Two-component curing epoxy resin composition

Abstract

The objective is to provide a two-component epoxy resin composition that has good injectability and storage stability, is less prone to sagging, and yields a cured product with excellent strength. [Solution] A two-component curable epoxy resin composition comprising an epoxy compound (A), an amine compound (B), an inorganic thixotropic agent (C1), and an organic thixotropic agent (C2), wherein the inorganic thixotropic agent (C1) is silica with a hydrophobic surface treatment, and the mass ratio (C1:C2) of the inorganic thixotropic agent (C1) to the organic thixotropic agent (C2) is in the range of 1:0.2 to 1:1.

Description

Technical Field

[0001] The present invention relates to a two-part curable epoxy resin composition.

Background Art

[0002] 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. On the other hand, in the civil engineering and construction fields, large two-part cartridge systems are often used for process reduction and simplification from the viewpoint of workability due to chronic labor shortages.

[0003] However, in large cartridge systems, solid-liquid separation of the base compound and the curing agent tends to occur, making it difficult to maintain uniformity. In addition, increasing the viscosity to maintain uniformity degrades discharge performance, so there remains a challenge to achieve both storage stability and discharge performance. For example, Patent Document 1 develops an epoxy resin composition that has a low viscosity and is less prone to sagging by adding an organic thixotropy-imparting agent, but it does not have sufficient storage stability in large cartridges.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of Invention

Problems to be Solved by the Invention

[0005] An object of the present invention is to provide a two-part curable epoxy resin composition that has good injectability and storage stability, is less prone to sagging, and can give a cured product with excellent strength.

Means for Solving the Problems

[0006] The present inventors have arrived at the present invention as a result of their studies in order to achieve the above objective. Specifically, the present invention is a two-component curable epoxy resin composition comprising an epoxy compound (A), an amine compound (B), an inorganic thixotropic agent (C1), and an organic thixotropic agent (C2), wherein the inorganic thixotropic agent (C1) is silica with a hydrophobic surface treatment, and the mass ratio (C1:C2) of the inorganic thixotropic agent (C1) to the organic thixotropic agent (C2) is in the range of 1:0.2 to 1:1. [Effects of the Invention]

[0007] The two-component curable epoxy resin composition of the present invention exhibits good injectability and storage stability, is less prone to sagging, and has excellent strength. [Modes for carrying out the invention]

[0008] The two-component curable epoxy resin composition of the present invention comprises an epoxy compound (A), an amine compound (B), an inorganic thixotropic agent (C1), and an organic thixotropic agent (C2), wherein the inorganic thixotropic agent (C1) is silica with a hydrophobic surface treatment, and the mass ratio (C1:C2) of the inorganic thixotropic agent (C1) to the organic thixotropic agent (C2) is in the range of 1:0.2 to 1:1.

[0009] <Epoxy compound (A)> The epoxy compound (A) in the present invention has two or more epoxy groups in its molecule, and examples include polyglycidyl ether (A1), polyglycidyl ester (A2), polyglycidylamine (A3) of the polyamine, and other epoxy compounds (A4). From the viewpoint of the mechanical strength and workability of the cured product, the number of epoxy groups is preferably 2 to 10, and more preferably 2 to 6.

[0010] Polyglycidyl ether (A1) Polyglycidyl ethers (A1) are polyglycidyl compounds having a structure in which a hydrogen atom bonded to a hydroxyl group of a polyol compound is replaced with a glycidyl group, and examples include the following polyglycidyl ethers (A11) to (A16). Diglycidyl ether (A11) of divalent phenol [with 6 to 30 carbon atoms (hereinafter sometimes abbreviated as C)] For example, diglycidyl ethers of bisphenols (bisphenol F, -A, -B, -AD, and -S, etc.), diglycidyl ethers of halogenated bisphenol A (tetrachlorobisphenol A, etc.), diglycidyl ethers of monocyclic divalent phenols (catechol, resorcinol, hydroquinone, etc.), diglycidyl ethers of condensed polycyclic divalent phenols [1,5-dihydroxynaphthalene, dihydroxybiphenyl, octachloro-4,4'-dihydroxybiphenyl, 9,9'-bis(4-hydroxyphenyl)fluorene, etc.], diglycidyl ethers obtained from the reaction of 2 moles of bisphenol A and 3 moles of epichlorohydrin, etc.

[0011] Polyglycidyl ethers (A12) of polyvalent (trivalent to hexavalent or higher) phenols For example, polyglycidyl ethers of polyhydric phenols (C6 or higher and number-average molecular weight of 5,000 or less (hereinafter, the number-average molecular weight may be abbreviated as Mn)), triglycidyl ethers of trihydric phenols [pyrogallol, dihydroxynaphthylcresol, tris(hydroxyphenyl)methane, dinaphthyltriol, p-glycidylphenyldimethyltriolbisphenol A, etc.], and tetraglycidyl ethers of tetrahydric phenols [tetrakis(4-hydroxyphenyl)ethane, 4,4'-oxybis(1,4-phenylethyl)tetracresol, bis(dihydroxynaphthalene, etc.)] Polyglycidyl ethers of phenol novolac resins (Mn 400-5,000), polyglycidyl ethers of cresol novolac resins (Mn 400-5,000), polyglycidyl ethers of limonene phenol novolac resins (Mn 400-5,000), polyglycidyl ethers of polyphenols (Mn 400-5,000) obtained by condensation reactions of phenol with glyoxal, glutaraldehyde, or formaldehyde, and polyglycidyl ethers of polyphenols (Mn 400-5,000) obtained by condensation reactions of resorcinol with acetone, etc.

