) [active hydrogen / epoxy group] is preferably 0.4 to 2.5, more preferably 0.4 to 2.5, from the viewpoint of the physical properties (mechanical strength) of the cured product. Is 0.5 to 2.0, particularly preferably 0.6 to 1.5.
The weight ratio (C / D) of (C) to (D) is preferably 30/70 to 98/2, more preferably 75/25 to 95/5, and even more preferably 80 /, from the viewpoint of the volume change rate. It is 20 to 92/8, particularly preferably 85/15 to 90/10.
The molar ratio (CaO / water) of calcium oxide and water (D) in the epoxy resin composition is preferably 0.1 to 5 from the viewpoint of volume change rate and physical properties (mechanical strength), and more preferably 1. ~ 4.
The weight ratio (C / E) between (C) and (E) is preferably 1 to 50, more preferably 2 to 30, from the viewpoint of adhesive strength (particularly, adhesive strength on a wet surface) and mechanical strength. , Particularly preferably 6 to 15.

[Ethylene oxide of polyol and / or alkylene oxide adduct (F) having 3 to 6 carbon atoms]
The epoxy resin composition of the present invention further contains a polyol ethylene oxide (hereinafter abbreviated as EO) and / or an adduct (F) having an alkylene oxide having 3 to 6 carbon atoms (hereinafter abbreviated as AO). Can be done. By containing (F), the thixotropic property of the epoxy resin composition can be enhanced. Further, the dispersion stability of water (D) with respect to the polyepoxyd (A) can be enhanced, and the day-to-day stability of the epoxy resin composition tends to be good.
Examples of the polyol include divalent to 8-valent or higher polyhydric alcohols (C2 to 30), divalent to 8-valent or higher polyhydric phenols (C6 to 40), and mixtures thereof.

Examples of the polyhydric alcohol include dihydric alcohols [eg, EG, PG, 1,3- or 1,4-butanediol, 1,6-HD, 3-methylpentanediol, diEG, NPG, 1,4-bis. (Hydroxymethyl) cyclohexane, 1,4-bis (hydroxyethyl) benzene, 2,2-bis (4,4'-hydroxycyclohexyl) propane], trihydric alcohols [eg GR, TMP], 4-8-valent alcohols [ For example, PE, diGR, α-methylglucoside, SO, xylit, mannit, diPE, glucose, fructose, sucrose] and the like.
The polyhydric phenol may be divalent [eg, hydroquinone, catechol, bisphenol-A, -F and S, naphthalenediol, anthracenediol], trivalent to octavalent or higher [eg, hydroxyquinol, pyrogallol, etc. Trishydroxyphenylisopropylbenzene [trade name "Trisphenol PA", manufactured by Mitsui Petrochemical Co., Ltd.], phenol novolak, cresol novolak] and the like can be mentioned.

Among these polyols, a polyhydric alcohol is preferable from the viewpoint of thixotropic properties of the epoxy resin composition, a polyhydric alcohol having a valence of 2 to 4 and C2 to 10 is more preferable, and a polyhydric alcohol having a valence of 2 to 3 is particularly preferable. ~ 6 polyhydric alcohols.
Examples of the AO include 1,2-propylene oxide (hereinafter abbreviated as PO), 1,3-propylene oxide, 1,2-, 2,3- or 1,3-butylene oxide, and 1,2-hexylene. Examples thereof include oxides, and PO is preferable from the viewpoint of thixotropic properties of the epoxy resin composition.

Of (F), from the viewpoint of thixotropic property, the one obtained by adding both EO and AO (C3 to 6) to the polyol is preferable. When both EO and AO (C3 to 6) are added, the addition form may be random addition or block addition, but from the viewpoint of thixotropic property, random addition is preferable.
The total average number of moles of EO and AO (C3 to 6) added to the polyol is preferably 3 to 150, more preferably 15 to 130, from the viewpoint of thixotropy and handleability of the epoxy resin composition.
The added molar number ratio (EO / AO) of EO and AO (C3 to 6) is preferably 0.2 to 10, more preferably 0.3 to 8 from the viewpoint of thixotropy of the composition and water resistance of the cured product. , Particularly preferably 0.5 to 7.
The Mn of the (F) is preferably 200 to 10,000, more preferably 1,000 to 8,000, from the viewpoint of thixotropy and handleability of the epoxy resin composition.

