JP2001240837A - Adhesive for adhering newly placed concrete to existing concrete - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive for adhering newly placed concrete to existing concrete, capable of curing at such a low temperature as 5 deg.C, having an appropriate useful service time, having a low viscosity, therefore excellent in workability and adhesiveness, and further scarcely causing safety problems such as air pollution, because of not using any solvent. SOLUTION: This adhesive for adhering newly placed concrete to existirng concrete is obtained by using an epoxy resin composition comprising a specific heterocyclic ring-containing compound, a polyepoxy compound, and an amino compound having two or more active hydrogen atoms derived from amino groups in a molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a reactive adhesive. More specifically, the present invention relates to an adhesive for joining new and old concretes having excellent adhesiveness, comprising a novel epoxy resin.

[0002]

2. Description of the Related Art Epoxy resins have good alkali resistance, and if a suitable curing agent or modifier is incorporated, a tough and flexible cured product can be obtained and the wettability with concrete is good. When producing a concrete building by passing on the new concrete to the old concrete, an epoxy resin-based adhesive is applied to the old concrete surface in order to secure the adhesiveness at the interface, and then it is not cured. The construction method of pouring a new concrete in is adopted.

[Problems to be solved by the invention]

However, with an epoxy resin-based adhesive, the epoxy resin does not cure at a low temperature, especially at 5 ° C. or lower, so that it is necessary to take measures such as heating at the construction site. In addition, many conventional epoxy resin-based adhesives use a volatile organic solvent, but today, when the problem of air pollution is taken up, an adhesive that does not use such a solvent is desired.

The present invention solves these problems, is capable of curing even at a low temperature such as 5 ° C., has an appropriate pot life, has low viscosity, and has good workability. An object of the present invention is to provide an adhesive for jointing old and new concretes, which is a non-organic solvent and has excellent adhesiveness.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have reached the present invention. That is, the present invention provides a heterocyclic compound (A) represented by the following general formula (1), a polyepoxy compound (B) having two or more epoxy groups in a molecule, and a compound derived from an amino group in a molecule. An adhesive for joining new and old concrete, comprising an amino compound (C) having two or more active hydrogens.

[0006]

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

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a compound containing a hetero ring is used.
The product (A) is represented by the general formula (1). Where n is
It is an integer of 1 to 10, preferably an integer of 2 to 8.
X¹, Y¹And Z¹Is an oxygen or sulfur atom, respectively.
You. Preferably X¹Is a sulfur atom (S) and Y¹, Z¹One
The other is a sulfur atom (S) and the other is an oxygen atom (O). R
^Two Constitutes a ring other than the oxygen atom in the cyclic ether group
Residue. This is a hydrocarbon group having 2 to 10 carbon atoms.
Trivalent hydrocarbon group> CH (CH_Two)_m− (M is 1 to 9
), And is, for example,> CHCH_Two−,
> CHCH_TwoCH _Two-,> CHCH_TwoCH_TwoCH_Two-,> C
HCH_TwoCH_TwoCH_TwoCH_TwoCH_Two-Etc .; tetravalent hydrocarbon groups
> CH (CH_Two)_mCH <(m is an integer of 0 to 8)
For example,> CHCH <,> CHCH_TwoCH
<,> CHCH_TwoCH_TwoCH <,> CHCH_TwoCH_TwoCH_Two
CH_TwoCH <and the like, preferably a trivalent hydrocarbon
And particularly preferably> CHCH_Two-,> CHCH_Two
CH_Two-. R¹Contains a hydrogen atom or a cyclic ether group
It is a residue of compound (D) and represented by general formula (5).
General formula

[0009]

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The cyclic ether group is not particularly limited as long as it has at least one oxygen atom in the ring, and examples thereof include compounds having 1 to 10 cyclic ether groups in the molecule. Examples of the cyclic ether group-containing compound (D) include an epoxy group-containing compound (D1) and an oxetane compound (D2) described below, and preferably the epoxy group-containing compound (D1). Examples of the epoxy group-containing compound (D1) include a monoepoxide (d11) and a polyepoxide (D1) having two or more epoxy groups in a molecule.
1). The monoepoxide (d11) is not particularly limited as long as it has one epoxy group in the molecule, and can be appropriately selected depending on the application and purpose. Examples include the following. For example, (d1
1-1) Hydrocarbon oxides having 2 to 24 carbon atoms (ethylene oxide, propylene oxide, 1-butene oxide, 2-butene oxide, α-olefin oxides having 5 to 24 carbon atoms, styrene oxide, etc.), (d11-2) )
Glycidyl ethers of hydrocarbons having 3 to 19 carbon atoms (n-
Butyl glycidyl ether, allyl glycidyl ether, 2-ethyl-hexyl glycidyl ether, 2-methyloctyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, p-sec-
Butylphenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, etc.), (d11-3)
Examples thereof include glycidyl esters of monocarboxylic acids having 3 to 30 carbon atoms (glycidyl acrylate, glycidyl methacrylate and the like), epihalohydrins such as epichlorohydrin and epibromohydrin, and hydroxyl-containing oxides such as glycidol. Preferred are hydrocarbon oxides having 2 to 24 carbon atoms and glycidyl ethers of hydrocarbons having 3 to 19 carbon atoms.