[0012] Diglycidyl ether (A13) of aliphatic diols (C2 or higher and Mn 5,000 or less) For example, diglycidyl ethers of aliphatic diols [dihydric alcohols [e.g., ethylene glycol, propylene glycol, tetramethylene glycol, neopentyl glycol, 1,6-hexanediol (hereinafter abbreviated as EG, PG, TMG, NPG, and 1,6-HD respectively)], polyalkylene glycols [e.g., polyethylene glycol (hereinafter abbreviated as PEG; molecular weight 106 or more and Mn 4,000 or less), polypropylene glycol (hereinafter abbreviated as PPG; molecular weight 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.];

[0013] Polyglycidyl ethers (A14) of aliphatic poly(trivalent to hexavalent or higher) all (C6 or higher and Mn 10,000 or less) For example, polyglycidyl ethers of aliphatic polyols [polyhydric (3-6 hydric) alcohols [trimethylolpropane, glycerin, pentaerythritol, sorbitol (hereinafter abbreviated as TMP, GR, PE, SO respectively)], intramolecular or intermolecular dehydrated products of polyhydric alcohols [poly(n=2-5)GR], and alkylene oxide adducts of these polyhydric alcohols [hereinafter abbreviated as AO; C2-6, e.g., ethylene oxide, 1,2-propylene oxide (hereinafter abbreviated as EO, PO respectively)], etc.;

[0014] Polyglycidyl ether (A15) of alicyclic poly(divalent to tetravalent or higher)ols For example, polyglycidyl ethers such as those with C3 or higher and Mn 5,000 or less, such as 1,2-cyclopropanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-cyclohexanediol, hydrogenated bisphenol A, 1,2,3-cyclopropanetriol, 1,3,5-cyclohexanetriol, sucrose, and AO (1-20 mol) adducts thereof;

[0015] Polyglycidyl ethers (A16) of aromatic aliphatic polyvalent (divalent to tetravalent or higher) alcohols Examples include polyglycidyl ethers such as those with C8 or higher and Mn 5,000 or lower, for example, AO(1-20 mol) adducts of divalent phenols {containing the aforementioned divalent phenols, such as bisphenol A}, aromatic aliphatic alcohols {for example, m- or p-xylylene glycol, benzenediethanol, 1,2-diphenylethane-1,2-diol, 1,1,2,2-tetraphenylethane-1,2-diol}, and AO(1-20 mol) adducts of aromatic aliphatic alcohols.

[0016] Polyglycidyl ester (A2) Polyglycidyl esters (A2) are polyglycidyl compounds having a structure in which a hydrogen atom of the carboxyl group of a polycarboxylic acid compound is replaced with a glycidyl group, and examples include the following polyglycidyl esters (A21) to (A22). Polyglycidyl ester of aromatic polyvalent (divalent to hexavalent or higher) carboxylic acid (A21) Polyglycidyl esters of aromatic polyvalent carboxylic acids (C6 to C20 or higher), for example, diglycidyl esters of aromatic dicarboxylic acids (ortho-, iso- and terephthalic acid, etc.), triglycidyl esters of aromatic tricarboxylic acids (trimellitic acid, etc.), etc.; Polyglycidyl ester of aliphatic or alicyclic-containing polyvalent carboxylic acid (C6 to C20 or higher) (A22) Examples include diglycidyl esters of aliphatic dicarboxylic acids (oxalic acid, maleic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, etc.), triglycidyl esters of aliphatic tricarboxylic acids (tricarballylic acid, etc.), (co)polymers of glycidyl (meth)acrylate (degree of polymerization is 2 to 10), polyglycidyl esters of alicyclic-containing polyvalent carboxylic acids (dimer acid, etc.), and nuclear hydrogenated products of the aforementioned (A21).

[0017] Polyglycidyl amine of polyamine (A3) The polyglycidyl amine of polyamine (A3) is a polyglycidyl compound having a structure in which hydrogen atoms bonded to nitrogen atoms contained in the polyamine are substituted with glycidyl groups. The polyamine is preferably an amine having 2 to 10 or more active hydrogens directly bonded to nitrogen atoms, with 6 to 20 or more carbon atoms, and examples of the polyglycidyl amine of polyamine (A3) include the following polyglycidyl amines of (A31) to (A33). Polyglycidyl amine of aromatic amine (A31) For example, N,N-diglycidylaniline, N,N-diglycidyltoluidine, N,N,N',N'-tetraglycidyldiaminodiphenylmethane, N,N,N',N'-tetraglycidyldiaminodiphenylsulfone, N,N,N',N'-tetraglycidyl-bis(4-amino-3,5-diethylphenyl)methane, N,N,O-triglycidylaminophenol, etc.; Polyglycidyl amine of aliphatic amine (A32) For example, N,N,N',N'-tetraglycidylhexamethylenediamine, etc.; Polyglycidylamine of aromatic aliphatic amine (A33) For example, N,N,N',N'-tetraglycidylxylylenediamine, etc.; Polyglycidylamine (A33) of alicyclic ring-containing or heterocyclic ring-containing amine (C6 to C20 or more, having 2 to 10 or more active hydrogens directly bonded to nitrogen atoms) Polyglycidylamine of alicyclic ring-containing amine (for example, hydrogenated product of N,N,N',N'-tetraglycidylxylylenediamine), polyglycidylamine of heterocyclic ring-containing amine (for example, trisglycidylmelamine), etc.;

[0018] Other epoxy compounds (A4) The other epoxy compounds are epoxy compounds other than the aforementioned (A1) to (A3), and examples include the following epoxy compounds (A41) to (A42). Aliphatic poly(divalent to hexavalent or higher) epoxide (A41) Those with C6 or more and Mn of 2,500 or less, for example, epoxidized polybutadiene, epoxidized soybean oil; Alicyclic poly(divalent to tetravalent or higher) epoxide (A42) Those with C6 or more and Mn of 2,500 or less, for example, vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, 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, and the like.

[0019] From the viewpoint of the mechanical strength of the cured product of the two-component curable epoxy resin composition, it is preferable to contain an epoxy compound having a bisphenol A type structure or a bisphenol F type structure in its molecule, more preferably to contain an epoxy compound having a bisphenol A type structure or a bisphenol F type structure among (A11) and (A12), and it is particularly preferable that the total weight of the epoxy compounds having a bisphenol A type structure or a bisphenol F type structure is 70 to 100% by weight based on the weight of epoxy compound (A). Epoxy compound (A) may be used alone or in combination of two or more types.

[0020] The epoxy equivalent (molecular weight per epoxy group) (g / eq) of epoxy compound (A) is preferably 120 to 200 g / eq, more preferably 130 to 180 g / eq, and particularly preferably 140 to 180 g / eq, from the viewpoint of workability (injectability, etc.) of the two-component curable epoxy resin composition, curability, and mechanical strength of the cured product. The epoxy equivalent (g / eq) of epoxy compound (A) shall be the value measured in accordance with JIS K 7236.

[0021] The viscosity (mPa·s) of epoxy compound (A) at 25°C is preferably 500 to 10,000 mPa·s, and more preferably 1,000 to 7,000 mPa·s, from the viewpoint of workability (injectability, etc.) and storage stability of the two-component curable epoxy resin composition. The viscosity (mPa·s) of epoxy compound (A) at 25°C can be measured using a B-type viscometer.