The production of (F), which is an EO and / or AO (C3-6) adduct of the polyol, can be carried out by a known method, and in the presence of a catalyst (alkali catalyst, amine catalyst, acid catalyst), normal pressure or It is performed in one step or multiple steps under pressure.

The GPC measurement conditions for Mn in the present invention are as follows.
Equipment: HLC-802A manufactured by Tosoh Corporation
Column: TSK gel GMH6 2 pieces Measurement temperature: 40 ° C
Sample solution: 0.5 wt% THF solution Injection amount: 200 μl
Detector: Refractive index detector Standard: Polystyrene

The amount of (F) used is based on the total weight of (A), (B), (C), (D) and (E), and the thixotropic property of the epoxy resin composition and the physical properties of the cured product (mechanical). From the viewpoint of strength and the like), it is preferably 0.1 to 5% by weight, more preferably 0.2 to 3% by weight, and particularly preferably 0.5 to 2% by weight.
The weight ratio (D / F) between (D) and (F) is 0.5 to 14 from the viewpoint of the secular stability of solution A when stored separately in the form of two solutions, which will be described later. preferable.

[Inorganic filler (G)]
The epoxy resin composition of the present invention may contain an inorganic filler (G), if necessary, in order to adjust the physical properties of the cured product (improve the compressive yield strength, compressive elastic modulus, etc.). Examples of the (G) include the following (G1) to (G7) and mixtures of two or more thereof, which are other than the above (C).
(G1) Silicates (eg talc, clay, mica, glass);
(G2) Oxides other than (C) [eg titanium oxide, alumina, silica];
(G3) Carbonates (eg calcium carbonate, magnesium carbonate, hydrotalcite);
(G4) Hydroxides (eg aluminum hydroxide, magnesium hydroxide, calcium hydroxide);
(G5) (sulphate) sulfate (eg barium sulfate, calcium sulfate, calcium sulfite);
(G6) Borate (eg zinc borate, barium borate, aluminum borate, calcium borate, sodium borate);
(G7) Nitride (eg, aluminum nitride, boron nitride, silicon nitride).

Of these (G), (G1), (G2), (G3) and (G4) are preferable, and (G1) is more preferable from the viewpoint of physical properties (mechanical strength, etc.) and industrial aspects of the cured product. ), (G2) and (G3), particularly preferred are silica and calcium carbonate.

The shape of (G) is preferably powder from the viewpoint of handleability of the epoxy resin composition. The volume average particle size of (G) is preferably 0.1 to 800 μm, more preferably 0.5 to 250 μm from the viewpoint of the viscosity and handleability of the epoxy resin composition.

The amount of (G) used is preferably 5 to 200 based on the total weight of (A), (B), (C), (D) and (E) from the viewpoint of physical properties and handleability of the cured product. By weight%, more preferably 10 to 190% by weight, and particularly preferably 20 to 180% by weight.

In the epoxy resin composition, as long as the effect of the present invention is not impaired, (1) a curing accelerator (tertiary amino compound, an alkaline compound other than the above (C), a Lewis basic compound, etc.), (1) 2) Adhesive-imparting agents (titanium coupling agents, etc.), (3) Antioxidants (hindered amines, hydroquinones, hindered phenols, sulfur-containing compounds, etc.), (4) Ultraviolet absorbers (benzophenones, benzotriazoles, etc.) , Salicylic acid esters, metal complex salts, etc.), (5) Plasticizers (phthalic acid esters, phosphoric acid esters, fatty acid esters, epoxidized soybean oil, castor oil, liquid paraffin alkyl polycyclic aromatic hydrocarbons, etc.), (6) ) Waxes (paraffin wax, microcrystallin wax, polymerized wax, beeswax, whale wax, low molecular weight polyolefin, etc.), (7) non-reactive diluents (benzyl alcohol, tar, pitumen, etc.), (8) reactive dilutions Agents (low molecular weight aliphatic glycidyl ethers, aromatic monoglycidyl ethers, etc.), (9) Organic fillers [aramid fiber powder, nylon fiber powder, acrylic fiber powder, acrylic resin powder, phenol resin powder, etc.], (10) Deodorization Agents [Activated charcoal, zeolite, etc.], (11) Pigments or dyes [Carbon black, lead tan, parared, navy blue, etc.], (12) Tixogenic agents [Bentnite, hydrogenated castor oil wax, calcium stearate, etc.], (13) Solvents (ethyl acetate, toluene, alcohol, ether, ketones, etc.), (14) foaming agents, (15) antifoaming agents, (16) antistatic agents, (17) antibacterial agents, (18) antifungal agents, (19) ) Additives (H) such as viscosity modifiers, (20) fragrances, and (21) flame retardants can be contained.