The polyepoxide (D11) contains 2
There is no particular limitation as long as it has two or more epoxy groups, and it can be appropriately selected according to the application and purpose. Preferably, it has 2 to 6 epoxy groups in the molecule. The epoxy equivalent (molecular weight per epoxy group) of the polyepoxide is usually from 65 to 1,000, and preferably 9 to 1,000.
0 to 500. When the epoxy equivalent is 1,000 or less, the adhesive of the present invention is a cross-linkable reaction type of (A) to (C), the cross-linked structure of which does not become loose, and the water resistance and chemical resistance of the cross-linked cured product. On the other hand, when the epoxy equivalent is 65 or more, the cured product has a crosslinked structure having good water resistance, chemical resistance, mechanical strength, and the like. Examples of the polyepoxide (D11) include the following (D
11-1) to (D11-5).

(D11-1) Glycidyl ether type (i) Diglycidyl ether of dihydric phenol Diglycidyl ether of dihydric phenol having 6 to 30 carbon atoms, for example, bisphenol F diglycidyl ether,
Bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl ether, tetrachlorobisphenol A diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, Hydroquinone diglycidyl ether, 1,5-dihydroxynaphthalenediglycidyl ether, dihydroxybiphenyldiglycidyl ether, octachloro-4,4'-dihydroxybiphenyldiglycidyl ether, tetramethylbiphenyldiglycidyl ether, 9,9'-bis (4- (Hydroxyphenyl) flow orange glycidyl ether, 2 mol of bisphenol A and epichloro Diglycidyl ether obtained from Drinks 3 moles of reaction.

(Ii) Trivalent to hexavalent or higher polyglycidyl ether of a polyhydric phenol having 6 to 50 or more carbon atoms and a molecular weight of 250 to 500
Polyglycidyl ethers of trivalent to hexavalent or higher polyhydric phenols of 0, for example, pyrogallol triglycidyl ether, dihydroxynaphthyl cresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, dinaphthyltriol triglycidyl ether, Tetrakis (4-hydroxyphenyl) ethanetetraglycidyl ether, trismethyl-
tert-butyl-butylhydroxymethane triglycidyl ether, 4,4′-oxybis (1,4-phenylethyl) tetracresol glycidyl ether, 4,
4'-oxybis (1,4-phenylethyl) phenyl glycidyl ether, bis (dihydroxynaphthalene)
Glycidyl ether of tetraglycidyl ether, phenol or cresol novolak resin (molecular weight 400 to 5000), glycidyl ether of limonene phenol novolak resin (molecular weight 400 to 5000), obtained by condensation reaction of phenol with glyoxal, glutaraldehyde, or formaldehyde. And a polyglycidyl ether of a polyphenol having a molecular weight of 400 to 5000 obtained by a condensation reaction of resorcinol and acetone.

(Iii) Diglycidyl ether of an aliphatic dihydric alcohol Diglycidyl ether of a diol having 2 to 100 carbon atoms and a molecular weight of 150 to 5000, for example, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl Ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol (molecular weight 150 to 400
0) Diglycidyl ether, polypropylene glycol (molecular weight: 180-5000) diglycidyl ether, polytetramethylene glycol (molecular weight: 200-500)
0) Diglycidyl ether, neopentyl glycol diglycidyl ether, alkylene oxide of bisphenol A [ethylene oxide or propylene oxide (1
To 20 mol)], and diglycidyl ether of an adduct. (Iv) Polyglycidyl ether of a trihydric to hexahydric or higher aliphatic alcohol having 3 to 50 or more carbon atoms and a molecular weight of 92 to 1000
Glycidyl ethers of trihydric to hexahydric or higher polyhydric alcohols of 0, for example, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether,
Sorbitol hexaglycidyl ether, poly (n = 2
To 5) glycerol polyglycidyl ether and the like.

(D11-2) Glycidyl ester type glycidyl ester of a divalent to hexavalent or higher aromatic polycarboxylic acid having 6 to 20 or more carbon atoms, and 6 to 20 or more carbon atoms of an aromatic polycarboxylic acid; Glycidyl esters of divalent to hexavalent or higher aliphatic or cycloaliphatic polycarboxylic acids are mentioned. (I) As the glycidyl ester of an aromatic polycarboxylic acid, for example, phthalic acids, diglycidyl phthalate, diglycidyl isophthalate, diglycidyl terephthalate, triglycidyl trimellitate, and the like; (ii) aliphatic or As the glycidyl ester of alicyclic polycarboxylic acid, the aromatic nucleus water additive of the phenolic glycidyl ester, diglycidyl dimer acid, diglycidyl oxalate, diglycidyl malate, diglycidyl succinate, diglycidyl gluta Rate, diglycidyl adipate, diglycidyl pimerate, a (co) polymer of glycidyl (meth) acrylate (polymerization degree is, for example, 2 to 10), triglycidyl tricarballylate, and the like.