[0022] The number-average molecular weight of epoxy compound (A) is obtained by measuring it using gel permeation column chromatography (GPC) under the following conditions. Model: HLC-8220GPC [Tosoh Corporation, liquid chromatograph] Column: TSK gel SuperH4000 TSK Gel SuperH3000 TSK gel SuperH2000 (All manufactured by Tosoh Corporation) Column temperature: 40℃ Detector: RI Solvent: tetrahydrofuran Flow rate: 0.6ml / min Sample concentration: 0.25% by weight Injection volume: 10μl Standard material: Polystyrene [Manufactured by Tosoh Corporation; TSK STANDARD]

[0023] <Amine compound (B)> The amine compound (B) of the present invention is not particularly limited as long as it is a compound having two or more active hydrogens derived from amino groups in its molecule, and can be appropriately selected depending on the application and purpose. From the viewpoint of the mechanical strength and handling properties of the resulting cured product, it is preferably a compound having 2 to 10 active hydrogens derived from amino groups in its molecule, and more preferably a compound having 3 to 8 active hydrogens derived from amino groups in its molecule. The active hydrogen equivalent (molecular weight per active hydrogen atom) of amine compound (B) is preferably 15 to 500, and more preferably 20 to 200. When the active hydrogen equivalent is 500 or less, the crosslinking structure does not become loose, and the physical properties such as adhesion and durability of the cured product tend to be good. When the active hydrogen equivalent is 15 or more, the physical properties such as adhesion, durability, and chemical resistance of the cured product tend to be good.

[0024] Examples of amine compounds (B) include the following aliphatic polyamines (2-18 carbon atoms, 2-7 functional groups, molecular weight 60-500) (B1), alicyclic polyamines (4-15 carbon atoms, 2-3 functional groups) (B2), heterocyclic polyamines (4-15 carbon atoms, 2-3 functional groups) (B3), polyamide polyamines (B4), polyether polyamines (B5), epoxy-added polyamines (B6), cyanoethylated polyamines (B7), and other polyamine compounds (B8). The number-average molecular weights of (B4) to (B8) can be measured using the same method as for the number-average molecular weight of the epoxy compound (A). Aliphatic polyamines (2-18 carbon atoms, 2-7 functional groups, molecular weight 60-500) (B1) (i) Aliphatic polyamines {alkylenediamines with 2 to 6 carbon atoms (ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, 2,5-dimethyl-2,5-hexamethylenediamine, etc.), polyalkylene (2 to 6 carbon atoms) polyamines [diethylenetriamine, iminobispropylamine, bis(hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.]}; (ii) Compounds in which the active hydrogen of (B1) is partially substituted with alkyl (1-4 carbon atoms) or hydroxyalkyl (2-4 carbon atoms) groups [e.g., dialkyl (1-3 carbon atoms) aminopropylamine, dialkyl (1-3 carbon atoms) aminohexamethyleneamine, aminoethylethanolamine, 3,3'-(methylimino)bis(1-propaneamine), etc.]; (iii) Alicyclic or heterocyclic aliphatic polyamines [such as 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5,5]undecane]; (iv) Aromatic ring-containing aliphatic amines (8-15 carbon atoms) (e.g., xylylenediamine, tetrachlor-p-xylylenediamine) are examples.

[0025] Alicyclic polyamines (4-15 carbon atoms, 2-3 functional groups) (B2) 1,3-diaminocyclohexane, isophoronediamine, mensendiamine, 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline), etc. Heterocyclic polyamines (4-15 carbon atoms, 2-3 functional groups) (B3) Piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4-bis(2-amino-2-methylpropyl)piperazine, etc. Polyamide polyamine (B4) Polyamide polyamines (number-average molecular weight 200-1000), etc., obtained by condensation of dicarboxylic acids (such as dimer acids) with an excess of polyamines (2 moles or more per mole of acid) (such as alkylenediamines and polyalkylene polyamines with 2-7 functional groups); Polyetherpolyamine (B5) Hydrogenated cyanoethylated polyether polyols (such as the aforementioned polyalkylene glycos) (number average molecular weight 100-1000), etc. Epoxy-added polyamine (B6) Epoxy-added polyamines (number average molecular weight 100-1000), etc., obtained by adding 1 mole of epoxy compound (the above epoxy compound (A) and monofunctional epoxide (F)) to polyamines (the above alkylenediamine, polyalkylene polyamine, etc.) in amounts of 1 to 30 moles;

[0026] Cyanoethylated polyamine (B7) Cyanoethylated polyamines obtained by the addition reaction of acrylonitrile with polyamines (such as the alkylenediamines and polyalkylene polyamines mentioned above), such as biscyanoethyldiethylenetriamine (number average molecular weight 100-500); Other polyamine compounds (B8) (i) Hydrazines (hydrazines, monoalkylhydrazines, etc.) (ii) Dihydrazides (such as succinate dihydrazide, adipic acid dihydrazide, isophthalate dihydrazide, terephthalate dihydrazide, etc.) (iii) Guanidines (butylguanidine, 1-cyanoguanidine, etc.) (iv) Dicyandiamides, etc., and mixtures of two or more of these. Of the above (B1) to (B8), (B1), (B2), (B3), (B4), and (B6) are preferred from the viewpoint of the mechanical strength of the resulting cured product, and (B1) and (B6) are particularly preferred.

[0027] <Inorganic thixotropic agent (C1)> The present invention relates to a two-component curable epoxy resin composition, preferably comprising a main component containing an epoxy compound (A) and a curing agent containing an amine compound (B). The two-component curable epoxy resin composition of the present invention contains an inorganic thixotropic agent (C1) and an organic thixotropic agent (C2), but (C1) and (C2) may be included in either the main component or the curing agent. From the viewpoint of workability and storage stability, the two-component curable epoxy resin composition of the present invention preferably contains an inorganic thixotropic agent (C1) in both the main component and the curing agent. Examples of inorganic thixotropic agents (C1) include hydrophobic silica.

[0028] Examples of silica particles include silica particles obtained by melting (fused silica), silica particles obtained by gas-phase reaction of silicon, silica particles obtained by sol-gel method, and silica particles obtained by combustion hydrolysis (a method of hydrolyzing volatile silicon compounds at high temperatures in an oxyhydrogen flame) (fumed silica). From the viewpoint of sedimentation properties, fumed silica is preferred as the silica.