The epoxy resin composition of the present invention is produced by the following method (1) or (2).
(1) (A), (B), (C), (D), (E), and if necessary, (F), (G), (H) are collectively mixed immediately before use to form a composition. ..
(2) Two liquids [a liquid containing (A) and a liquid B containing (B)] are separately produced and mixed at the time of use to form a composition. (C), (D) and (E) are preferably mixed with the liquid A or the liquid B in advance, and the (C) and (E) are further mixed with the liquid B and the (D) with the liquid A. preferable. Further, (F) to be contained as necessary may be mixed with the liquid A and / or the liquid B in advance, or may be mixed at the time of use, but from the viewpoint of thixotropic property and handleability, the liquid A and / or the liquid B may be mixed. It is preferable to mix with the liquid A in advance from the viewpoint of the dispersion stability of the water (D) and the circadian stability of the liquid A. From the same viewpoint, it is preferable to mix (G) and (H), which are contained if necessary, with the liquid A and / or the liquid B in advance.
Among the forms of these compositions, the form (2) is preferable from an industrial point of view.
In any of these cases (1) and (2), the reactions of (A) and (B), (C) and (D), and (D) and (E) proceed promptly after mixing, respectively. It is desirable to use. The pot life after mixing (A), (B), (C), (D) and (E) is (A), (B), (C), (D) and (E). When each temperature is 15 to 35 ° C., it is preferably 5 to 180 minutes, more preferably 10 to 90 minutes.
Here, the pot life means that each component [total amount 120 g] whose temperature has been adjusted to 25 ° C. is mixed, and the viscosity in a constant temperature bath at 25 ° C. after uniform mixing from the start of mixing is 100. It shall mean the time until reaching (Pa · s).

Examples of the mixing method of (A), (B), (C), (D), (E), and (F), (G), (H) to be contained as necessary in the present invention include a universal mixer and the like. A method using the mixer of the above and a method of using the mixer described later can be mentioned.
The viscosity (Pa · s) of the epoxy resin composition at 25 ° C. is preferably 20 to 90, more preferably 30 to 85, and particularly preferably 40 to 80, from the viewpoint of sagging prevention and handleability.

The measurement conditions for the viscosity are as follows, for example.
Equipment: BH type viscometer [model number "TVB-22H", manufactured by Toki Sangyo Co., Ltd.]
Rotation speed: 20 rpm
Spindle No .: No. 7

The epoxy resin composition of the present invention is excellent in handleability and physical properties of a cured product, and has extremely little volume shrinkage during curing or moderate volume expansion. Therefore, it can be used for various uses, adhesives, molded products, grout materials for reinforcing bar joints, etc., and is particularly suitable as a grout material for reinforcing bar joints. The volume shrinkage and volume expansion can be evaluated by the volume change rate (%) before and after curing, which will be described later. The volume change rate is preferably 97 to 110%, more preferably 98 to 105%, and particularly preferably 99 to 103%.
Further, especially in applications where dimensional stability is desired, the volume change rate is preferably 99 to 101%.

The epoxy resin composition of the present invention has extremely small volume shrinkage during curing or moderately expands during curing, so that volume shrinkage can be suppressed and adhesiveness to a wet surface is excellent. In addition, since the effect of deterioration of physical properties due to the formulation of silane coupling is small and a cured product with excellent mechanical strength can be obtained, it may be used in a state where the adhesive surface is wet due to rainfall or the like. It can be preferably used as (repair / reinforcement work for structures such as concrete structures and steel structures, crack injection, and adhesives for post-construction anchors), and is particularly useful as adhesives for post-construction anchors.
"Post-construction anchor" means to bury anchor members such as anchor bolts and stirrups later in concrete structures (hereinafter referred to as base materials) that have already been manufactured in the fields of civil engineering, construction, machinery, etc. It is a construction method to be done. The epoxy resin composition of the present invention can be used as an adhesive between the base material and the anchor member when the metal anchor member is embedded in the base material. Specifically, the anchor member is charged into the hole formed in the base material, and the epoxy resin composition of the present invention is poured into the hole to firmly bond the hole wall portion and the anchor member. Can be done.

