JP2001146568A - Concrete primer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a one-pack epoxy resin based concrete primer which is moisture-curable at normal temperatures and at low temperatures and excels in storage stability. SOLUTION: This concrete primer comprises (A) a heterocycle-containing compound represented by the formula (wherein (n) is an integer of 1-10; X1, Y1, and Z1 are each independently O or S; R1 is a residue of a cyclic ether- containing compound or H; and R2 is a 2-10C hydrocarbon group), (B) a polyepoxide, and/or (C) a compound which forms a primary or secondary amino group by the reaction with water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a concrete primer, and more particularly, to a one-part low-temperature curable primer made of a novel epoxy resin.

[0002]

2. Description of the Related Art A two-component epoxy resin-based concrete primer which has been conventionally used is a ketimine-based one-component epoxy resin-based concrete primer. Since this primer is a one-pack type, it can be used as it is without the need for mixing, weighing and the like, and thus has the advantage of excellent workability.

[0003]

However, ketimine-based one-pack concrete primers have a low curing speed at room temperature and hardly cure at a temperature of 5 ° C. or lower, and thus cannot be used practically.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that a compound containing a heterocyclic-containing compound and a compound capable of forming a primary and / or secondary amino group by reaction with water. It has been found that the above-mentioned problem can be solved by using a one-pack type epoxy resin-based concrete primer using, and the present invention has been completed. That is, the present invention provides a heterocyclic-containing compound (A) represented by the following general formula (1), a polyepoxide (B), and / or a compound that generates a primary or secondary amino group by reaction with water. It is a concrete primer characterized by comprising (C). General formula

[0005]

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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 . ]

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the hetero ring-containing compound (A) is represented by the general formula (1). Where n
Is an integer of 1 to 10, preferably 2 to 8, X ¹ , Y ¹ and Z
¹ is an oxygen or sulfur atom, respectively. Preferably X ¹
Is a sulfur atom (S), and ^one of Y ¹ and Z ¹ is a sulfur atom (S)
And the other is an oxygen atom (O). R ² has 2 to 10 carbon atoms
And a trivalent hydrocarbon group> CH (C
H ₂ ) _m — (m is an integer of 1 to 9), for example,> CHCH ₂ —,> CHCH ₂ CH ₂ —,> CHCH _{2
CH 2 CH 2 -,> CHCH} 2 CH 2 CH 2 CH 2 CH 2 -
Etc .; tetravalent hydrocarbon group> CH (CH ₂ ) _m CH <(m is 0
-8), for example,> CHCH
<,> CHCH ₂ CH <,> CHCH ₂ CH ₂ CH <,>
CHCH ₂ CH ₂ CH ₂ CH ₂ CH <and the like, preferably a trivalent hydrocarbon group, particularly preferably> CH
CH ₂ — and> CHCH ₂ CH ₂ —. R ¹ is a hydrogen atom or a residue of a cyclic ether group-containing compound (D);
₂ is a residue constituting a ring other than an oxygen atom in the cyclic ether group. (D) is represented by the general formula (7). General formula

[0008]

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The cyclic ether group is not particularly limited as long as it has one oxygen atom in the ring, and examples thereof include compounds having 1 to 10 cyclic ether groups in the molecule. Examples of the cyclic ether group-containing compound (D) include an epoxy group-containing compound (D1) and an oxetane compound (D2) described below, and preferably the epoxy group-containing compound (D1). Epoxy group-containing compound (D
1) includes monoepoxide (d11) and polyepoxide (D11) having two or more epoxy groups in the molecule. The monoepoxide (d11) is not particularly limited as long as it has one epoxy group in the molecule, and can be appropriately selected depending on the use and purpose. Examples include the following. For example, 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.), Glycidyl ethers of hydrocarbons (n-butyl glycidyl ether, allyl glycidyl ether, 2-ethyl-hexyl glycidyl ether,
2-methyloctyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, p-s
ec-butylphenyl glycidyl ether, p-ter
t-butylphenyl glycidyl ether, etc.), having 3 carbon atoms
And glycidyl esters of monocarboxylic acids (e.g., glycidyl acrylate and glycidyl methacrylate), 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 10 carbon atoms.

The polyepoxide (D11) is not particularly limited as long as it has 2 to 6 or more epoxy groups in the molecule, and can be appropriately selected depending on the use and purpose. Preferred are those having 2 to 6 epoxy groups in the molecule. The epoxy equivalent (molecular weight per epoxy group) of the polyepoxide is usually 64 to 10
00, preferably 90-500. When the epoxy equivalent is 1,000 or less, the crosslinked structure is not loose, and the cured product has good physical properties such as water resistance, chemical resistance, and mechanical strength. On the other hand, when the epoxy equivalent is 64 or more, the cured product has A crosslinked structure having good water resistance, chemical resistance, mechanical strength, and the like is obtained. Examples of the polyepoxide (D11) include the following (D11-1) to (D11-5).

(D11-1) Glycidyl ether type
(I) Diglycidyl ether of dihydric phenols Diglycidyl ether of dihydric phenols 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 or the like;

(Ii) Trivalent to hexavalent or higher polyglycidyl ethers of polyhydric phenols 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) ethane tetraglycidyl ether, p-glycidylphenyldimethyltolyl bisphenol A glycidyl ether, trismethyl-tert-butyl-butylhydroxymethanetriglycidyl ether, 4,4'-oxybis (1,4-phenylethyl) Tetracresol glycidyl ether, 4,4'-oxybis (1,4-
Phenylethyl) phenylglycidyl ether, bis (dihydroxynaphthalene) tetraglycidyl ether, glycidyl ether of phenol or cresol novolak resin (molecular weight 400 to 5000), glycidyl ether of limonenephenol novolak resin (molecular weight 400 to 5000), phenol and glyoxal, glue Polyphenols obtained by the condensation reaction of taraldehyde or formaldehyde (molecular weight 400 to 50)
00) and a molecular weight of 400 to 50 obtained by a condensation reaction of resorcinol and acetone.
And polyglycidyl ether of polyphenol No. 00.