[0029] From the viewpoint of sedimentation properties, the average particle size of silica is preferably 1 to 100 nm, more preferably 1 to 50 nm, and most preferably 5 to 40 nm. Here, the average particle diameter is the average particle diameter of primary particles calculated from the BET specific surface area, and is the average primary particle diameter measured from approximately 300 particles in a photograph (25k) observed with a transmission electron microscope [JEOL Ltd. JEM-F200]. Here, the average primary particle diameter is the particle diameter (equivalent circle diameter) of each particle, where the diameter of a circle with an area equivalent to the area obtained from the photograph is defined as the particle diameter (equivalent circle diameter), and this is averaged over all measured particles.

[0030] Hydrophobic surface-treated silica refers to silica particles whose surface has been hydrophobically treated. Using hydrophobic surface-treated silica improves the dispersibility of silica in the main agent and curing agent, resulting in good storage stability. Specific examples of hydrophobic surface-treated agents include methacrylate silane (surface modification group: methacrylate group), dimethyldichlorosilane (surface modification group: dimethylsilyl group), hexamethyldisilazane (surface modification group: trimethylsilyl group), monoalkylsilane (surface modification group: alkylsilyl group (octylsilyl group, etc.)), and silicone oil (surface modification group: dimethylpolysiloxane group).

[0031] <Organothixotropic agent (C2)> From the viewpoint of workability and storage stability, the two-component curable epoxy resin composition of the present invention preferably contains an organic thixotropic agent (C2) in both the main component and the curing agent. Examples of organic thixotropic agents (C2) include hydrogenated castor oil, polyamide wax, oxidized polyethylene wax, sulfate esters, fatty acid esters, and polyols.

[0032] Of the above, polyols are preferred from the viewpoint of injectability.

[0033] Examples of polyols include divalent to octavalent or higher polyhydric alcohols (C2-30), divalent to octavalent or higher polyhydric phenols (C6-40), and mixtures thereof. Examples of dihydric to octavalent alcohols include dihydric alcohols [e.g., EG, PG, 1,3- and 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 [e.g., GR, TMP], tetrahydric to octavalent alcohols [e.g., PE, diGR, α-methylglucoside, SO, xylitol, mannitol, diPE, glucose, fructose, sucrose], and AO adducts thereof.

[0034] Examples of divalent to octavalent or higher phenols include divalent phenols [e.g., hydroquinone, catechol, bisphenol-A, -F and S, naphthalenediol, anthracenediol], trivalent to octavalent or higher phenols [e.g., hydroxyquinol, pyrogallol, trishydroxyphenylisopropylbenzene [trade name "Trisphenol PA", manufactured by Mitsui Petrochemical Co., Ltd.], phenol novolac, cresol novolac], and AO adducts thereof.

[0035] Examples of the aforementioned AO include EO and alkylene oxides having 3 to 6 carbon atoms (e.g., PO, 1,2-, 2,3- or 1,3-butylene oxide, 1,2-hexylene oxide, etc.). From the viewpoint of thixotropy, a combination of EO and an alkylene oxide having 3 to 6 carbon atoms is preferred, and a combination of EO and PO is even more preferred.

[0036] Of these polyols, from the viewpoint of injectability, resistance to dripping, and thixotropy, AO adducts of polyhydric alcohols are preferred, more preferably EO adducts of polyhydric alcohols and alkylene oxide adducts having 3 to 6 carbon atoms, even more preferably EO adducts of C3 to 6 dihydric alcohols and alkylene oxide adducts having 3 to 6 carbon atoms, particularly preferred EO adducts of C3 to 6 dihydric alcohols and PO adducts, and most preferably EO adducts of C3 to 6 dihydric alcohols and PO adducts. Storage stability tends to improve as the valency of the polyol increases, and injectability tends to improve as the valency decreases. When adding both ethylene oxide (EO) and alkylene oxide (AO(C3-6)) having 3 to 6 carbon atoms, the addition method can be either random addition or block addition, but random addition is preferred from the viewpoint of thixotropy.

[0037] The average total number of moles of EO and AO (C3-6) added to the polyhydric alcohol is preferably 3 to 150, and more preferably 15 to 130, from the viewpoint of thixotropy and workability of the two-component curable epoxy resin composition. The addition molar ratio of EO to AO (C3-6) (EO / AO) is preferably 0.2-10, more preferably 0.3-8, and particularly preferably 0.5-7 from the viewpoint of storage stability, injectability, thixotropy, and water resistance of the cured product. A larger addition molar ratio (EO / AO) tends to improve the dispersibility of the inorganic filler (D), while a smaller ratio tends to improve the injectability. The manganese content of the polyol is preferably 200 to 10,000, more preferably 1,000 to 8,000, and particularly preferably 1,000 to 6,000, from the viewpoint of miscibility with other components, thixotropy, and workability.

[0038] The production of EO and / or AO(C3-6) adducts of polyhydric alcohols can be carried out by known methods, in one or multiple steps under atmospheric pressure or under pressure in the presence of a catalyst (alkaline catalyst, amine catalyst, acid catalyst).

[0039] The two-component curable epoxy resin composition of the present invention has a mass ratio (C1:C2) of inorganic thixotropic agent (C1) to organic thixotropic agent (C2) in the range of 1:0.2 to 1:1. If the mass ratio of C2 to C1 falls below 0.2, the viscosity increases and the discharge performance deteriorates. On the other hand, if it exceeds 1, the sagging and storage stability (settling) deteriorates.

[0040] <Inorganic filler (D)> From the viewpoint of workability and storage stability, it is preferable that the two-component curable epoxy resin composition of the present invention contains the inorganic filler (D) in both the main component and the curing agent. Examples of inorganic fillers (D) in the present invention include silicates (D1), oxides (D2), carbonates (D3), hydroxides (D4), (sulfites) (D5), borates (D6), nitrides (D7), and mixtures of two or more of these. (However, those corresponding to (C1) above are excluded.) By including an inorganic filler (D), the mechanical strength and heat resistance of the cured product of the two-component epoxy resin composition can be improved. Silicates (D1) (e.g., talc, clay, mica, glass, quartz); Oxides (D2) [e.g., titanium oxide, alumina, silica excluding (C1)]; Carbonates (D3) (e.g., calcium carbonate, magnesium carbonate, hydrotalcite); Hydroxides (D4) (e.g., aluminum hydroxide, magnesium hydroxide, calcium hydroxide); (Sulfites) (D5) (e.g., barium sulfate, calcium sulfate, calcium sulfite); Borates (D6) (e.g., zinc borate, barium metaborate, aluminum borate, calcium borate, sodium borate); Nitrides (D7) (e.g., aluminum nitride, boron nitride, silicon nitride).