Further, since the epoxy resin composition of the present invention has excellent adhesiveness to a wet surface, the influence of the water content of wood on the adhesive strength is small, so that it can be preferably used as an adhesive for wood, and in particular. It is useful as an adhesive for the GIR method.
The "GIR method" is a construction method in which a hole is made in wood and an adhesive is injected and filled in a gap between a rod-shaped joint fitting inserted therein.

Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not limited thereto. The part in the embodiment represents a weight part.

[Manufacturing of EO and / or AO (C3-6) adduct (F) of polyol]
Production Example 1
30 parts of propylene glycol and 0.15 parts of potassium hydroxide as a catalyst were charged in an autoclave, and a mixture of 693 parts of EO and 277 parts of PO was blown into the autoclave and reacted at 110 ° C. After aging at 130 ° C., the catalyst is removed by adsorption treatment with a magnesium oxide-based adsorbent [trade name "Kyoward 600", manufactured by Kyowa Chemical Industry Co., Ltd.], and EO and PO adducts of propylene glycol (F-1). (Mn3,000, average number of moles of EO and PO added 52, EO / PO added mole ratio = 3.3) 992 parts were obtained.

Production of Liquid A (Production Examples 2 to 7)
Using a universal mixer [trade name “Universal Mixer 5DMV-01-r”, manufactured by Dalton Co., Ltd.], the mixture was blended according to Table 1 to obtain Liquid A. 30 g of the obtained solution A was placed in a centrifuge tube (50 mL), and an accelerated test was performed with a centrifuge (2000 rpm × 30 minutes × 4 times, total 2 hours). The state of the liquid after centrifugation was visually confirmed and evaluated according to the following evaluation criteria. The results are shown in Table 1.
◯: No separation even after 2 hours Δ: Not separated after 1 hour, but separated after 2 hours ×: Separated after 30 minutes or 1 hour

表１の結果から重量比（Ｄ／Ｆ）が０．７～１４である製造例２～４は、分離しにくく、経日安定性が良好であることが分かる。

From the results in Table 1, it can be seen that Production Examples 2 to 4 having a weight ratio (D / F) of 0.7 to 14 are difficult to separate and have good circadian stability.

Examples 1 to 13 and Comparative Examples 1 to 5
Using a universal mixer [trade name "Universal Mixer 5DMV-01-r", manufactured by Dalton Co., Ltd.], liquids A and B were mixed according to Table 2, respectively, and mixed while defoaming under reduced pressure (temperature 25). The temperature was changed to 5 minutes with a stirring time of 4 kPa) to obtain solutions A and B. Furthermore, using a centrifugal defoamer [trade name "Awatori Rentaro ARV930TWIN", manufactured by Shinky Co., Ltd.], solutions A and B are mixed at the weight ratios shown in Table 2 (temperature 25 ° C., stirring time 3 minutes). , Rotation speed 1400 rpm) to obtain an epoxy resin composition. The performance of the composition was evaluated by the following test method. The results are shown in Table 2.

Each abbreviation in Table 2 is as follows.
A-1: Bisphenol F type diglycidyl ether [trade name "JER807", manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 175]
A-2: Neopentyl glycol diglycidyl ether [Product name: "Ex-211", manufactured by Nagase ChemteX Corporation,
Epoxy equivalent 138]
B-1: Xylylenediamine [Product name "Ancamin 2422", manufactured by Air Products Japan Co., Ltd.,
Active hydrogen equivalent 34, number of active hydrogen directly linked to N atom 4]
B-2: 1,3-bisaminomethylcyclohexane [Product name "1-3BAC", manufactured by Mitsubishi Gas Chemical Company, Inc.,
Active hydrogen equivalent 36, 4 active hydrogens directly linked to N atom]
C-1: Calcium oxide [Product name "Pacific Hyper Expand (for structure)",
Made by Pacific Material Co., Ltd., calcium oxide content 70% by weight,
Volume average particle diameter 50 μm]
C-2: Calcium sulfoluminate [Product name "Denka Power CSA Type S", manufactured by Denki Kagaku Kogyo Co., Ltd.,
Calcium oxide content 50% by weight, volume average particle diameter 60 μm]
D-1: Ion-exchanged water E-1: N-2- (aminoethyl) -3-aminopropyltrimethoxysilane [Product name "KBM-603", manufactured by Shin-Etsu Chemical Co., Ltd.]
E-2: 3-Aminopropyltrimethoxysilane [Product name "KBM-903", manufactured by Shin-Etsu Chemical Co., Ltd.]
E-3: 3-glycidoxypropyltrimethoxysilane [trade name "KBM-403", manufactured by Shin-Etsu Chemical Co., Ltd.]
E-4: 3-Mercaptopropyltrimethoxysilane [Product name "KBM-803", manufactured by Shin-Etsu Chemical Co., Ltd.]
F-1: Propylene glycol EO / PO random adduct [Mn3,000 obtained in Production Example 1, average number of moles of EO and PO added 52,
EO / PO addition molar ratio = 3.3]
G-1: Calcium carbonate [Product name "Softon 1500", manufactured by Shiraishi Calcium Co., Ltd.,
Volume average particle diameter 1.5 μm]
G-2: Silica [Product name: HS-106, manufactured by Micron Co., Ltd., volume average particle diameter 20 μm]