(Iii) Diglycidyl ether of an aliphatic dihydric alcohol Diglycidyl ether of a diol having 2 to 100 carbon atoms and a molecular weight of 62 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: 106 to 400
0) Diglycidyl ether, polypropylene glycol (molecular weight 134 to 5000) diglycidyl ether, polytetramethylene glycol (molecular weight 162 to 500)
0) Diglycidyl ether, neopentyl glycol diglycidyl ether, alkylene oxide of bisphenol A [ethylene oxide or propylene oxide (1
(Iv) polyglycidyl ether of a trivalent to hexavalent or higher aliphatic alcohol having 3 to 50 or more carbon atoms and a molecular weight of 92 to 1000.
Glycidyl ethers of polyhydric alcohols having 0 to 3 or 6 valences, for example, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether,
Pentaerythritol tetraglycidyl ether, sorbitol hexaglycidyl ether, poly (n = 2
5) Glycerol polyglycidyl ether and the like.

(D11-2) Glycidyl ester type glycidyl ester of a divalent to hexavalent or higher valent 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. As glycidylamines of aromatic amines, N, N-diglycidylaniline,
N, N-diglycidyl toluidine, N, N, N ', N'
-Tetraglycidyldiaminodiphenylmethane, N,
N, N ', N'-tetraglycidyldiaminodiphenylsulfone, N, N, N', N'-tetraglycidyldiethyldiphenylmethane, N, N, O-triglycidylaminophenol and the like. Examples of the aliphatic amine glycidylamine include N, N, N ', N'-tetraglycidylxylylenediamine, N, N, N', N'-tetraglycidylhexamethylenediamine and the like. Examples of the alicyclic amine include hydrogenated compounds of N, N, N ', N'-tetraglycidylxylylenediamine.
Glycidylamine as a heterocyclic amine includes trisglycidylmelamine and the like.

(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
Epoxidized polybutadiene having a molecular weight of 90
2,500), epoxidized soybean oil (molecular weight 130-
2,500). (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.
These polyepoxides can be used in combination of two or more. 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), an alicyclic carboxylic acid oxetane compound having 8 to 30 carbon atoms (such as bisoxetane cyclohexanedicarboxylate), and an aromatic isocyanate oxetane compound [(D11-
2) Oxetane, MDI bis oxetane, etc.].

The method for producing the heterocyclic-containing compound (A) in the concrete primer of the present invention is not particularly limited. For example, the cyclic ether group-containing compound (D) and 0.5 to 10 equivalents of the cyclic ether group are used. In the presence of a catalyst in a solvent.
The solvent is not particularly limited as long as it does not hinder the reaction and dissolves the raw materials and products, and usually an aprotic solvent is used. For example, ethers (tetrahydrofuran, dioxane, diethyl cellosolve, dioxolan,
Trioxane, dibutyl cellosolve, diethyl carbitol, dibutyl carbitol, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, etc.), esters (methyl acetate, ethyl acetate, n-butyl acetate, etc.), and other polar solvents (Acetonitrile, dimethylformamide, N-methylpyrrolidone,
Dimethyl sulfoxide and the like, and preferably, tetrahydrofuran, acetone, ethyl acetate and the like. The catalyst is a halide of an alkali metal or an alkaline earth metal, such as lithium chloride, lithium bromide, lithium iodide, potassium chloride, calcium bromide, and the like.
Preferred is lithium bromide. The amount of the catalyst is 0.001 to 1.0 times equivalent to the cyclic ether group of (D). Preferably it is 0.01 to 0.1 times equivalent. The reaction temperature is generally 0-100 ° C, preferably 20-70 ° C. The heterocyclic compound (A1) using the epoxy group-containing compound (D1) as the cyclic ether group-containing compound (D) is represented by the following general formulas (2) and (3). General formula

[0019]

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[0020]

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Wherein n is an integer of 1 to 10. Y ² , Z ²
One is S and the other is O, and more preferably, Y ² is O and Z ² is S. R ³ is polyepoxide (B1)
Or it is a residue of monoepoxide (b1). R ⁴ is the residue of (D11-5). The method for producing the hetero ring-containing compound (A1) is a case where the epoxy group-containing compound (D1) is used as the cyclic ether group-containing compound (D) in the method for producing the hetero ring-containing compound (A).
The epoxy group-containing compound (D1) is not particularly limited as long as it is a compound having one or two or more epoxy groups in a molecule. The weight average molecular weight of the hetero ring-containing compound (A) is from 120 to 12,000, preferably from 200 to 12,000.
8,000. The heterocycle equivalent is usually 120 to 1,2.
00, preferably 200-800. 25 ° C
Is usually 5 to 20,000 mPa · s,
It is preferably 10 to 10,000 mPa · s, more preferably 5,000 mPa · s or less, and particularly preferably 10 to 1,000 mPa. Specific examples of the hetero ring-containing compound (A) obtained as described above include those described in Table 1.

[0022]

[Table 1]

The polyepoxide (B) used in the concrete primer of the present invention is the same as the above-mentioned polyepoxide (D11), and is preferably (D11-1). It is preferable that the polyepoxide has no active hydrogen or, if it has active hydrogen, has an active hydrogen equivalent of 4000 or more.

In the present invention, the compound (C) which forms a primary and / or secondary amino group by reaction with water is not particularly limited, and can be appropriately selected depending on the use and purpose. Preferably, it is a compound having 2 to 10 active hydrogens derived from a primary amino group and / or a secondary amino group generated by a reaction with water in the molecule, more preferably 3 to
It is a compound having six. (C) the active hydrogen 1
The molecular weight per piece is usually from 14 to 500, preferably from 20 to 300. When the active hydrogen equivalent is 500 or less, the crosslinked structure does not become loose and the cured product has chemical resistance,
Physical properties such as mechanical strength are also good. On the other hand, when the active hydrogen equivalent is 14 or more, physical properties such as chemical resistance and mechanical strength of the cured product are good. In the concrete primer of the present invention, the (C) includes a heterocyclic compound (C1) and a ketimine compound (C2). (C1) and (C2) may be used alone or as a mixture. As the (C1), at least two heterocyclic groups (c1) represented by the following general formula (4) are present in the molecule.
The compound is not particularly limited as long as it is a hetero ring-containing compound having at least one compound, and preferably a compound represented by the following general formula (5) (C
11). General formula

[0025]

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Wherein m is 1 or an integer of 2 to 10, R ⁵
And R ⁶ each independently represent a hydrogen atom, a linear or branched alkyl or alkenyl group having 1 to 6 carbon atoms, or an aryl group having a carbon number of 6-8, R ⁵ and R ⁶ combine with the carbon The cycloalkyl ring of Formulas 5 to 7 may be formed. R ⁷ represents an alkylene group having 2 to 10 carbon atoms. R
⁸ is a hydrogen atom or a methyl group. R ⁹ is a residue of the amino compound (E) or the polyol (F). ]