[0041] Of these (D) materials, (D1), (D2), (D3), and (D4) are preferred from the viewpoint of workability, mechanical strength of the cured product, and industrial use. More preferably, (D1), (D2), and (D3) are preferred. Particularly preferred are silica and calcium carbonate, excluding (C1), and most preferably, calcium carbonate.

[0042] The shape of (D) is preferably in powder form from the viewpoint of the workability of the two-component curable epoxy resin composition. Furthermore, the average particle size of (D) is preferably 0.1 to 800 μm, more preferably 0.5 to 250 μm, and particularly preferably 0.8 to 100 μm from the viewpoint of the viscosity and workability of the two-component curable epoxy resin composition.

[0043] The present invention relates to a two-component curable epoxy resin composition, preferably comprising a main component containing an epoxy compound (A) and a curing agent containing an amine compound (B). <Main ingredient> The content of epoxy compound (A) in the main component is preferably 40 to 70% by weight, and more preferably 45 to 65% by weight, based on the weight of the main component, from the viewpoint of the mechanical strength and storage stability of the cured product. The epoxy concentration in the main component (concentration of epoxy groups per gram of main component, mmol / g) is preferably 1.5 to 4.5, and more preferably 1.7 to 4.0, from the viewpoint of injectionability and mechanical strength of the cured product. The epoxy concentration can be calculated using epoxy equivalents. The viscosity of the main component at 25°C is preferably 10 to 200 Pa·s, and more preferably 20 to 80 Pa·s, from the viewpoint of injectability and storage stability. The viscosity of the main component at 25°C can be measured using a BH-type viscometer. The content of the inorganic thixotropic agent (C1) in the main component is preferably 0.3 to 4% by weight, and more preferably 0.5 to 4% by weight, based on the weight of the main component, from the viewpoint of injectability and storage stability. The content of the organic thixotropic agent (C2) in the main component is preferably 0.2 to 2% by weight, and more preferably 0.5 to 1.5% by weight, based on the weight of the main component, from the viewpoint of injectability and storage stability. The weight ratio [(C1+C2) / A] of the total weight of the inorganic thixotropic agent (C1) and the organic thixotropic agent (C2) in the main component to the weight of the epoxy compound (A) is preferably 0.01 to 0.08 from the viewpoint of workability and storage stability. The content of inorganic filler (D) in the main component is preferably 10 to 55% by weight, and more preferably 20 to 45% by weight, based on the weight of the main component, from the viewpoint of mechanical strength, injectability, and storage stability of the cured product. The weight ratio [D / A] of the inorganic filler (D) to the epoxy compound (A) in the main component is preferably 0.1 to 3.0, and more preferably 0.1 to 1.0, from the viewpoint of storage stability and other factors.

[0044] The content of amine compound (B) in the curing agent is preferably 20 to 70% by weight, and more preferably 30 to 60% by weight, based on the weight of the curing agent, from the viewpoint of injectability and storage stability. The content of the inorganic thixotropic agent (C1) in the curing agent is preferably 1 to 5% by weight, and more preferably 1 to 4% by weight, based on the weight of the curing agent, from the viewpoint of injectionability and storage stability. The content of the organic thixotropic agent (C2) in the curing agent is preferably 0.2 to 2% by weight, and more preferably 0.5 to 1.5% by weight, based on the weight of the curing agent, from the viewpoint of injectionability and storage stability. The weight ratio [(C1+C2) / B] of the total weight of the inorganic thixotropic agent (C1) and the organic thixotropic agent (C2) in the curing agent to the weight of the amine compound (B) is preferably 0.01 to 0.08 from the viewpoint of workability and storage stability. The content of inorganic filler (D) in the curing agent is preferably 10 to 60% by weight, and more preferably 20 to 50% by weight, based on the weight of the curing agent, from the viewpoint of mechanical strength, injectability, and storage stability of the cured product. The weight ratio [D / B] of the inorganic filler (D) to the weight of the amine compound (B) in the curing agent is preferably 0.1 to 3.0, and more preferably 0.1 to 1.5, from the viewpoint of storage stability and other factors. The weight ratio [(C1+C2) / (B+D)] of the total weight of the inorganic thixotropic agent (C1) and the organic thixotropic agent (C2) in the curing agent to the total weight of the amine compound (B) and the inorganic filler (D) is preferably 0.01 to 0.5 from the viewpoint of workability and storage stability.

[0045] <Two-component curing epoxy resin composition> The content of amine compound (B) in the two-component curable epoxy resin composition is preferably 12 to 35 parts by weight, and more preferably 15 to 30 parts by weight, per 100 parts by weight of epoxy compound (A), from the viewpoint of the strength of the cured product and workability.

[0046] The total weight of (C1) and (C2) in the two-component curable epoxy resin composition is preferably 0.5 to 10% by weight, and more preferably 2 to 8% by weight, based on the weight of the two-component curable epoxy resin composition, from the viewpoint of workability and storage stability.

[0047] The content of inorganic filler (D) in the two-component curable epoxy resin composition is preferably 10 to 50% by weight, based on the weight of the two-component curable epoxy resin composition, from the viewpoint of workability and the mechanical strength of the cured product.

[0048] <Monofunctional Epoxide (F)> The two-component curable epoxy resin composition of the present invention may further contain a monofunctional epoxide (F) having one epoxy group in its molecule. Including (F) can make it easier to adjust the viscosity and pot life of the two-component curable epoxy resin composition. (F) is not particularly limited as long as it is a compound having one epoxy group in its molecule, but examples include alkyl monoglycidyl ethers (such as butyl glycidyl ether and 2-ethylhexyl glycidyl ether), allyl glycidyl ether, glycerol monoglycidyl ether, alkylphenol monoglycidyl ether, styrene oxide, phenyl glycidyl ether, cresyl glycidyl ether and glycidyl methacrylate, and mixtures of two or more of these.

[0049] From the viewpoint of the heat resistance of the cured product of the two-component epoxy resin composition, the amount of monofunctional epoxide (F) used is preferably 3% by weight or less based on the total weight of (A), (B), and (C) above.