<Test method>
[Volume change rate before and after curing] (Unit:%)
(1) The epoxy resin composition whose temperature was adjusted to 25 ° C. was measured with a high-precision electronic hydrometer [model number "SD-200L", manufactured by Alpha Mirage Co., Ltd.] by the specific gravity bottle method according to JIS K0061. The specific gravity before curing (d1) was used.
(2) The obtained epoxy resin composition was formed into a plate having a thickness of about 10 mm, cured at 25 ° C. for 5 days, and then a rectangular test piece having a thickness of about 10 × 10 × 30 mm was cut out. The test piece whose temperature was adjusted to 25 ° C. was measured with a high-precision electronic hydrometer [model number "SD-200L", manufactured by Alpha Mirage Co., Ltd.] by the balance method according to JIS K0061, and the specific gravity after curing (d2). ).
(3) The volume change rate was calculated from the specific gravity (d1) before curing and the specific gravity (d2) after curing by the following equation (1). If the rate of change in volume is less than 100%, the composition is shrunk, and if it is larger, it is expanded.
[Volume change rate (%) before and after curing] = (1 / d2) x 100 / (1 / d1) (1)
d1: Specific density before curing d2: Specific density after curing

[Compressive yield strength (compressive yield stress), compressive elastic modulus (compressive elastic modulus)] (Unit: N / mm ² for both)
The kneaded epoxy resin composition was formed into a plate having a thickness of about 10 mm, and cured at 25 ° C. for 5 days to cure. A rectangular parallelepiped test piece having a thickness of about 10 mm, a width of about 10 mm, and a length of about 30 mm was cut out and measured according to JIS K7181 except that the test speed was changed to 2 mm / min.

[Adhesive strength between steel plates (superimposed shear adhesive strength)] (Unit: N / mm ² )
A cold-rolled steel sheet with a thickness of about 1.6 mm, a width of about 25 mm, and a length of about 100 mm specified in JIS G3141 is washed with acetone, and the stacking length is 12.5 mm and the thickness of the adhesive layer is 0.2 mm. A test piece was obtained by adhering two cold-rolled steel sheets with an epoxy resin composition kneaded so as to be. After curing the test piece at 25 ° C. for 5 days, the adhesive strength (superimposed shear adhesive strength) of the normal surface was measured according to JIS K6850 at a test rate of 10 mm / min.
As for the adhesive strength of the wet surface (superimposed shear adhesive strength), the two cold-rolled steel sheets after being washed with acetone were placed in a high-temperature and high-humidity device (75 ° C, 95%) overnight. It was measured in the same manner as on a normal surface except that a test piece was obtained by adhering with an epoxy resin composition which was immediately kneaded after being taken out of a high temperature and high humidity device. The values of the superposed shear adhesive strength shown in Table 2 are the average values of the results of the five tests.