In the hetero ring-containing compound (C11) represented by the general formula (5), R ⁵ and R ⁶ represent a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n- Butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, neopentyl, tert-pentyl, n-hexyl, iso-hexyl, vinyl, allyl Group, propenyl group, phenyl group and benzyl group. Also,
R ⁵ , R ⁶ and a cyclopentyl ring, a cyclohexyl ring and a cycloheptyl ring in which the carbon atoms to which R ⁵ and R ⁶ are bonded are combined. From the viewpoint of curing speed, at least one of R ⁵ and R ⁶ is preferably a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, and at least one of R ⁵ and R ⁶ is preferred. Is particularly preferably a hydrogen atom, a methyl group or an ethyl group. Examples of R ⁷ include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, and an octamethylene group. Among them, ethylene, propylene, tetramethylene and pentamethylene groups are preferred from the viewpoint of curing speed.

As the amino compound (E), the following (P
1) to (P9). (P1) 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) alicyclic or heterocyclic-containing aliphatic polyamine [3,9-bis (3-aminopropyl) -2,4,8,
10-tetraoxaspiro [5,5] undecane and the like]; (iv) aromatic ring-containing aliphatic amines (8 to 15 carbon atoms)
(P2) alicyclic polyamine (4 to 15 carbon atoms, 2 to 3 functional groups): 1,3-diaminocyclohexane, isophoronediamine, mensendiamine; 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline)
(P3) Heterocyclic polyamine (4 to 15 carbon atoms, 2 to 3 functional groups): piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4-bis (2-amino-2- Methylpropyl) piperazine and the like;

(P4) Aromatic polyamines (C6 to C6)
20, functional groups 2-3, molecular weight 100-1000); (i) unsubstituted aromatic polyamines [1,2-, 1,3- and 1,4-phenylenediamine, 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) aromatic having a nucleus-substituted alkyl group [C1-C4 alkyl group such as methyl, ethyl, n- and i-propyl, butyl, etc.] Group polyamines such as 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-diaminonaphthalene, 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'-diaminodiphenyl sulfone, etc.] Mixtures of 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 (P5) 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.
(P6) polyether polyamine: hydride of cyanoethylated polyether polyol (such as the above-mentioned polyalkylene glycol) (molecular weight: 100 to 1,000), etc .; (P7) epoxy-added polyamine: epoxy compound (polyepoxide (B1)) And an epoxy-added polyamine (having a molecular weight of 100) obtained by adding 1 to 30 moles of a monoamine (such as ethylene oxide, propylene oxide, or phenylglycidyl ether) to 1 mole of a polyamine (such as the above-mentioned alkylene diamine or polyalkylene polyamine). ~ 1000) and the like;

(P8) 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)
(P9) Other polyamine 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 of these. Of the above (P1) to (P9), in order to impart high-speed curability to the curable composition of the present invention, (P1) is preferable.
1), (P2), (P3) and (P5), and particularly preferred is (P1).

The polyol (F) is not particularly limited as long as it is a compound having two or more hydroxyl groups in the molecule.
Polyhydric alcohol (F-1), polyalkylene ether polyol (F-2), polyester polyol (F-3), polymer polyol (F-4), polybutadiene polyol (F-5), castor oil system Polyol (F
-6), acrylic polyol (F-7) and their 2
Mixtures of more than one species. Examples of the divalent to octavalent polyhydric alcohol (F-1) include hydrocarbon polyhydric alcohols which may have an ether group having 2 to 12 carbon atoms. Specifically, ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, neopentyl glycol, 1,4-bis ( Dihydric alcohols such as hydroxymethyl) cyclohexane, 1,4-bis (hydroxyethyl) benzene, 2,2-bis (4,4′-hydroxycyclohexyl) propane; trihydric alcohols such as glycerin and trimethylolpropane; pentaerythritol , Diglycerin, α-methylglucoside, sorbitol, xylitol, mannitol, dipentaerythritol, glucose, fructose, sucrose, etc.
And octahydric alcohols.

Polyalkylene ether polyol (F-
Examples of 2) include a compound having a structure in which an alkylene oxide (hereinafter abbreviated as AO) is added to an active hydrogen atom-containing polyfunctional compound (a) having 2 to 8 functional groups, and a mixture of two or more of these compounds. The number average molecular weight of the polyalkylene ether polyol (F-2) is usually from 500 to 20,000.
0, preferably 500 to 10,000, more preferably 1,000 to 3,000.

The functionality of (F-2) is usually from 2 to
8, preferably 2-3, particularly preferably 2.
It is preferred that the degree of unsaturation of (F-2) is small,
It is 1 meq / g or less, preferably 0.05 meq / g or less, more preferably 0.02 meq / g or less.
The primary hydroxyl group content of (F-2) is not particularly limited, but is preferably 30 to 100%, more preferably 50 to 100%, and particularly preferably 70 to 100%. Polyester polyols (F-3) include low molecular weight diols and / or condensed polyester diols obtained by reacting a polyalkylene ether diol having a molecular weight of 1000 or less with a dicarboxylic acid, polylactone diols obtained by ring-opening polymerization of lactones, Polycarbonate diols obtained by reacting a low molecular diol with a carbonic acid diester of a lower alcohol (such as methanol) are included.

Examples of the low molecular diol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-, 1,3-butanediol, neopentyl glycol and 1,6-hexanediol; Molecular diols [for example, those described in JP-B-45-1474: bis (hydroxymethyl) cyclohexane, bis (hydroxyethyl) benzene, EO adducts of bisphenol A, etc.], and mixtures of two or more of these. . Examples of the polyalkylene ether diol having a molecular weight of 1,000 or less include polytetramethylene ether glycol, polypropylene glycol, polyethylene glycol, and a mixture of two or more thereof. Examples of the dicarboxylic acids include aliphatic dicarboxylic acids (succinic acid, adipic acid, azelaic acid, sebacic acid, etc.), aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, phthalic acid, etc.), and ester-forming derivatives of these dicarboxylic acids. [Acid anhydrides, lower alkyl (C1-4) esters and the like] and mixtures of two or more of these; lactones include ε-caprolactone, γ-butyrolactone,
γ-valerolactone, and a mixture of two or more thereof.

