JP3048674B2 - Aqueous adhesive composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-based adhesive composition, and more particularly to a water-based adhesive composition, which exhibits high water resistance, heat resistance and durability by cold pressing, and furthermore, has no contamination to wood and has a hardening agent. Even if blended, the adhesive performance will not decrease over time.
There, of the preferred aqueous adhesive composition as wood adhesives.

[0002]

2. Description of the Related Art Conventionally, formalin-based adhesives composed of urea-formalin resin, acid-curable phenol-formalin resin, resorcinol-formalin resin, etc. have been used as water-resistant adhesives for wood that can be cold pressed. Have been. However, these adhesives require that the cold pressing conditions be at a temperature of 2 ° C.
At 0 ° C., a long press of 16 hours or more was required, and there was a problem in production efficiency. In addition, acid-curable phenol-formalin resin adhesives and resorcinol-formalin resin adhesives have both high water resistance and durability, but the adhesive itself has a reddish-brown color. In addition, since the adhesive layer is colored and a strong acid substance is used in the catalyst used for the acid-curable phenol-formalin resin adhesive, the adhered material causes wood contamination and wood deterioration, However, there is a drawback that the commercial value of the product is lowered and the use is restricted.

Recently, as an improvement over these conventional adhesives, an adhesive comprising a maleic imide-based copolymer and a polymer aqueous emulsion, and a polyhydric alcohol di- or tri-emulsion are added to the adhesive. An aqueous adhesive comprising a glycidyl ether compound has been proposed ( Japanese Patent Publication No. 55-1954). A continuous boiling test in which a tetrafunctional epoxy compound having a tertiary amino nitrogen atom was blended as an adhesive having a higher water-resistant adhesive strength than that described in JP-B-55-1954. Wood adhesive showing sufficient adhesiveness is disclosed in
245680. However, Japanese Patent Publication No. 55-1954 and Japanese Patent Application Laid-Open No. 60-245
The adhesive proposed in the 680 gazette exhibits good adhesive strength in a boiling and continuous boiling test in which heat is applied during the test to accelerate the curing, but there is contamination with wood, and practically, There is a problem.

Further, in recent years, an aqueous polymer compound containing polyvinyl alcohol has been used as a main component, and a solvent which has little mutual solubility with water but dissolves an isocyanate compound or an isocyanate-based polymer is blended. Aqueous polymer-isocyanate-based adhesives composed of a curing agent are widely used and can be cold-pressed and have high water resistance. However, when this adhesive is used in the summer (30-40 ° C), it takes about 1-2 hours,
There is a problem that foaming causes an increase in viscosity and a rapid decrease in water resistance.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned drawbacks of the prior art, and particularly to exhibit high water resistance, heat resistance and durability by cold pressing. and an object further, there is no contamination to the timber, even when a curing agent, there is no decrease in the bonding performance over time, especially, to provide a suitable aqueous adhesive composition as wood adhesives And

[0006]

SUMMARY OF THE INVENTION The present invention provides an aqueous solution of a polyvinyl alcohol polymer having a carboxyl group in the molecule and a tetrafunctional epoxy compound having a tertiary amino nitrogen atom. And the general formula shown in the following chemical formula 1.

Embedded image (Where D represents an alkylene group having 1 to 10 carbon atoms, an arylene group, an alkylenedioxy group or a sulfonyl group) represented by the following formula: Amino group-containing acrylic emulsion having
Amino group-containing aqueous acrylic having john or active hydrogen
And a water-based adhesive composition containing a resin as an essential component.