(D11-3) Glycidylamine-type glycidylamine, an aromatic amine having 6 to 20 or more carbon atoms and having 2 to 10 or more active hydrogen atoms, and an aliphatic, alicyclic or heterocyclic ring Glycidylamine of the formula amines may be mentioned. (I) As glycidylamine of aromatic amines,
N, N-diglycidylaniline, N, N-diglycidyltoluidine, N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane, N, N, N ′, N′-tetraglycidyldiaminodiphenylsulfone, N, N ,
N ′, N′-tetraglycidyldiethyldiphenylmethane, N, N, O-triglycidylaminophenol and the like; (ii) glycidylamines of aliphatic amines include
N, N, N ', N'-tetraglycidylxylylenediamine, N, N, N', N'-tetraglycidylhexamethylenediamine and the like; (iii) glycidylamines of alicyclic amines include N, N , N ', N'-tetraglycidylxylylenediamine hydrogenated compound and the like. Examples of the glycidylamine of the heterocyclic amine include trisglycidylmelamine.

(D11-4) Chain aliphatic epoxide A chain aliphatic epoxide having 6 to 50 or more carbon atoms and having 2 to 6 or more valences, for example, an epoxy equivalent of 130 to
1,000 epoxidized polybutadiene (molecular weight 90-
2,500), epoxidized soybean oil (molecular weight 130-2,
500) and the like. (D11-5) Alicyclic epoxide having 6 to 50 or more carbon atoms and having a molecular weight of 90 to 250
0, an alicyclic epoxide having 1 to 4 or more epoxy groups, for example, vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxydioxide Cyclopentyl ether,
3,4 epoxy-6-methylcyclohexylmethyl 3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, and bis (3,4
-Epoxy-6-methylcyclohexylmethyl) butylamine and the like. It also includes a nuclear hydrogenated product of the phenolic epoxy compound. (D11-1)-
Other than (D11-5), any epoxy resin having a glycidyl group capable of reacting with active hydrogen can be used.
In addition, two or more of these polyepoxy compounds can be used in combination. Of these, glycidyl ether type (D11-1) and glycidyl ester type (D11-
The glycidyl ether type (D11-1) is particularly preferable. Of (D11-1), preferred are dihydric phenols and diglycidyl ethers of dihydric aliphatic alcohols.

As the oxetane compound (D2), an aliphatic oxetane compound having 6 to 20 carbon atoms (3-ethyl-
3-hydroxymethyloxetane, etc.), having 7 to 30 carbon atoms
Aromatic oxetane compounds (benzyloxetane, xylylenebisoxetane, etc.), aliphatic carboxylic acid oxetane compounds having 6 to 30 carbon atoms (adipate bisoxetane, etc.), and aromatic carboxylic acid oxetane compounds having 8 to 30 carbon atoms (Such as terephthalate bisoxetane), alicyclic carboxylic acid oxetane compounds having 8 to 30 carbon atoms (such as bisoxetane cyclohexanedicarboxylate), aromatic isocyanate oxetane compounds (such as MDI bisoxetane), and sulfur having 2 to 20 carbon atoms Oxetane compounds (thiirane, 2-methylthiirane, 2,2-dimethylthiirane, 2-hexylthiirane, 2-phenylthiirane, etc.) and the like. Cyclic ether group-containing compound (D)
As the heterocyclic-containing compound (A1) using the epoxy-containing compound (D1), the following general formulas (2) and (3)
Indicated by General formula

[0019]

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[0020]

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Wherein n is an integer of 1 to 10. One of Y ² and Z ² is S and the other is O, preferably, Y ² is O, Z ²
Is S. R ³ is a residue of the polyepoxy compound (D11) or the monoepoxy compound (d11). R ⁴ is the residue of an alicyclic epoxide. Here, particularly preferably,
n is 1, Y ² is O, Z ² is S, and R ³ is a residue excluding the epoxy group of the monoglycidyl compound (d11-2). ]

The method for producing the heterocyclic compound (A) of the present invention is not particularly limited. For example, 0.5 to 10 equivalents of carbon disulfide, equivalent to the cyclic ether group of the cyclic ether group-containing compound (D), It can be obtained by reacting one or more compounds selected from the group consisting of carbonyl sulfide and carbon dioxide in a solvent in the presence of a catalyst. Preferably it is carbon disulfide. The solvent is not particularly limited as long as it does not inhibit the reaction and dissolves the raw materials and products, and an aprotic solvent is usually used. For example, ethers (tetrahydrofuran, dioxane, diethyl cellosolve, dioxolan, trioxane, dibutyl cellosolve, diethyl carbitol, dibutyl carbitol, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, etc.), esters (methyl acetate, methyl acetate, etc.) Ethyl acetate, n-butyl acetate, etc.) and other polar solvents (acetonitrile, dimethylformamide,
N-methylpyrrolidone, dimethylsulfoxide, etc.) and the like, preferably tetrahydrofuran, acetone,
Ethyl acetate and the like. The catalyst is a halide of an alkali metal or an alkaline earth metal, and examples thereof include lithium chloride, lithium bromide, lithium iodide, potassium chloride, and calcium bromide, with lithium bromide being preferred. The amount of the catalyst is 0.1 to the cyclic ether group of (D).
001 to 1.0 times equivalent. Preferably 0.01 to
0.1 equivalent.

The reaction temperature is usually from 0 to 100 ° C, preferably from 20 to 70 ° C. The weight average molecular weight of the hetero ring-containing compound (A) produced as described above is 120 to 12,0.
00, preferably 200 to 8,000. The heterocyclic equivalent is usually from 120 to 1,200, preferably from 200 to 800. The viscosity at 25 ° C is usually 20P
a · s or less, preferably 10 Pa · s or less, more preferably 5 Pa · s or less, and particularly preferably 1 Pa · s or less.
Pa · s or less. Specific examples of the hetero ring-containing compound (A) obtained as described above include those shown in Table 1.