These polyester polyols (F-
Specific examples of 3) include polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyneopentyl adipate diol, polyethylene propylene adipate diol, polyethylene butylene adipate diol, polybutylene hexamethylene adipate diol, and polydiethylene adipate diol Poly (polytetramethylene ether) adipate diol, polyethylene azelate diol, polyethylene sebacate diol, polybutylene azelate diol, polyester diol such as polybutylene sebacate diol, polylactone diol such as polycaprolactone diol or triol, poly Polycarbonate diols such as hexamethylene carbonate diol; It is. Polymer polyol (F-
As 4), in a polyol (the polyalkylene ether polyol and / or the polyester polyol), a radical polymerizable monomer [for example, styrene, (meth) acrylonitrile, (meth) acrylate,
Vinyl chloride and a mixture of two or more of these), and the polymer is finely dispersed. After the completion of the polymerization reaction, the resulting polymer polyol can be used for the production of polyurethane without any post-treatment, but impurities such as organic solvents, decomposition products of polymerization initiators and unreacted monomers are removed. It is desirable to remove by conventional means.

The polymer polyol (F-
4) is usually 30 to 70%, preferably 40 to 60%,
More preferably 45-55%, most preferably 50-5%.
5% polymerized total monomer, ie polymer is polio
Translucent to opaque white or tan dispersion. Polybutadiene polyol (F-5)
Are those having a 1,2-vinyl structure,
Examples include those having a vinyl structure and a 1,4-trans structure, and those having a 1,4-trans structure.
The ratio between the 1,2-vinyl structure and the 1,4-trans structure can be variously changed, and for example, the molar ratio is 100: 0 to 100: 0.
0: 100. In addition, polybutadiene glycol (F
-5) includes homopolymers and copolymers (styrene butadiene copolymer, acrylonitrile butadiene copolymer, etc.) and hydrogenated products thereof (hydrogenation rate:
For example, 20 to 100%). The number average molecular weight of the polybutadiene glycol (F-5) is usually 500 to 1
It is 0000. The castor oil-based polyol (F-6) includes castor oil and modified castor oil (such as castor oil modified with a polyhydric alcohol such as trimethylolpropane and pentaerythritol). The equivalent (molecular weight per hydroxyl group) of the polyol (F) is usually from 100 to
It is 10,000, preferably 250 to 5,000, more preferably 500 to 1,500.

The hetero ring-containing compound (C11) represented by the general formula (5) has a number average molecular weight of usually 400 to 20,000.
00, preferably from 600 to 2,000. The viscosity (25 ° C.) is usually 200 to 200,000 cp,
It is preferably 400 to 50,000 cp. The heterocycle equivalent is usually from 150 to 2,000, preferably from 150 to 500.

The heterocycle-containing compound (C11) is usually a compound (cX1) having a secondary amine bonded to at least one hydroxyalkyl group in the molecule and a carbonyl compound (cY), that is, a compound having a ketone group in the molecule. (E.g., acetone, ethyl methyl ketone, methyl isobutyl ketone, etc.) or a compound having an aldehyde group (e.g., acetaldehyde, benzaldehyde, formaldehyde, etc.), which is obtained by a dehydration-condensation reaction. Produces a secondary amine bonded to a hydroxyalkyl group and a corresponding ketone or aldehyde, and acts as a curing agent for an epoxy resin. The method for producing the heterocyclic-containing compound (C11) is described in Japanese Patent Application No. 0088.
No. 10 describes this in detail. Therefore, the heterocyclic-containing compound is stable even in a system mixed with an epoxy resin unless water is mixed from the outside, and is very useful as a curing agent for a one-pack type epoxy resin composition.

The ketimine compound (C2) is represented by the following general formula (6). General formula

[0042]

Embedded image

Wherein p is an integer of 2 to 10; R ¹⁰ and R ¹¹
Are each independently a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 6 carbon atoms, or an aryl group having a carbon number of 6 to 8, carbon atoms bonded R ¹⁰ and R ¹¹ is 5 To 7 cycloalkyl rings may be formed. R ¹² is a residue of the amino compound (E). In the ketimine compound (C2) represented by the general formula (6), as R ¹⁰ and R ¹¹ , a heterocyclic-containing compound (C
The same as R ⁵ and R ⁶ in 1) can be mentioned, and the preferable ones are also the same. In the ketimine compound (C2) represented by the general formula (6), the amino compound (E) constituting R ¹² is also a heterocyclic-containing compound (C
The same as (E) in 1) can be mentioned, and the same is preferable for preferable ones.

In the concrete primer of the present invention, the ratio of (B) to (C) is such that the number of active hydrogens generated by the reaction with water in (C) is one per epoxy group in (B). , 0.5 to 2.0, and preferably 0.7 to 1.3. When the ratio is 0.5 or more or 2.0 or less, it is preferable that the curability does not decrease and the water resistance and mechanical strength of the cured product do not decrease. The ratio of (B) and the hetero ring-containing compound (A) is such that the hetero ring group in (A) is preferably from 0.01 to 1 epoxy group in (B).
1.0, preferably 0.05 to 0.8. When the ratio is 0.01 or more or 1.0 or less, it is preferable that the curability does not decrease and the water resistance and mechanical strength of the cured product do not decrease. The amount of the heterocyclic-containing compound (A) to be added is generally 0.1 to 200 parts, preferably 0.5 to 100 parts, more preferably 1 to 100 parts of (C) in the concrete primer. Parts to 80 parts. If the addition amount is 0.1 part or more, the curing acceleration effect and the viscosity reduction effect are sufficient, and if it is less than 200 parts, the cured product has good physical properties such as water resistance, chemical resistance, and mechanical strength. .

The concrete primer of the present invention may further contain a basic compound (G) if necessary for the purpose of further accelerating the curing speed. Examples of the basic compound (G) include a tertiary amine compound (G1), an alkali compound (G2) such as sodium methylate, sodium hydroxide, sodium hydroxide, lithium carbonate, triethylphosphine,
Lewis base compounds such as triphenylphosphine (G3)
And the like. Of these, a tertiary amine compound (G1) is preferred.