[0007] The polyvinyl alcohol polymer having a carboxyl group which constitutes an aqueous solution of the polyvinyl alcohol polymer having a carboxyl group in the molecule used in the present invention includes, for example, vinyl acetate and ethylenically unsaturated polymer. It can be obtained by saponifying a copolymer obtained by copolymerizing dicarboxylic acid or its monoester, diester or anhydride. Examples of the ethylenically unsaturated dicarboxylic acids or monoesters, diesters or anhydrides thereof include maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, dimethyl maleate, and maleic acid lower alcohol esters such as diethyl maleate. , acrylic acid or methacrylic acid or crotonic acid or itaconic acid and fumaric - le acid and its monoester exemplified in the maleic acid, and the like can be illustrated diester or anhydride, carboxy <br/> in the molecule The polyvinyl alcohol polymer having a sil group can be obtained by the methods described in JP-B-51-38753 and JP-A-53-91995. The average degree of saponification and the average degree of polymerization of the polyvinyl alcohol containing the carboxyl group are not particularly limited, but the residual acetic acid group is 0.1 to 0.2.
Those having a range of 1 to 15 mol% and an average degree of polymerization of 500 to 2600 are preferred. Here, the content of the carboxyl group is suitably in the range of 0.05 to 30 mol%, preferably 1 to 15 mol%. When the content of the carboxyl group is 0.
If the amount is less than 05 mol%, the crosslinking of the adhesive of the present invention is insufficient at the time of practical use, so that the adhesive force cannot be exhibited.
If it exceeds, the contribution to water resistance is reduced, and it is not economical.

The tetrafunctional epoxy compound having a tertiary amino nitrogen atom used in the present invention is an N, N-diglycylamino group-containing compound represented by the general formula (1).
D in the formula is alkylene having 1 to 10 carbon atoms such as linear alkylene, branched alkylene or cyclic alkylene, phenylene, alkyl-substituted phenylene, halogen-substituted phenylene, alkylenediphenylene, and hydrogen in phenylene is alkyl- or halogen-substituted. And arylene such as alkylenediphenylene, sulfonyldiarylene, alkylenedioxy, and a polymer of alkyleneoxy. Specific examples of the N, N-diglycidylamino group-containing compound include N, N, N ′, N′-tetraglycidylethylenediamine, N, N, N ′, N′-tetraglycidylhexamethylenediamine, 1,3 -Screw (N, N-
Diglycidylaminomethyl) cyclohexane, 1-
(N, N-diglycidylaminomethyl) -1,5,5-
Trimethyl-3- (N, N-diglycidylamino) cyclohexane, N, N, N ', N'-tetraglycidyl)
-Diaminotoluene, N, N, N ', N'-tetraglycidyl-1,3-xylylenediamine, N, N, N',
N'-tetraglycidyl-4,4-diaminodiphenylmethane, disubstituted halogen or tetrasubstituted halogen, bis (N, N-diglycidylaminophenyl) sulfone, bis (N, N-diglycidylaminophenoxyphenyl) ) Sulfone, 4 '-(N, N-diglycidylamino) phenyl ester of 4- (N, N-diglycidylamino) benzenesulfonic acid, bis (N, N-diglycidylaminotrimethylene) alkylene glycol, Bis (N, N-diglycidylaminotrimethylene) alkylene glycol, bis (N, N-diglycidylaminotrimethylene) -nona (butylene glycol) and the like can be mentioned. Further, in addition to the compound represented by the above general formula, N, N-
Diglycidylamino-2,4-bis (glycidyloxy) aniline can also be used. Among them, preferred are N, N, N ', N'-tetraglycidyl-
1,3-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane and the like.