[0024]

[Table 1]

As the polyepoxy compound (B) having two or more epoxy groups in the molecule of the present invention, the same as (D11) can be mentioned. Preferably it is (D11-1).

The amino compound (C) of the present invention is not particularly limited as long as it has two or more active hydrogens derived from amino groups in the molecule, and can be appropriately selected according to the use and purpose. Preferred are compounds having 2 to 10 active hydrogens derived from amino groups in the molecule, and more preferred are compounds having 3 to 6 active hydrogens. The active hydrogen equivalent (molecular weight per active hydrogen) of (C) is usually 15 to 50.
0, preferably 20 to 200. When the active hydrogen equivalent is 500 or less, the crosslinked structure does not become loose and the cured product has good physical properties such as adhesion and durability. When the active hydrogen equivalent is 15 or more, the cured product has good physical properties such as adhesion, durability, and chemical resistance.

Examples of the amino compound (C) include the following (C1) to (C9). (C1) aliphatic polyamines (2 to 18 carbon atoms, 2 to 7 functional groups, 60 to 500 molecular weight); (i) aliphatic polyamine ポ リ alkylene diamine having 2 to 6 carbon atoms (ethylenediamine, propylenediamine, trimethylenediamine) , Tetramethylenediamine, hexamethylenediamine, etc.), polyalkylene (C2-C2)
6) polyamines [diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.]}; (ii) their alkyl (1 to 4 carbon atoms) or hydroxyalkyl (C2-C4) substituted [dialkyl (C1-C3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine,
2,5-dimethyl-2,5-hexamethylenediamine,
(Iii) an alicyclic or heterocyclic-containing aliphatic polyamine [3.
9-bis (3-aminopropyl) -2,4,8,10-
Tetraoxaspiro [5,5] undecane, etc.]; (iv) aromatic ring-containing aliphatic amines (8 to 15 carbon atoms)
(Xylylenediamine, tetrachloro-p-xylylenediamine, etc.);

(C2) an alicyclic polyamine (having 4 to 1 carbon atoms)
5, functional group number 2-3); 1,3-diaminocyclohexane, isophoronediamine, mensendiamine, 4,4 ′
-Methylenedicyclohexanediamine (hydrogenated methylenedianiline) and the like; (C3) heterocyclic polyamine (4 to 15 carbon atoms, 2 to 3 functional groups): piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine (C4) aromatic polyamines (6 to 20 carbon atoms, 2 to 3 functional groups, 100 to 1000 molecular weight); (i) unsubstituted fragrances, 1,4 bis (2-amino-2-methylpropyl) piperazine and the like; Group polyamines [1,2-, 1,3- and 1,4-phenylenediamines, 2,4'- and 4,4
'-Diphenylmethanediamine, crude diphenylmethanediamine (polyphenylpolymethylenepolyamine), diaminodiphenylsulfone, benzidine, thiodianiline, bis (3,4-diaminophenyl) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, triphenyl Methane-4,4 ', 4 "-triamine, naphthylenediamine and the like;

(Ii) A nucleus-substituted alkyl group [C1-C1 such as methyl, ethyl, n- and i-propyl, butyl, etc.]
Aromatic polyamine having a (4 alkyl group), for example, 2,
4- and 2,6-tolylenediamine, crude tolylenediamine, diethyltolylenediamine, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4 '
-Bis (o-toluidine), dianisidine, diaminoditolyl sulfone, 1,3-dimethyl-2,4-diaminobenzene, 1,3-diethyl-2,4-diaminobenzene, 1,3-dimethyl-2,6 -Diaminobenzene,
1,4-diethyl-2,5-diaminobenzene, 1,4
-Diisopropyl-2,5-diaminobenzene, 1,4
-Dibutyl-2,5-diaminobenzene, 2,4-diaminomesitylene, 1,3,5-triethyl-2,4-diaminobenzene, 1,3,5-triisopropyl-2,
4-diaminobenzene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 2,3-dimethyl-1,4-diamino Naphthalene, 2,6-dimethyl-
1,5-diaminonaphthalene, 2,6-diisopropyl-1,5-diaminonaphthalene, 2,6-dibutyl-
1,5-diaminonaphthalene, 3,3 ′, 5,5′-tetramethylbenzidine, 3,3 ′, 5,5′-tetraisopropylbenzidine, 3,3 ′, 5,5′-tetramethyl-4, 4'-diaminodiphenylmethane, 3,3
', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 3,3', 5,5'-tetraisopropyl-4,4'-diaminodiphenylmethane, 3,3 ',
5,5'-tetrabutyl-4,4'-diaminodiphenylmethane, 3,5-diethyl-3'-methyl-2 ', 4
-Diaminodiphenylmethane, 3,5-diisopropyl-3'-methyl-2 ', 4-diaminodiphenylmethane, 3,3'-diethyl-2,2'-diaminodiphenylmethane, 4,4'-diamino-3,3'- Dimethyldiphenylmethane, 3,3 ', 5,5'-tetraethyl-
4,4'-diaminobenzophenone, 3,3 ', 5,5
'-Tetraisopropyl-4,4'-diaminobenzophenone, 3,3', 5,5'-tetraethyl-4,4 '
-Diaminodiphenyl ether, 3,3 ', 5,5'-
Tetraisopropyl-4,4'-diaminodiphenylsulfone and the like, and mixtures of these isomers in various proportions;