The above (G1) is not particularly limited as long as it is a compound having a tertiary amino group in the molecule, and examples thereof include the following. (I) an aliphatic amine having 3 to 20 carbon atoms and an amino group having 1 to 4 trimethylamine, triethylamine, tetraethylmethylenediamine, tetramethylpropane-1,3-diamine, tetramethylhexane-1,6-diamine, pentamethyldiethylenetriamine, Pentamethyldipropylenetriamine, bis (2-dimethylaminoethyl) ether, ethylene glycol (3-dimethyl) aminopropyl ether, dimethylaminoethanol, dimethylaminoethoxyethanol, N, N, N'-trimethylaminoethyl-ethanolamine, (Ii) an aromatic amine having 9 to 20 carbon atoms and an amino group having 1 to 4 dimethylbenzylamine, N, N-dimethylaminomethylphenol (commonly called “DMP-10”), tris (N ,
N-dimethylaminomethyl) phenol (commonly called "DMP
(Iii) a heterocyclic compound having 4 to 20 carbon atoms and 1 to 6 amino groups, 1,2-dimethylimidazole, dimethylpiperazine,
N-methyl-N '-(2-dimethylamino) -ethylpiperazine, N-methylmorpholine, N- (N', N'-
Dimethylaminoethyl) morpholine, N-methyl-N '
-(2-hydroxyethyl) morpholine, 1,8-diazabicyclo (5,4,0) -undecene-7 (commonly referred to as "D
BU "), 1,5-diazabicyclo (4,3,0) -nonene-5 (commonly called" DBN "), 6-dibutylamino-
1,8-diazabicyclo (5,4,0) -undecene-
7 (commonly called “DBA-DBU”), triethylenediamine, hexamethylenetetramine and the like.

As for (G) and (G1), the kind and the amount of addition may be appropriately selected according to the curing speed and the pot life to be obtained. Usually, 100 parts by weight of the heterocyclic-containing compound (A) is used. Is added in an amount of about 0.1 to 50 parts by weight. In order to increase the curing speed of the concrete primer, a catalyst may be added as needed. The concrete primer of the present invention further comprises a dehydrating agent, a flexibility-imparting agent, an adhesion-imparting agent, a curing accelerating catalyst, a filler, a plasticizer, a coloring inhibitor, a leveling agent, an antioxidant, a pigment, a dispersant. One or more selected from the group consisting of agents, reactive diluents, solvents, water retention agents, wetting agents, and surfactants may be blended. The compounding amount is 50 parts by weight or less, preferably 30 parts by weight or less, particularly preferably 20 parts by weight or less based on 100 parts by weight of the whole.

The dehydrating agent prevents the water mixed in the concrete primer of the present invention for any reason from reacting with the heterocyclic compound (C1) or the ketimine compound (C2), thereby improving the one-pack storage stability. It is to improve.
Examples of the dehydrating agent include a silane coupling agent, a monoisocyanate compound, a carbodiimide compound, and a zeolite. Specifically, vinyl trimethoxysilane,
Trimethyl orthoformate, 2,2-dimethoxypropane,
Synthetic zeolites and the like are mentioned, and vinyltrimethoxysilane and 2,2-dimethoxypropane are preferred. The compounding amount is 20 parts by weight or less based on 100 parts by weight of the primer,
Preferably it is 10 parts by weight or less.

Examples of the catalyst for the hydrolysis reaction of the heterocyclic compound (C1) and the ketimine compound (C2) include phosphoric acid ester, p-toluenesulfonic acid, formic acid, acetic acid, propionic acid and dibutyltin dilaurate. Examples of the catalyst for the reaction between the primary or secondary amine generated by hydrolysis and the epoxy group include tertiary amines, phenols, and triphenylphosphine. Of these, tertiary amines and phenols are preferable, and aliphatic tertiary amines such as N, N-dimethylpropylamine, N, N, N ′, N′-tetramethylhexamethylenediamine; N-methylpyrrolidine And alicyclic tertiary amines such as N, N, N'-dimethylpiperazine; and aromatic tertiary amines such as benzyldimethylamine and dimethylaminomethylphenol.

The adhesiveness-imparting agent is used not only at the time of application under normal conditions, but also to particularly improve the adhesiveness at the time of application under water-containing concrete or high humidity. As the adhesion imparting agent, a silane coupling agent,
Examples thereof include a titanium coupling agent and an aluminum coupling agent, and preferably include a silane compound having a hydrolyzable silyl group. Examples of such a silane compound include vinylalkyl (1 to 4 carbon atoms) alkoxy (1 to 4 carbon atoms) silane [for example, vinyltrimethoxysilane,
Vinyltriethoxysilane, etc.), (meth) acryloyloxyalkyl (C1-4) alkoxy (C1
4) silane [for example, γ-methacryloxypropyltrimethoxysilane and the like], alkyl (1 to 4 carbon atoms) alkoxy (1 to 4 carbon) silane [for example, methyltrimethoxysilane, methyltriethoxysilane and the like], amino (molecule) 1 to 4) alkyl (2 to 15 carbon atoms) alkoxy (1 to 4 carbon atoms) silane [for example, γ- (2-aminoethyl) aminopropyltrimethoxysilane, aminopropyltrimethoxysilane, N-phenylamino Propylmethyldimethoxysilane, etc.), epoxy (1 to 4 per molecule)
Alkyl (C1-4) Alkoxy (C1-4)
4) silane [for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, etc.], mercapto (1 to 4 in the molecule) alkyl (1 to 4 carbon atoms) alkoxy (1 to 4 carbon atoms) To 4) silanes [for example, γ-mercaptopropyltrimethoxysilane and the like] and the like. Of these, preferred are vinylalkylalkoxysilane, (meth) acryloyloxyalkylalkoxysilane, and epoxyalkylalkoxysilane, and particularly preferred are vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and γ-glycidoxy. Propyltrimethoxysilane. The amount of these silane compounds used is as follows:
The amount is preferably 0.1 to 50 parts by weight, more preferably 1 to 10 parts by weight, based on 00 parts by weight. When it is 0.1 part by weight or more, the adhesiveness (particularly, the adhesiveness on a wet surface) is improved,
If it is 50 parts by weight or less, it reacts with moisture at the time of use and does not hinder ring opening of the heterocyclic group. These silane compounds may be used in combination of two or more.