[0050] The two-component curable epoxy resin composition of the present invention may further optionally contain, to the extent that it does not impair the effects of the present invention, (1) curing accelerators (tertiary amino compounds, alkali compounds other than those in (B) and (C) above, Lewis base compounds and phenol group-containing compounds, etc.), (2) adhesion promoters (titanium coupling agents, etc.), (3) antioxidants (hindered amines, hydroquinones, hindered phenols, sulfur-containing compounds, etc.), (4) ultraviolet absorbers (benzophenones, benzotriazoles, salicylic acid esters, metal complex salts, etc.), (5) plasticizers (phthalate esters, phosphate esters, fatty acid esters, epoxidized soybean oil, castor oil, liquid paraffin alkyl polycyclic aromatic hydrocarbons, etc.), and (6) waxes (paraffin wax, microcrystalline wax, heavy (1) Additives (G) such as (1) synthetic wax, beeswax, whale wax, low molecular weight polyolefin, etc., (2) non-reactive diluents (benzyl alcohol, tar, pichumen, etc.), (3) reactive diluents (low molecular weight aliphatic glycidyl ether, aromatic monoglycidyl ether, etc.), (4) organic fillers [aramid fiber powder, nylon fiber powder, acrylic fiber powder, acrylic resin powder, phenol resin powder, etc.], (5) deodorizers [activated carbon, zeolite, etc.], (6) pigments or dyes [carbon black, red lead, para red, Prussian blue, etc.], (7) solvents (ethyl acetate, toluene, alcohol, ether, ketone, etc.), (8) foaming agents, (9) defoaming agents, (10) antistatic agents, (11) antifungal agents, (12) viscosity modifiers, (13) fragrances, and (14) flame retardants may be included.

[0051] The two-component curable epoxy resin composition of the present invention is manufactured and used by the following method. The two components are prepared separately in the form of a main component containing an epoxy compound (A), an inorganic thixotropic agent (C1), an organic thixotropic agent (C2), and an inorganic filler (D) added as needed, and a curing agent containing an amine compound (B), an inorganic thixotropic agent (C1), an organic thixotropic agent (C2), and an inorganic filler (D) added as needed. These are then mixed at the time of use to obtain a two-component curable epoxy resin composition. The method for mixing (A), (B), (C1), (C2) and (D) which may be added as needed in the present invention is not particularly limited, but examples include using a mixer such as a universal mixer, using a blender, or using a cartridge. When using, it is preferable to use a cartridge from the viewpoint of workability and storage stability.

[0052] The initial viscosity (Pa·s) of the two-component curable epoxy resin composition of the present invention at 25°C is preferably 100 Pa·s or less, and more preferably 20 to 70 Pa·s, from the viewpoint of workability (injectability and fillability, etc.). Initial viscosity refers to the viscosity measured after the main component and hardener have been heated to a predetermined temperature, mixed in a predetermined ratio (the ratio of amounts that will result in the desired two-component curable epoxy resin composition) for 2 minutes, and then set in a B-type viscometer and heated for several minutes (for example, 6 minutes after the start of mixing) while maintaining the temperature in a constant temperature bath.

[0053] The above initial viscosity can be measured, for example, under the following conditions. Equipment: BH-type viscometer [Model number "TVB-22H", manufactured by Toki Sangyo Co., Ltd.] Rotation speed: 20 rpm Spindle No.: No. 7

[0054] The thixoindex of the main component of the two-component curable epoxy resin composition of the present invention is preferably 5 to 8 from the viewpoint of storage stability and the like. Furthermore, the thixoindex of the curing agent of the two-component curable epoxy resin composition of the present invention is preferably 4 to 8 from the viewpoint of storage stability and the like. In this invention, the thixoindex is the value obtained by dividing the viscosity (mPa·s) measured at 25°C using a B-type viscometer at a rotation speed of 2 rpm by the viscosity (mPa·s) measured at 25°C using a B-type viscometer at a rotation speed of 20 rpm [viscosity measured at 2 rpm (mPa·s) / viscosity measured at 20 rpm (mPa·s)]. The thixoindex can be adjusted to the above range by adjusting the degree of hydrophobicity and the amount of the inorganic thixotropic agent (C1) or by adjusting the amount of the organic thixotropic agent (C2) added.

[0055] <Cured product obtained by curing a two-component epoxy resin composition> The cured product of the present invention is a cured product obtained by curing the above-mentioned two-component curable epoxy resin composition. It is obtained by mixing a main component containing the epoxy compound (A), an inorganic thixotropic agent (C1), an organic thixotropic agent (C2), and an inorganic filler (D) added as necessary, and a curing agent containing the amine compound (B), an inorganic thixotropic agent (C1), an organic thixotropic agent (C2), and an inorganic filler (D) added as necessary, as described above, and allowing the curing reaction to proceed by curing as necessary. When used as an adhesive for civil engineering and construction, the curing temperature is not particularly limited as it is applied on-site without temperature control, but is preferably 5 to 40°C, and more preferably 15 to 30°C. The curing time for the two-component epoxy resin composition at 5 to 40°C is preferably 100 to 340 hours, and more preferably 120 to 240 hours. The curing time refers to the time it takes for the resin strength (compressive strength at 25°C) to reach the strength required for practical use (for example, 60 MPa or more when used as an adhesive for civil engineering and construction) after curing at a specified temperature. The compressive strength at 25°C can be measured in accordance with JIS K 7181.

[0056] The compressive strength at 25°C of the cured product (cured product from the first curing reaction) obtained by curing the two-component curable epoxy resin composition of the present invention at the above curing temperature (25°C) for 5 days is preferably 60 to 120 MPa, and more preferably 70 to 120 MPa, from the viewpoint of mechanical strength and other factors.

[0057] The two-component curing epoxy resin composition of the present invention can be used with a two-component cartridge system, and even when the cartridge is enlarged, it has good workability (injectability and fillingability, etc.), as well as excellent storage stability and strength of the cured product. Therefore, it can be used in various applications such as adhesives, resin fillers (for repair and reinforcement work of structures such as concrete structures and steel structures, crack injection, adhesives for post-installed anchors, etc.), and molded products. It is particularly suitable for use as an adhesive and resin filler for civil engineering and construction.

[0058] This specification discloses the following:

[0059] (1) The present disclosure is a two-component curable epoxy resin composition comprising an epoxy compound (A), an amine compound (B), an inorganic thixotropic agent (C1), and an organic thixotropic agent (C2), wherein the inorganic thixotropic agent (C1) is silica with a hydrophobic surface treatment, and the mass ratio (C1:C2) of the inorganic thixotropic agent (C1) to the organic thixotropic agent (C2) is in the range of 1:0.2 to 1:1.

[0060] Disclosure (2) is a two-component curable epoxy resin composition according to Disclosure (1), wherein the average particle size of the inorganic thixotropic agent (C1) is 1 to 100 nm.

[0061] Disclosure (3) is a two-component curable epoxy resin composition according to Disclosure (1) or (2), wherein the organic thixotropic agent (C2) is a polyol.