(Iii) Nuclear-substituted electron-withdrawing groups (Cl, B
aromatic polyamines having halogens such as r, I and F; alkoxy groups such as methoxy and ethoxy; nitro groups) [methylenebis-o-chloroaniline, 4-chloro-o-phenylenediamine, 2-chloro-1,4 -Phenylenediamine, 3-amino-4-chloroaniline, 4-bromo-1,3-phenylenediamine, 2,5-dichloro-
1,4-phenylenediamine, 5-nitro-1,3-phenylenediamine, 3-dimethoxy-4-aminoaniline; 4,4'-diamino-3,3'-dimethyl-5,5
'-Dibromo-diphenylmethane, 3,3'-dichlorobenzidine, 3,3'-dimethoxybenzidine, bis (4-amino-3-chlorophenyl) oxide, bis (4-amino-2-chlorophenyl) propane, bis (4- Amino-2-chlorophenyl) sulfone, bis (4-amino-3-methoxyphenyl) decane, bis (4-aminophenyl) sulfide, bis (4-aminophenyl) telluride, bis (4-aminophenyl) selenide, bis ( 4-amino-3-methoxyphenyl) disulfide, 4,4'-methylenebis (2-iodoaniline), 4,4'-methylenebis (2-bromoaniline), 4,4'-methylenebis (2-fluoroaniline), 4-aminophenyl-2-chloroaniline and the like];

(Iv) Aromatic polyamine having a secondary amino group [-NH2 of the aromatic polyamine of (i) to (iii) above]
In which a part or all of is replaced by -NH-R '(R' is an alkyl group such as a lower alkyl group such as methyl and ethyl)] [4,4'-di (methylamino) diphenylmethane, 1-methyl (C5) polyamide polyamine: dicarboxylic acid (such as dimer acid) and excess (more than 2 moles per mole of acid) polyamines (the above alkylene having 2 to 7 functional groups) Polyamidepolyamine (number average molecular weight 200-1000) obtained by condensation with diamine, polyalkylenepolyamine, etc.
(C6) Polyether polyamine: hydride of cyanoethylated product of polyether polyol (such as the above-mentioned polyalkylene glycol) (molecular weight: 100 to 1,000), and the like; (C7) Epoxy-added polyamine: epoxy compound (the above polyepoxide (D11) and Monoepoxide (d
11)) Epoxy-added polyamines (molecular weight 100 to 1000) obtained by adding 1 to 30 moles of 1 mole to polyamines (such as the above-mentioned alkylenediamines and polyalkylene polyamines);

(C8) Cyanoethylated polyamine: cyanoethylated polyamine obtained by addition reaction of acrylonitrile with polyamines (such as the above-mentioned alkylenediamines and polyalkylenepolyamines), (biscyanoethyldiethylenetriamine and the like) (molecular weight 100 to 500)
(C9) Other polyamino compounds: (i) hydrazines (hydrazine, monoalkylhydrazine, etc.);
i) dihydrazides (succinic dihydrazide, adipic dihydrazide, isophthalic dihydrazide,
(Iii) guanidines (such as butylguanidine and 1-cyanoguanidine);
(Iv) dicyandiamide and the like; and a mixture of two or more thereof. Of the above (C1) to (C9), (C) is preferred in order to provide the adhesive of the present invention with high-speed curability.
1), (C2), (C3) and (C5), and particularly preferred is (C1).

In the adhesive of the present invention, (A):
The compounding ratio of (B) :( C) is% by weight when the total amount of (A) to (C) is 100, and preferably 5 to 40: 1.
0 to 90: 5 to 60, more preferably 10 to 4
0:10 to 80: 5 to 50, particularly preferably 15
４０40: 10 to 75: 5 to 30. When (A) is 5 or more, low-temperature curability becomes good, and when it is 40 or less, it has an appropriate pot life and workability becomes good. (B) is 1
When it is 0 or more, the adhesiveness becomes good, and when it is 90 or less, the viscosity of the system becomes small and the workability becomes good. (C) is 5
When it is above, the adhesiveness becomes good, and when it is below 60, amine brushing does not occur.

The adhesive of the present invention contains the amino compound (C) as an essential component as a curing agent, but further contains a basic compound (E) as a curing accelerating catalyst, if necessary, for the purpose of further promoting curability. Can be done. Examples of the basic compound (E) include a tertiary amino compound (E1), an alkali compound (E2) such as sodium methylate, sodium hydroxide, sodium hydroxide, lithium carbonate, and the like, triethylphosphine,
Lewis base compounds such as triphenylphosphine (E3)
And the like. Among these, a tertiary amino compound (E1) is preferable.