The filler is used when the concrete primer of the present invention is used as a non-primer type top coat. This filler is usually a finely pulverized solid, and the main purpose of the compounding is represented by functions such as performance such as strength and elastic modulus, durability such as weather resistance, conductivity, and thermal conductivity. Improvement of physical properties, improvement of moldability such as fluidity and shrinkage,
Or, it is an economic improvement such as increasing the amount of resources and saving resources.
The amount of the filler is preferably 0.1 to 200 parts by weight, more preferably 1 to 100 parts by weight, based on 100 parts by weight of the epoxy resin.
To 100 parts by weight, particularly preferably 3 to 50 parts by weight. Examples of the filler include calcium carbonate, carbon black, clay, talc, titanium oxide, quicklime, kaolin, zeolite, diatomaceous earth, vinyl chloride paste resin, vinylidene chloride resin balloon, and the like, and used alone or in combination. be able to. Examples of the reactive diluent include a low-molecular epoxy compound having an inner molecular weight of 500 or less (eg, styrene oxide, butylene oxide, etc.) of the epoxy resin, and a diluent having a molecular weight of 1000 or less.
To 4-functional acrylates (e.g., ethylene glycol diacrylate, propylene glycol diacrylate, etc.), low-molecular-weight heterocycle-containing compounds [e.g., monooxazoline compounds [Zoldine MS-p manufactured by Angus Co., Ltd.]
rus, etc.]] can also be used. These additives need to be sufficiently dehydrated before addition.

In order to improve the storage stability of the concrete primer of the present invention, in addition to the hetero ring-containing compound (A), the hetero ring-containing compound (C1) and the ketimine compound (C2), the polyepoxide also contains active hydrogen. If they do not have them, or if they have active hydrogen, those having an active hydrogen equivalent of 4000 or more are preferred. In the concrete primer of the present invention, the active hydrogen equivalent of (C) during storage is preferably 2,000 or more, more preferably 20,000 or more, and particularly preferably 40,000 or more. When the active hydrogen equivalent is 2000 or more, the storage stability of the concrete primer is good. If it has active hydrogen, by inactivating the group having active hydrogen to a group that does not react with the epoxy resin, it is assumed that it does not have active hydrogen, or
The active hydrogen equivalent can be within the required range. The inactivation of the active hydrogen group can be performed by monoisocyanate compounds (ethyl isocyanate, n-butyl isocyanate, phenyl isocyanate, etc.), acid anhydrides (acetic anhydride, succinic anhydride), acid halides (benzoyl chloride, etc.) or alkyl halides (Methyl chloride, methyl bromide, ethyl chloride, etc.).

Further, a polyalkylene ether having a hydrolyzable silyl group at a molecular chain terminal, which is called a modified silicone resin, may be added as a flexibility-imparting agent. More specifically, poly (methyldimethoxysilyl ether)
And the like, and commercially available products can be used. Polyalkylene (C2-6) ether (weight average molecular weight; 3)
00 to 10000) or those obtained by linking 2 to 5 of them (for example, linked by a methylene group) to the terminal of which is bonded to a 1-3 functional (preferably bifunctional) hydrolyzable silyl group. The hydrolyzable silyl group is represented by the following general formula (17).

[0054]

Embedded image

[Wherein D is -O-, -S-, -NHCO
—, —OCO—, —NH—, —ON <, and R ⁷ , R ⁸
Represents hydrogen, halogen, an alkyl group having 1 to 10 carbon atoms, an aryl group, or an arylalkyl group, and n represents 0 or 1 to 3
Represents an integer. Specific examples include a halogenosilyl group, an acyloxysilyl group, an amidosilyl group, an aminoxysilyl group, an alkenyloxysilyl group, an aminosilyl group, an oximesilyl group, an alkoxysilyl group, and a thioalkoxysilyl group.
Preferred are alkoxysilyl groups. The weight average molecular weight is preferably from 400 to 600,000. These polyalkylene ethers may be used alone or in a combination of two or more. The amount of the modified silicone resin used is preferably 10 to 500 parts, more preferably 50 parts based on 100 parts of the epoxy resin.
~ 200 parts. If it is less than 500 parts, the adhesiveness is not deteriorated, and if it is more than 10 parts, the flexibility of the cured epoxy resin is good.

When the one-pack type concrete primer is used, such a modified silicone resin is cured by moisture in the air in the presence of a modified silicone resin catalyst. As the modified silicone resin catalyst, tin compounds such as dibutyltin oxide, metal salts of carboxylic acids such as lead octylate,
Examples thereof include amine salts such as dibutylamine-2-ethylhexoate, and the amount is preferably 0.1 to 10 parts based on 100 parts of the modified silicone resin.

As a catalyst for the reaction between the primary or secondary amine produced by the hydrolysis and the epoxy group of (B), the tertiary amines and phosphines, triphenylphosphine and tributylphosphine having 3 to 30 carbon atoms. Hydrocarbon phosphines and the like can be mentioned. Of these, tertiary amines are preferred, and N, N-dimethylpropylamine, N, N,
Aliphatic tertiary amines such as N ', N'-tetramethylhexamethylenediamine; N-methylpyrrolidine, N, N'
-Alicyclic tertiary amines such as dimethylpiperazine; aromatic tertiary amines such as benzyldimethylamine and dimethylaminomethylphenol are particularly preferable.

The primer of the present invention may further contain a deodorant (H). The deodorant (H) is not particularly limited, but may be activated carbon, zeolite, silica sol,
Silica gel and the like. Among these, zeolite is preferred. In addition, the addition amount is preferably a weight ratio of the heterocyclic compound (A): deodorant (H) = 1: 0.01 to 0.5, more preferably,
1: 0.05 to 0.3.

The concrete primer of the present invention
(A), (B), (C) and, if necessary, an adhesiveness-imparting agent, a dehydrating agent, a filler, and other various additives are blended and produced according to a conventional method. can get. That is, first, (A), (B), (C) and, if necessary, various solid additives such as a filler are charged into a predetermined amount, usually a high-viscosity mixing stirrer, and the like. Preferably at a temperature of 50-100 ° C. and 700-1 mm
Mix and stir under reduced pressure of Hg, preferably 400 to 1 mmHg to obtain a mixture. Next, the heterocyclic-containing compound (C1) and / or the ketimine compound (C2), a dehydrating agent,
And various kinds of liquid additives are added in a predetermined amount, and preferably, the mixture is further stirred under reduced pressure at room temperature at 760 to 500 mmHg to obtain a desired concrete primer. The storage stability of the thus obtained concrete primer of the present invention is particularly excellent, and is also suitable as a one-pack type concrete primer. Furthermore, it is not only concrete, but also glass,
It is very effective as a base coat for buildings made of metal, wood and the like.