[0062] Disclosure (4) is a two-component curable epoxy resin composition according to any of Disclosures (1) to (3) using a two-component cartridge system.

[0063] Disclosure (5) is a two-component curing epoxy resin composition described in any of Disclosures (1) to (4) which is an adhesive for civil engineering and construction. [Examples]

[0064] The present invention will be further described by the following examples, but the present invention is not limited thereto.

[0065] <Manufacturing Example 1: Manufacturing of Amine Compound (B-2)> At room temperature, 489 g (2.11 mol) of pentaethylenehexamine was mixed with 173 g (0.46 mol) of bisphenol A diglycidyl ether, and the mixture was stirred for 5 minutes. The reaction temperature was then raised to 40°C and the reaction was carried out for 1 hour to obtain the reaction product (B-2) of pentaethylenehexamine and bisphenol A diglycidyl ether. The active hydrogen equivalent was 42 g / eq, and the number-average molecular weight was 400.

[0066] <Manufacturing Example 2: Manufacturing of PG EO and PO adducts (C2-1)> 25 parts by weight of propylene glycol (PG) and 0.15 parts by weight of potassium hydroxide as a catalyst were charged into an autoclave. A mixture of 696 parts by weight of EO and 79 parts by weight of PO2 was blown in and the mixture was reacted at 110°C. After aging at 130°C, the catalyst was removed by adsorption treatment with a magnesium oxide-based adsorbent [product name "Kyoward 600", manufactured by Kyowa Chemical Industry Co., Ltd.] to obtain PG EO and PO adduct (C2-1) (Mn 3,000, average number of added moles of EO and PO 62.6, EO / PO added molar ratio = 3.3).

[0067] <Manufacturing Example 3: Manufacturing of EO and PO adducts (C2-2) of PG> In Production Example 2, the synthesis was carried out in the same manner except that 76 parts by weight of propylene glycol (PG), 659 parts by weight of EO, and 264 parts by weight of PO were used, and a PG adduct of EO and PO (C2-2) (Mn 1,000, average number of added moles of EO and PO 19.5, EO / PO addition molar ratio = 3.3) was obtained.

[0068] <Manufacturing Example 4: Manufacturing of EO and PO adducts (C2-3) of PG> In Production Example 2, the synthesis was carried out in the same manner except that propylene glycol (PG) was used in parts 13 by weight, EO in parts 706 by weight, and PO in parts 282 by weight, to obtain PG adduct with EO and PO (C2-3) (Mn 6,000, average number of added moles of EO and PO 122, EO / PO molar ratio = 3.3).

[0069] <Manufacturing Example 5: Manufacturing of EO and PO adducts (C2-4) of PG> In Production Example 2, the synthesis was carried out in the same manner except that 25 parts by weight of propylene glycol (PG), 268 parts by weight of EO, and 707 parts by weight of PO were used, and a PG adduct of EO and PO (C2-4) (Mn 3,000, average number of added moles of EO and PO 55.5, EO / PO addition molar ratio = 0.5) was obtained.

[0070] <Manufacturing Example 6: Manufacturing of EO and PO adducts (C2-5) of PG> In Production Example 2, the synthesis was carried out in the same manner except that 25 parts by weight of propylene glycol (PG), 821 parts by weight of EO, and 154 parts by weight of PO were used, and a PG adduct of EO and PO (C2-5) (Mn 3,000, average number of added moles of EO and PO 64, EO / PO addition molar ratio = 7) was obtained.

[0071] <Example 1: Production of a two-component curable epoxy resin composition (X-1)> Using a universal mixer [product name "Universal Mixer 5DMV-01-r", manufactured by Dalton Co., Ltd.], 60.0 parts by weight of bisphenol F diglycidyl ether (A-1), 3.0 parts by weight of fumed silica (C1-1), 1.0 part by weight of polyol EO and PO adducts (C2-1), and 36.0 parts by weight of calcium carbonate (D-1) were mixed under reduced pressure while degassing (temperature 25°C, stirring time 60 minutes, pressure 4kPa) to obtain the main component. Furthermore, 12.8 parts by weight of xylylenediamine (B-1), 10.4 parts by weight of the reaction product of pentaethylenehexamine and bisphenol A diglycidyl ether (B-2), 0.8 parts by weight of fumed silica (C1-1), 0.2 parts by weight of fumed silica (C1-3), 0.5 parts by weight of EO and PO adducts of polyols (C2-1), and 22.2 parts by weight of calcium carbonate (D-1) were mixed under reduced pressure while degassing (temperature 25°C, stirring time 60 minutes, pressure 4 kPa) to obtain a curing agent. The obtained main components and curing agents were mixed using a centrifugal degasser [product name "Awatori Rentaro ARV930TWIN", manufactured by Thinky Co., Ltd.] (temperature 25°C, stirring time 3 minutes, rotation speed 1400 rpm) to obtain a two-component curing epoxy resin composition (X-1).

[0072] <Examples 2-10: Production of two-component curable epoxy resin compositions (X-2)-(X-10)> Each example was prepared in the same manner as in Example 1, except that the raw materials (parts by weight) listed in Table 1 were used. Next, the prepared main components and curing agents were mixed using a centrifugal degasser [product name "Awatori Rentaro ARV930TWIN", manufactured by Thinky Co., Ltd.] (temperature 25°C, stirring time 3 minutes, rotation speed 1400 rpm) to obtain two-component curable epoxy resin compositions (X-2) to (X-10).

[0073] <Comparative Examples 1-4: Manufacturing of comparative two-component curable epoxy resin compositions (comparison X-1)-(comparison X-4)> Each comparative example was prepared in the same manner as in Example 1, except that the raw materials (parts by weight) listed in Table 1 were used. Next, the prepared main components and curing agents were mixed using a centrifugal degasser [product name "Awatori Rentaro ARV930TWIN", manufactured by Thinky Co., Ltd.] (temperature 25°C, stirring time 3 minutes, rotation speed 1400 rpm) to obtain two-component curable epoxy resin compositions (ratio X-1) to (ratio X-4).

[0074] The performance of each two-component curable epoxy resin composition obtained in the examples and comparative examples was evaluated using the following test methods. Note that (1) and (2) viscosity and (3) sedimentation were measured using the methods described below before mixing each main component and each curing agent obtained above. (4) thixoindex, (5) sagging, (6) injectability, and (7) compression yield strength were measured after mixing each main component and each curing agent obtained above using the methods described below. The measurement and evaluation results are shown in Table 1.