The tertiary amino compound (E1) preferred as (E) is not particularly limited as long as it has a tertiary amino group in the molecule.
1) to (E1-3). (E1-1) an aliphatic tertiary amine having 3 to 20 carbon atoms and 1 to 4 amino groups; trimethylamine, triethylamine,
Dimethylcyclohexylamine, dimethylbenzylamine, 1,3-dimethylimidazolidinone, 1,2-dimethylimidazole, tetraethylmethylenediamine, tetramethylpropane-1,3-diamine, tetramethylhexane-1,6-diamine, pentamethyl Diethylenetriamine, pentamethyldipropylenetriamine, tetramethylguanidine, bis (2-dimethylaminoethyl) ether, ethylene glycol (3-dimethyl) aminopropyl ether, and the like; (E1-2) having 9 to 20 carbon atoms and 1 to 4 amino groups. Aromatic tertiary amines; N, N-dimethylaminomethylphenol (commonly called "DMP-10"), tris (N, N-dimethylaminomethylphenol (commonly called "DMP-30"))
(E1-3) a nitrogen-containing heterocyclic compound having 4 to 20 carbon atoms and 1 to 6 amino groups; 1,8-diazabicyclo (5,4,
0) -undecene-7 (commonly called "DBU"), 1,5-diazabicyclo (4,3,0) -nonene-5 (commonly called "DBU")
N "), 6-dibutylamino-1,8-diazabicyclo (5,4,0) -undecene-7 (commonly called" DBA-DB
U "), triethylenediamine, hexamethylenetetramine, dimethylpiperazine, N-methyl-N '-(2-
Dimethylamino) -ethylpiperazine, N-methylmorpholine, N- (N ′, N′-dimethylaminoethyl) morpholine, dimethylaminoethanol, dimethylaminoethoxyethanol, N, N, N′-trimethylaminoethyl-ethanolamine, N-methyl-N '-(2-
Hydroxyethyl) morpholine and the like.

The type and amount of the tertiary amino compound (E1) may be appropriately selected according to the curing speed and the pot life to be obtained.
It is preferable to add about 0.1 to 50 parts by weight based on parts by weight.

Examples of the adhesion improver that can be used to further improve the adhesion of the adhesive of the present invention include silane coupling agents, titanium coupling agents, aluminum coupling agents and the like. Examples of such a silane coupling agent include vinylalkyl (1 to 4 carbon atoms) alkoxy (1 to 4 carbon atoms) silane [eg, vinyltrimethoxysilane, vinyltriethoxysilane, etc.], (meth) acryloyloxyalkyl ( C1-C4) silane [for example, γ-methacryloxypropyltrimethoxysilane, etc.], alkyl (C1-C4) alkoxy (C1-C1)
~ 4) silanes [e.g., methyltrimethoxysilane, methyltriethoxysilane, etc.], amino (1-4 in the molecule)
) Alkyl (C 2-15) alkoxy (C 1
To 4) silanes [eg, γ- (2-aminoethyl) aminopropyltrimethoxysilane, aminopropyltrimethoxysilane, N-phenylaminopropylmethyldimethoxysilane, etc.], epoxy (1 to 4 per molecule) alkyl (carbon Formulas 1-4) alkoxy (C 1-4) silanes [eg γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, etc.], mercapto (1 to 4 per molecule) alkyl ( C1-C4 alkoxy (C1-C4) silane [for example, γ-mercaptotrimethoxysilane and the like] and the like. As the titanium coupling agent, Ti (OC ₁₇ H)
₃₅ ) ₄ , Ti (OiC ₃ H ₇ ) ₂ [OC (CH ₃ ) HC
OCH ₃ ] ₂ Ti (On-C ₄ H ₉ ) ₂ [OC ₂ H ₄ N (C ₂
H ₄ OH) ₂ ] ₂ , titanium-i-propoxyoctylene glycolate, i-propoxytitanium tri-i-stearate, (ethylene glycolato) titanium bis (dioctyl phosphate) and the like. Examples of the aluminum coupling agent include tributoxy aluminum and tri stearoxy aluminum. These coupling agents are
Two or more kinds may be used in combination. Although any coupling agent can be used, a silane coupling agent is preferred from the viewpoint of handling and cost. Among them, preferred are vinylalkylalkoxysilane, (meth) acryloyloxyalkylalkoxysilane, aminoalkylalkoxysilane and epoxyalkylalkoxysilane, and particularly preferred are vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane,
γ- (2-aminoethyl) aminopropyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane.

The adhesive of the present invention may optionally contain (1)
Hindered amines, hydroquinones, hindered phenols, antioxidants such as sulfur-containing compounds, (2) benzophenones, benzotriazoles, salicylates, metal complex salts and other ultraviolet absorbers, (3) metal soaps, Inorganic and organic salts of heavy metals (eg, zinc, tin, lead, cadmium, etc.), stabilizers such as organic tin compounds, (4) phthalic acid esters, phosphate esters, fatty acid esters, epoxidized soybean oil, castor oil, liquid paraffin alkyl Plasticizers such as polycyclic aromatic hydrocarbons, (5) paraffin wax, microcrystalline wax, polymerized wax, beeswax,
Waxes such as whale wax, low molecular weight polyolefin, (6)
Non-reactive diluents such as benzyl alcohol, tar, and bitumen; (7) reactive diluents such as low-molecular aliphatic glycidyl ether and aromatic monoglycidyl ether; (8) calcium carbonate, kaolin, talc, mica, bentonite, Clay, sericite, asbestos, glass fiber powder,
Carbon fiber powder, aramid fiber powder, nylon fiber powder, acrylic fiber powder, glass balloon, shirasu balloon, coal powder,
Fillers such as acrylic resin powder, phenol resin powder, metal powder, ceramic powder, zeolite, slate powder, etc. (9)
Deodorants such as activated carbon, zeolite, silica sol, and silica gel (10) carbon black, titanium oxide, red iron oxide,
Pigments or dyes such as lead red, para red, navy blue, etc., (11) solvents such as ethyl acetate, toluene, alcohols, ethers, ketones, etc., (12) foaming agents, (13) defoamers, (14) dehydrating agents , (1
5) Antistatic agents, (16) antibacterial agents, (17) fungicides, (18) viscosity modifiers, (19) fragrances, (20) flame retardants and the like can be added.