The actual curing reaction when the concrete primer of the present invention is used is as follows: active hydrogen derived from amino groups generated by the reaction of (C) with water in the air;
The reaction proceeds by the reaction of the active hydrogen derived from the thiol group generated by the reaction with the (A) with the (B). That is, since the curing reaction proceeds only from the surface in contact with air, when the ratio of the contact area with air to the volume is small, such as when the concrete primer is in a container, the curing speed is extremely slow. Become. Conversely, when the ratio of the surface area to the volume is increased by pouring or thinly coating concrete, the curing speed is greatly increased to a practical level. Therefore, when the concrete primer is in the container, the pot life becomes tens to hundreds of times longer than that of the conventional two-liquid type, and the unused concrete primer is repeatedly used. And time and quantity constraints during construction are greatly reduced. The curing temperature of the concrete primer of the present invention is preferably -10 ° C or higher, more preferably-
The temperature is 5 to 100C, and particularly preferably -5 to 40C. The humidity conditions are preferably 20-100% R.F. H. And particularly preferably 20 to 80% R.I. H. It is. The curing time is a few minutes to 100 hours.

A concrete structure using the concrete primer of the present invention comprises concrete, a concrete primer, and a topcoat. Concrete is conventionally known and is not particularly limited. The construction method using the concrete primer of the present invention can be carried out according to a conventional method. As an application base material, in addition to indoor concrete floors and outer walls such as floors, walls, corridors, or stairs of buildings such as houses or various factories,
Concrete floors such as leisure facilities, sports facilities, transportation facilities, roads, and parking lots. Depending on the thickness of the coating or the shape of the floor surface, it can be applied to any of these floors by a sinking method, a mortar method, a lining method, or a coating method. Therefore, the sinking method or the coating method is preferred. As a coating method of the coating method, a general method such as brush coating, spray coating, and various coater coatings can be used. The application amount of the concrete primer of the present invention is not particularly limited, but is 10 to 10 in primer coating.
The thickness is preferably 300 μm and 50 to 500 μm for base coat application, and the base coat application can be performed once to three times. The paint applied on the concrete primer of the present invention can be used without any particular limitation, for example, an ordinary overcoat paint, such as an alkyd resin, an epoxy resin, a latex, a silicon alkyd resin, a urethane resin, and a silicone acrylic resin. And fluororesin-based paints can be used. The coating amount is a solid content, preferably 5 to 1
000 μm, more preferably 10-500 μm
And particularly preferably 50 to 300 μm. The curing conditions and the like of the top coat vary depending on the type of the paint and may be ordinary curing conditions and are not particularly limited.

[0062]

The present invention will be further described with reference to the following examples.
The present invention is not limited to this. In addition, a part shows a mass part below. 1) Production of heterocycle-containing compound (A1) -1 In a reaction vessel, 76 parts of carbon disulfide, 5 parts of lithium bromide, TH
After F120 parts were charged and dissolved by stirring, 58 parts of 2-ethylhexyl 190 parts were added dropwise while maintaining the temperature at 20 ° C or lower, and the mixture was aged at 40 ° C for 5 hours. Under reduced pressure, THF and excess carbon disulfide were distilled off, followed by filtration. The obtained hetero ring-containing compound was a yellow liquid having a viscosity of 43 mPa · s and a hetero ring group equivalent of 262.

2) Production of Heterocycle-Containing Compound (C1) -1 In a reaction vessel equipped with a stirrer, a heating device, a cooling pipe and a reflux pipe equipped with a water separator, 1000 parts of methyl methacrylate, 200 parts of monoethanolamine, Hydroquinone 2.4 parts and methanol 50 parts are charged and 50
After reacting at 15 ° C. for 15 hours, 3.6 parts of hydroquinone was added, and excess methyl methacrylate and methanol were removed at 20 ° C. under reduced pressure. Next, 390 parts of acetone, 9.2 parts of paratoluenesulfonic acid, and synthetic zeolite 40 were placed in a container.
After 0 parts were charged, the atmosphere was replaced with nitrogen, the vessel was sealed, and a dehydration reaction was performed at room temperature for 10 hours while stirring. After the reaction is completed, acid adsorbent KW
-1000 (manufactured by Kyowa Chemical Industry Co., Ltd.)
Stirred at C for 3 hours. After cooling, 10 parts of Celite # 600 (manufactured by Showa Chemical Industry Co., Ltd .; diatomaceous earth A) was filtered as a filter aid, and acetone remaining in the filtrate was distilled off by heating to obtain Intermediate M. Intermediate M had a number average molecular weight of 201 and a viscosity (20 ° C .; B-type viscometer) of 50 mPa · s.

In a similar reaction vessel, 500 parts of Intermediate M and 6 mol of propylene oxide adsorbed with sorbitol 200
And 20 parts of sodium methylate, and the mixture was purged with nitrogen, heated to 100 ° C., and subjected to a transesterification reaction. After neutralization, acid adsorbent KW-1000 (manufactured by Kyowa Chemical Industry Co., Ltd.)
20 parts were charged and further stirred for 1 hour. Next, 10 parts of diatomaceous earth A was filtered at 70 ° C. as a filter aid to obtain heterocycle-containing compound B. The obtained B has a number average molecular weight of 17
00, molecular weight 300 per one heterocyclic group, viscosity (2
0 ° C .; B-type viscometer) It was a red-brown liquid of 15000 mPa · s. 3) Ketimine H Ketimine H used was Epicure H-3 (manufactured by Yuka Shell Epoxy Co .; a modified product of a ketimine compound of a polycondensate of epichlorohydrin and meta-xylylenediamine).