[0075] [Table 1]

[0076] The abbreviations in Table 1 are as follows: <Epoxy resin (A)> A-1: Bisphenol F diglycidyl ether [Product name "jER807", manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 175g / eq]

[0077] <Amine compound (B)> B-1: Xylylenediamine [Product name "Ankamin 2422", manufactured by Air Products Japan Co., Ltd., active hydrogen equivalent 34]

[0078] <Inorganic thixotropic agent (C1)> C1-1: Hydrophobic surface-treated fumed silica [Product name "AEROSIL R972", manufactured by Nippon Aerosil Co., Ltd., average particle size 16 nm, surface modification group: dimethylsilyl group] C1-2: Hydrophobic surface-treated fumed silica [Product name "AEROSIL RY-200S", manufactured by Nippon Aerosil Co., Ltd., average particle size 16 nm, surface modification group: dimethylpolysiloxane group] C1-3: Hydrophobic surface-treated fumed silica [Product name "AEROSIL RY-50", manufactured by Nippon Aerosil Co., Ltd., average particle size 40 nm, surface modification group: dimethylpolysiloxane group] C1-4: Hydrophobic surface-treated fumed silica [Product name "AEROSIL R976", manufactured by Nippon Aerosil Co., Ltd., average particle size 7 nm, surface modification group: dimethylsilyl group] C1'-1: Fumed Silica [Product Name: "HS-106", manufactured by Micron Inc., average particle size 20 μm] C1'-2: Fumed silica [Product name "AEROSIL 200", manufactured by Nippon Aerosil Co., Ltd., average particle size 12 nm]

[0079] <Inorganic filler (D)> D-1: Calcium carbonate [Product name "Softon 1200", manufactured by Shiraishi Calcium Co., Ltd., average particle size 1.8 μm]

[0080] <Testing Method> (1) Viscosity of the main component (at 25°C) [Unit: Pa·s] After the main component was temperature-controlled in a 25°C constant temperature bath, measurement was started using a BH-type viscometer [model number "TVB-22H", manufactured by Toki Sangyo Co., Ltd.] under the following conditions, and the viscosity (Pa·s) was measured 2 minutes after the start. <Measurement conditions> Temperature: 25℃ Rotation speed: 20 rpm Spindle No: 7

[0081] (2) Hardener viscosity (25℃) [Unit: Pa·s] The initial viscosity (Pa·s) at 25°C was measured in the same manner as in (1) above, except that the main component was changed to a hardening agent.

[0082] (3) Storage stability (sedimentation) Before mixing, 50g of each main component and hardener was placed in a centrifuge tube after being heated to 25°C. Centrifugation was performed using a benchtop centrifuge [H-36, manufactured by Kokusan Co., Ltd.] at a rotation speed of 3000 rpm for 30 minutes. The appearance was visually observed every 30 minutes to check for the presence or absence of sedimentation of the inorganic filler (D) in each main component and hardener. The time (minutes) until sedimentation of (D) occurred was judged based on the evaluation criteria below, and the results are shown in Table 1. For practical use, a score of ○ or higher is preferable. <Evaluation Criteria> ◎: 180 minutes or more 〇: 135 minutes or more, less than 180 minutes △: 90 minutes or more, less than 135 minutes ×: Less than 90 minutes

[0083] (4) Thixoindex For the main component and each hardener, the thixoindex is calculated by dividing the viscosity (mPa·s) measured at 25°C using a B-type viscometer at a rotation speed of 2 rpm by the viscosity (mPa·s) measured at 25°C using a B-type viscometer at a rotation speed of 20 rpm [viscosity measured at 2 rpm (mPa·s) / viscosity measured at 20 rpm (mPa·s)].

[0084] (5) Drooping Fill 600 mL of each main component and 300 mL of each hardener into separate cartridges, maintain a temperature of 25°C, and inject them into the rebar joints (size: D29) using a manual gun. After injection, visually check for any sagging from the rebar joints. 〇: No sauce ×: Sauce present

[0085] (6) Injectability [unit: seconds, s] Each main component was filled into a 600 mL cartridge, and each hardener into a 300 mL cartridge. The cartridges were then heated to 25°C and extruded using a manual gun. The time from the start of extrusion until the epoxy resin composition was completely extruded was measured.

[0086] (7) Compression yield strength [Unit: N / mm] 2 ] The mixed epoxy resin composition was molded into a plate approximately 10 mm thick and cured at 25°C for 5 days. A rectangular test specimen approximately 10 mm thick x 10 mm wide x 30 mm long was cut out and measured according to JIS K7181, except that the test speed was changed to 2 mm / min.

[0087] The results in Table 1 show that the two-component epoxy resin compositions of Examples 1 to 10 have good workability and storage stability, are less prone to sagging, and exhibit excellent strength in the cured product. On the other hand, the two-component curable epoxy resin composition of Comparative Example 1, which did not contain (C1), had poor storage stability, sagging, and poor injectability. The two-component curable epoxy resin composition of Comparative Example 2, which did not contain (C2), lacked sufficient settling properties and had poor injectability. Furthermore, Comparative Examples 3 and 4, which did not use hydrophobic surface-treated silica as the inorganic thixotropic agent (C1), had poor storage stability. [Industrial applicability]

[0088] The two-component curable epoxy resin composition of the present invention has good workability (injectability and fillability, etc.) and storage stability, is less prone to sagging, and can produce a cured product with excellent strength. Therefore, it can be used in various applications such as adhesives, resin fillers, and molded products, and is particularly suitable for use as an adhesive and resin filler for civil engineering and construction.

Claims

1. A two-component curable epoxy resin composition comprising an epoxy compound (A), an amine compound (B), an inorganic thixotropic agent (C1), and an organic thixotropic agent (C2), wherein the inorganic thixotropic agent (C1) is silica with a hydrophobic surface treatment, and the mass ratio (C1:C2) of the inorganic thixotropic agent (C1) to the organic thixotropic agent (C2) is in the range of 1:0.2 to 1:

1.

2. The two-component curable epoxy resin composition according to claim 1, wherein the average particle size of the inorganic thixotropic agent (C1) is 1 to 100 nm.

3. The two-component curable epoxy resin composition according to claim 1 or 2, wherein the organic thixotropic agent (C2) is a polyol.

4. A two-component curable epoxy resin composition according to claim 1 or 2, using a two-component cartridge system.

5. A two-component curable epoxy resin composition according to claim 1 or 2, which is an adhesive for civil engineering and construction.

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