The adhesive of the present invention is a reactive adhesive,
The curing mechanism is as follows. First, (C) reacts with (A) to open a ring to generate an SH group, and the SH group reacts with (B). In this case, (C) also reacts with (B), but the reaction rate with (B) is higher for the SH group than for (C). Accordingly, the following (i) or (ii) is exemplified as a storage and use form of each component of the adhesive for joining new and old concrete of the present invention. (I) The hetero ring-containing compound (A), the epoxy group-containing compound (B), and the amino compound (C) are stored in three independent liquid forms, and the three components are mixed and cured at the time of use. The basic compound (E), which is an optional component, may be stored alone as the fourth component, and may be used by mixing with other components at the time of use.
It can also be stored in the form added in (A) and / or (C). (Ii) The mixture of the hetero ring-containing compound (A) and the epoxy group-containing compound (B) and the amino compound (C) are stored in two separate liquid forms, and the two components are mixed and cured at the time of use. The basic compound (E), which is an optional component, is
As a component, it can be stored alone, mixed with other components at the time of use, or stored as added in (C).

The adhesive of the present invention can be mixed with (A), (B), (C) and other compounds using a conventional mixer such as a universal mixer. (C) is usually blended at the time of use. The adhesive is 25 ° C. in view of workability of the coating film, curability and adhesiveness.
Is preferably 2.5 to 4 Pa · s, and at 0 ° C., preferably 5 to 7 Pa · s. The adhesive can be cured at a low temperature, and can be sufficiently cured even in a low-temperature environment of 5 ° C. or less. The cured product is excellent in physical properties such as adhesiveness, durability, and chemical resistance.

The jointing operation of new and old concrete using the adhesive of the present invention can be carried out according to a conventional method. Specifically, dust and dirt attached to the surface of the old concrete surface are removed, and then the jointing adhesive is applied using a brush, a roller, etc., and new concrete is poured in before the adhesive is hardened. Or it is a method of pouring. Further, from the cured form of the adhesive of the present invention, the coating thickness of the adhesive is preferably 5 mm or less, and 1
It can be applied over and over once or several times. The adhesive for jointing of the present invention is excellent in adhesiveness to concrete, so its application is not limited to jointing of old and new concrete, embedding anchor bolts, repairing crack injection of concrete, repairing concrete floating, It can be used effectively for protective coating of concrete floors, adhesion of tiles, etc.

[0042]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. Parts in Examples and Comparative Examples represent parts by mass.

The test method of the evaluation items in the examples is as follows. [Chemical resistance]; The adhesive for jointing new and old concrete of the present invention is 0.1 mm on a steel plate specified by JIS A5400.
After coating using a film applicator, the coating surface was cured at 0 ° C and 25 ° C.
Performed according to SA5400. In addition, ○ indicates no change, Δ indicates fading, and × indicates swelling or peeling. [Mixed viscosity]: The adhesive for jointing new and old concretes of the present invention blended with the compositions shown in Tables 2 and 3 at 0 ° C and 25 ° C was stirred, and 2 minutes later, measured with a BL-type rotational viscometer. (Unit: mPa · s) [Adhesive strength]; 30 × 30 × 5c at 0 ° C. and 25 ° C.
m, a 1.5-mm-thick adhesive for jointing the old and new concretes of the present invention blended with the composition of Tables 2 and 3 with a wool roller B-23 on the surface of a sidewalk PC board having a thickness of 1.5 mm and cured for 7 days. It was measured by the Kenken-type adhesive strength test method. (Unit: K
gf / cm ² )

Production Example 1 A reaction vessel was charged with 90 parts of carbon disulfide, 5 parts of lithium bromide, and 120 parts of tetrahydrofuran (THF) and stirred and dissolved. While maintaining the inside of the reaction vessel at 20 ° C. or less, 58 parts of 2
-After dropwise addition of ethylhexyl glycidyl ether, 4
Aged at 0 ° C. for 5 hours. After distilling off THF and excess carbon disulfide under reduced pressure, the mixture was filtered to obtain a solution having a viscosity of 40 m at 25 ° C.
A pale yellow liquid heterocyclic compound (A-1) having a Pa · s and heterocyclic group equivalent of 262 was obtained. Production Example 2 90 parts of carbon disulfide and 5 parts of lithium chloride in a reaction vessel, TH
F140 parts were charged and stirred and dissolved.
While maintaining the temperature at 0 ° C. or lower, 140 parts of trimethylolpropane triglycidyl ether (epoxy equivalent: 140) was added dropwise, followed by aging at 40 ° C. for 5 hours. THF under reduced pressure
After distilling off excess carbon disulfide and filtration,
A heterocyclic compound (A-2) as a pale yellow liquid having a viscosity of 130 mPa · s and a heterocyclic group equivalent of 218 was obtained.