4) Production of one-pack type concrete primer Epicoat 807 (manufactured by Yuka Shell Epoxy Co .; bisphenol F-type epoxy resin) previously dehydrated at 80 ° C. and 20 mmHg at the ratios shown in Table 2, and Denacol EX -20
1 (manufactured by Nagase Kasei Co., Ltd .; resorcin diglycidyl ether) and heterocycle-containing compound (A1) -1 were cooled to room temperature, and then vinyltrimethoxysilane (Toray Co., Ltd.)
Dow Corning Silicone Co., Ltd.), γ-glycoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.), a heterocycle-containing compound (C1) -1 and / or ketimine H as an adhesion-imparting agent were added, and the mixture was stirred under reduced pressure again. A one-part concrete primer was manufactured. 5) Table 2 shows the measurement results of the physical properties and storage stability of the concrete primer of the present invention at low and normal temperatures. (I) Viscosity: measured at 0 ° C. and 25 ° C. in a nitrogen atmosphere by a BL or BH type rotational viscometer. (Ii) Drying time to the touch: The composition having the composition shown in Table 2 was prepared by JI
After applying to a steel plate specified in SA5400 using a 0.1 mm film applicator, it is cured at 0 ° C, 30% humidity and 25 ° C, 60% humidity until the surface resin of the coating film does not stick to the finger. Time. (Iii) Appearance: The state of the coating film surface was visually observed. Glossy, swelling, no peeling, etc. were rated as ○, and swelling, peeling, etc. were rated x. (Iv) Pencil hardness, cross cut test, abrasion resistance test: A composition having the composition shown in Table 2 was applied to a steel sheet specified by JIS A5400 using a 0.1 mm film applicator, and then heated at 20 ° C. The pencil hardness, cross cut test, and abrasion resistance of the coating film surface cured at 65% humidity were measured according to JIS A5400.
It went according to.

(V) Adhesion strength: A composition having the composition shown in Table 2 was applied on a concrete plate and cured at 20 ° C. and 65% for 7 days. It was measured with a Kenken type adhesion tester, and the state of the adhesive surface layer at that time was observed. If the material is destroyed by 100% concrete,
A part where the material was destroyed was rated as Δ, and a part where the concrete and the resin peeled off at the interface was rated as ×. (Vi) Storage stability: The compositions having the formulations shown in Table 2 were placed in a closed container purged with nitrogen, and allowed to stand in an atmosphere at 40 ° C. for 3 months, and then visually observed for appearance and fluidity. The case where there was fluidity and there was no change in appearance was evaluated as ○, the case where there was fluidity but increased the viscosity was rated as Δ, and the case where gelation occurred was evaluated as ×.

6) When the concrete primer obtained in 4) was applied to concrete, as shown in Table 2, all showed good low-temperature and room-temperature curability.

[0068]

[Table 2]

In the same manner as in Examples 1 to 3, primers not using the heterocycle-containing compound (A1) -1 were prepared according to the formulation examples shown in Table 2, and the same tests were conducted. The results are shown in Table 2.

From Examples 1 to 3 and Comparative Examples 1 and 2, it was found that when the concrete primer of the present invention was used, the curability at low and normal temperatures was superior to that of the conventional one-component concrete primer.

[0071]

The concrete primer of the present invention has the following effects. (1) Possibility of one-part type, which is a disadvantage of two-part type, such as a quantitative error when mixing the main agent and the curing agent, poor mixing, poor adhesion due to excess pot life, and pot life due to temperature changes in the workplace. Can be prevented from being deteriorated due to the variation in the injection property. (2) Since the effect speed at normal temperature is high, and curing is possible even at 0 ° C., construction in winter, which was difficult in the past, is possible. (3) Excellent storage stability.

Claims (16)

[Claims] 1. A heterocyclic-containing compound (A) represented by the following general formula (1), a polyepoxide (B), and a compound which forms a primary and / or secondary amino group by reacting with water ( A concrete primer characterized by comprising C). General formula [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 concrete primer according to claim 1, wherein (A) is a heterocyclic-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 (B1) or monoepoxide (b1). In the formula (3), R
⁴ is the residue of an alicyclic epoxide. ] 3. The viscosity at 25 ° C. of (A) is 1
The pressure is from 1 mPa · s to 1000 mPa · s.
The described concrete primer. 4. The (C) is a dehydration condensate of a primary amine and / or a secondary amine, a hydroxyl group-containing compound (cX) and a carbonyl compound (cY).
The concrete primer according to any one of the above. 5. The compound represented by the following general formula (C):
Having at least two heterocyclic groups represented by (4)
5. The composition according to claim 4, comprising a terror ring-containing compound (C1).
Cleat primer. General formula[Wherein, R^FiveAnd R⁶Are each independently a hydrogen atom or a straight chain
Or a branched alkyl or alkenyl having 1 to 6 carbon atoms
Or an aryl group having 6 to 10 carbon atoms,^FiveWhen
R⁶Combines to form a cycloalkyl ring having 5 to 7 carbon atoms
It may be. R ⁷Is an alkylene group having 1 to 10 carbon atoms
Represents ] 6. The concrete primer according to claim 5, wherein the compound (C1) is (C11) represented by the following general formula (5). General formula [In the formula, m is an integer of 1 to 10, and R ⁵ , R ⁶ and R ⁷ are the same as those in the general formula (4). R ⁹ is a residue of the amino compound (E) or the polyol compound (F). ] 7. The concrete primer according to claim 4, wherein said (C) comprises a ketimine compound (C2) represented by the following general formula (6). General formula [Wherein, p is an integer of 2 to 10; R ¹⁰ and R ¹¹ are each independently a hydrogen atom, a linear or branched alkyl or alkenyl group having 1 to 6 carbon atoms, or a C ⁶ to C 8 alkyl group. An aryl group wherein R ¹⁰ and R ¹¹ are
May form a cycloalkyl ring. R ¹² represents a residue of the amino compound (E). ] 8. The concrete primer according to claim 5, wherein (C) is a mixture of (C1) and (C2). 9. In the concrete primer,
The concrete according to any one of claims 1 to 8, wherein the amount of active hydrogen generated by decomposition of the group in (C) by moisture is 0.5 to 2.0 equivalents to 1 equivalent of the epoxy group in (B). -Top primer-. 10. A dehydrating agent, further comprising:
Flexibility imparting agent, adhesion imparting agent, curing accelerating catalyst, filler, plasticizer, coloring inhibitor, leveling agent, antioxidant,
Pigments, dispersants, reactive diluents, solvents, water retention agents, wetting agents,
The concrete primer according to any one of claims 1 to 9, further comprising at least one additive selected from the group consisting of a surfactant and a surfactant. 11. The concrete primer according to claim 10, wherein said additive is an adhesion-imparting agent. 12. The concrete primer according to claim 11, wherein the adhesion-imparting agent is a silane coupling agent. 13. The method for applying a concrete primer according to claim 1, wherein the method is selected from the group consisting of a sink pan method, a mortar method, a lining method, and a coating method. 14. A concrete structure comprising the concrete primer according to claim 1, concrete, and a topcoat. 15. A non-primer type top coat for concrete, comprising a filler and a filler added to the concrete primer according to claim 1. 16. A concrete structure comprising the non-primer type top coat of claim 15 and concrete.