[Adhesive strength between woods (compressive shear adhesive strength)] (Unit: N / mm ² )
<Normal test>
An epoxy resin composition in which 25 mm × 30 mm × 15 mm thick white wood is used as an adherend and the 25 mm × 30 mm surfaces of the two adherends are kneaded so that the thickness of the adhesive layer is 0.2 mm. A test piece was obtained by adhering with. After curing at 25 ° C. for 5 days, the compression shear adhesion strength was measured according to JIS K6852 at a test rate of 2 mm / min. In addition, the state of fracture in the adherend when the test piece was fractured was investigated, and the percentage of the fractured area with respect to the shear area was read to obtain the xylem fracture rate (unit:%), which is shown in parentheses. The values of the compression shear adhesive strength and the xylem breaking rate shown in Table 2 are the average values of the results of the five tests.
<Hot water resistance test>
A test piece was obtained in the same manner as in the normal test and cured at 25 ° C. for 5 days. The test piece was immersed in warm water at 60 ° C. for 3 hours, then immersed in water at room temperature until it cooled, and the test was carried out in a wet state.
<Repeated boiling test>
A test piece was obtained in the same manner as in the normal test and cured at 25 ° C. for 5 days. The test piece is immersed in boiling water for 4 hours, dried in air at 60 ° C. for 20 hours, and then immersed in boiling water again for 4 hours. After this treatment, it was immersed in water at room temperature until it cooled, and the test was carried out in a wet state.

From the results in Table 2, the epoxy resin compositions of Examples 1 to 13 can suppress volume shrinkage during curing, have excellent adhesion to a wet surface, and obtain a cured product having excellent mechanical strength. You can see that you can do it.
On the other hand, when the same Comparative Example 1 and Example 1 are compared except that the leavening agent (C) is not used, the volume change due to curing is large, the adhesiveness is low, and the adhesiveness is extremely inferior especially under wet conditions. I understand. Further, when the same Comparative Example 2 and Example 1 are compared except that the silane coupling agent (E) is not used, the volume change due to curing is large, the adhesiveness is low, and the adhesiveness is extremely high especially under wet conditions. It turns out to be inferior. Further, Comparative Example 3 using a large amount of the silane coupling agent (E) has the same or higher adhesiveness as that of Example 7 except that the swelling agent (C) is used, but is due to curing. It can be seen that the volume change is large and the mechanical strength (compressive yield strength, compressive elastic modulus) is extremely low. Further, it can be seen that Comparative Example 4 having a molar ratio (CaO / alkoxy group) of less than 1 has the same volume shrinkage as that of Example 1, but is inferior in adhesiveness and extremely inferior in mechanical strength. .. Further, it can be seen that Comparative Example 5 having a molar ratio (CaO / alkoxy group) of more than 40 has the same mechanical strength as that of Example 6, but has a large volume change and extremely low adhesiveness.

The epoxy resin composition of the present invention can suppress volume shrinkage of the epoxy resin composition during curing, and can obtain a cured product having excellent adhesiveness to a wet surface and excellent mechanical strength. It can be used for repair / reinforcement work of structures such as concrete structures and steel structures, crack injection, and as an adhesive for post-installed anchors, and is particularly useful as an adhesive for post-installed anchors. It can also be preferably used as an adhesive for wood, and is particularly useful as an adhesive for the GIR method.

Claims (7)

An epoxy resin composition containing a polyepoxide (A), a polyamine (B) having 2 to 50 active hydrogens directly linked to N atoms, a swelling agent (C), water (D), and a silane coupling agent (E). The swelling agent (C) contains calcium oxide, and the silane coupling agent (E) is at least selected from the group consisting of at least one alkoxy group bonded to a silicon atom and an amino group, a mercapto group and an epoxy group. It is a compound having at least one functional group of one kind, and has a molar ratio (CaO /) of calcium oxide in the swelling agent (C) and an alkoxy group bonded to a silicon atom in the silane coupling agent (E). An epoxy resin composition having 1 to 40 alkoxy groups). The claim that the content of the silane coupling agent (E) is 0.5 to 5% by weight based on the total weight of the (A), (B), (C), (D) and (E). The epoxy resin composition according to 1. The epoxy resin composition according to claim 1 or 2, which contains ethylene oxide of a polyol and / or an alkylene oxide adduct (F) having 3 to 6 carbon atoms. The epoxy resin composition according to claim 3, wherein the weight ratio (D / F) of the water (D) and the alkylene oxide adduct (F) is 0.5 to 14. The epoxy resin composition according to any one of claims 1 to 4, wherein the molar ratio (CaO / water) of calcium oxide and water (D) in the epoxy resin composition is 0.1 to 5. The epoxy resin composition according to any one of claims 1 to 5, which is an adhesive for civil engineering and construction. A cured product obtained by curing the epoxy resin composition according to any one of claims 1 to 6.