Production Example 3 90 parts of carbon disulfide, 5 parts of lithium bromide and TH
F120 parts were charged and stirred and dissolved.
While maintaining the temperature at 0 ° C. or lower, 58 parts of trimethylene oxide were added dropwise, and the mixture was aged at 40 ° C. for 5 hours. Under reduced pressure, T
After distilling off HF and excess carbon disulfide, the mixture was filtered to obtain 2
A slightly yellow liquid heterocyclic compound (A-3) having a viscosity of 40 mPa · s at 5 ° C and a heterocyclic group equivalent of 140 was obtained.

Examples 1 to 5 and Comparative Examples 1 to 3 Each component was mixed and stirred at the compounding amounts shown in Tables 2 and 3, and a performance evaluation test as an adhesive for joining new and old concrete was conducted by the above-mentioned test method. went. The following were used as polyepoxide (B). Polyepoxide (B-1); Epicoat 828 (manufactured by Yuka Shell Epoxy Co., Ltd .; bisphenol A diglycidyl ether, epoxy equivalent 190, viscosity 11 Pa · s) An amino compound having two or more active hydrogens derived from amino groups in a molecule ( The following was used as C). Aliphatic polyamine (C-1); meta-xylylenediamine (active hydrogen equivalent: 36, viscosity: 7 mPa · s) The following were used as a curing accelerator. DMP-30 (E-2); tris (N, N-dimethylaminomethyl) phenol "Capcur 3-800" (active hydrogen equivalent: 28, manufactured by Henkel KK) in Tables 2 and 3.
0, viscosity 1.8 Pa · s) is a polymercaptan compound. Ketimine M was synthesized by a dehydration reaction between polyoxypropylene diamine and methyl isobutyl ketone. 0 ° C of Examples 1 to 5 and Comparative Examples 1 to 5
Are shown in Table 2, and the evaluation results at 25 ° C. are shown in Table 3.

[0047]

[Table 2]

[0048]

[Table 3]

[0049]

The adhesive for joining new and old concrete according to the present invention has the following advantages: (1) It has curability even at a low temperature such as room temperature to 5 ° C. (2) It has low viscosity, has an appropriate pot life, and is excellent in workability. (3) It has excellent adhesive properties and excellent cured physical properties such as chemical resistance. Therefore, it is very useful as an adhesive for splicing concrete, glass, metal, wood and the like. And so on. (4) Since no organic solvent is used, it is suitable for recoating and can reduce safety problems such as air pollution.

Continued on front page F-term (reference) 2E172 DD04 4J036 AA01 DA04 DC01 DC03 DC04 DC06 DC09 DC10 DC11 DC14 DD04 FA12 FB13 FB14 FB15 4J040 EC031 EC051 EC061 EC071 EC081 EC091 EC101 EC121 EC211 EC241 EC261 GA11 HB43 HCB05 HC23 HC08 HC11 HD20 HD30 HD35 HD36 HD37 HD41 HD43 HD45 KA14 KA23 KA24 KA26 KA29 KA31 KA35 KA42 KA43 MA06 NA12

Claims (8)

[Claims] 1. A heterocyclic compound (A) represented by the following general formula (1), a polyepoxy compound (B) containing two or more epoxy groups in the molecule, and an amino group in the molecule. An adhesive for joining new and old concrete, comprising an amino compound (C) having two or more active hydrogens. Embedded image [In the formula (1), n is an integer of 1 to 10, X ¹ , Y ¹ and Z ¹
Are each independently an oxygen or sulfur atom; R ¹ is a residue or a hydrogen atom of the cyclic ether group-containing compound (D); R ² is a hydrocarbon group having 2 to 10 carbon atoms. ] 2. The adhesive according to claim 1, wherein (A) is a hetero ring-containing compound (A1) represented by the following general formula (2) or (3). General formula Embedded image [In the formula (2), n is an integer of 1 to 10, one of Y ² and Z ² is S and the other is O; R ³ is a residue of polyepoxide (D11) or monoepoxide (d11). In the formula (3), R
⁴ is the residue of an alicyclic epoxide. ] 3. The compound (A1) is represented by the following general formula (4)
2. The compound (A2) which is a hetero ring-containing compound represented by the formula:
Or the adhesive according to 2. Embedded image [In the formula (4), one of Y ² and Z ² is S and the other is O; R ⁵ is a residue excluding the glycidyl group of monoglycidyl ether (d11-2). 4. The adhesive according to claim 1, wherein (C) is an aliphatic polyamino compound. 5. The adhesive composition further comprises a curing accelerator, an adhesion promoter, a dehydrating agent, a filler, a plasticizer, an antioxidant, a pigment, a reactive diluent, and a solvent. The adhesive according to any one of claims 1 to 4, further comprising one or more additives. 6. The adhesive according to claim 5, wherein the additive is an adhesion enhancer. 7. The adhesive according to claim 6, wherein the adhesion improver is a silane coupling agent. 8. A cured product obtained by curing the adhesive according to claim 1.