As the amino group-containing acrylic emulsion having active hydrogen used in the present invention, for example, an amino group-containing emulsion having active hydrogen obtained by modifying a carboxyl group-containing acrylic emulsion with alkyleneimine is exemplified. The acrylic emulsion containing a carboxyl group specifically refers to a monomer (A) such as a monocarboxylic acid such as (meth) acrylic acid, cinnamic acid, crotonic acid, or the like such as an itaconic acid, maleic acid, or fumaric acid. One or a mixture of two or more selected from the group of unsaturated monomers containing a carboxyl group such as a saturated dicarboxylic acid or a monoester thereof, and the monomer (A) are optionally used.
Flip and copolymerizable monomer, specifically, the monomer (B) (meth) acrylamide, N- methylol - Le (meth) acrylamide, 2-hydroxyethyl (meth) acrylate - DOO,
2-hydroxypropyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate,
n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate,
Isobutyl (meth) acrylate, t-butyl (meth)
Acrylate, 2-ethylhexyl (meth) acrylate
, Cylohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate
, (Meth) acrylonitrile, dimethylaminoethyl (meth) acrylate, diethylethylamino (meth)
One or a mixture of two or more selected from the group of acrylates, styrenes and the like can be obtained by a generally known method, for example, in the presence of a polymerization catalyst such as potassium peroxide, an anionic or nonionic one. It is a polymer obtained by emulsion polymerization in water using an emulsifier such as a surfactant, and these are industrially produced, for example, as a carboxyl group-containing acrylic emulsion. The amount of the carboxyl group (—COOH) is required to be 2% by weight or more as the monomer (A), and is preferably
2.5 to 15% by weight. In addition, these carboxyl group-containing emulsions at the time of the above-mentioned emulsion polymerization are, in advance, a monomer having two or more copolymerizable unsaturations in one molecule, such as sivinylbenzene,
One in which the inside of the emulsion is crosslinked, one in which the degree of polymerization is controlled using a chain transfer agent such as t-dodecyl mercaptan,
Alternatively, emulsion polymerization may be carried out by a known method such as a multilayer structure (core-shell type) emulsion obtained by sequentially polymerizing a mixture of two or more types of monomers and a power feed method.

[0010] The amino group-containing aqueous acrylic resin having active hydrogen used in the present invention, for example, an amino group-containing aqueous acrylic with modified active hydrogen of an aqueous acrylic resin containing a carboxyl group by an alkylene imine
For example. The water-based acrylic resin containing a carboxyl group specifically refers to one or a mixture of two or more carboxyl-containing unsaturated monomers of the monomer (A) described for the emulsion containing a carboxyl group. And an aqueous resin obtained by solution polymerization of a monomer (A) and one or two or more kinds of mixtures selected from the group of monomers (B) copolymerizable as required , or a solution polymerization. Even if the polymer obtained by the method is not water-soluble, the polymer may be mixed with a basic substance such as ammonia, an amine compound such as trimethylamine, triethylamine, monoethanolamine, or a basic substance such as sodium hydroxide or potassium hydroxide. It is an aqueous resin obtained by summing. Further, carboxyl group-containing poval, lignin, rosin and the like are also included.

An amino group-containing acrylic emulsion having active hydrogen modified by the above alkyleneimine,
Aqueous acrylic resins, A containing a carboxyl group
It can be produced by modifying a cryl emulsion or an aqueous acrylic resin with an alkylene imine. Examples of the alkylene imine include ethylene imine, propylene imine, and butylene imine.
Further, N- (2-aminoethyl) aziridine, N- (2
N- (2-aminoalkyl) such as -aminopropyl) aziridine and N- (2-aminoethyl) propyleneimine
Substituted alkylene imines can be used as well. The amount of modification with the alkylene imine is 0.2 to 0.2 to the carboxyl group of the emulsion containing a carboxyl group.
A range of 2.5 mole times is sufficient, and preferably 0.5 mole.
１．５1.5 mole times. Amino group-containing acrylic emulsion or aqueous containing active hydrogen is an acrylic Emar job down or aqueous acrylic resin containing these carboxyl group which has been modified by alkylene imine
The acrylic resin may be used alone or as a mixture of two or more.

In the present invention, the amount of the tetrafunctional epoxy compound having a tertiary amino nitrogen atom is determined by the solid content of the aqueous solution of the polyvinyl alcohol polymer having a carboxyl group in the molecule and the active hydrogen. Acrylic Emma Having Amino Group
The total of the solids Rujon or aqueous acrylic resin 10
0.5 to 100 parts by weight, preferably 2 parts by weight per 0 parts by weight
To 65 parts by weight, and less than 0.5 part by weight,
If the water resistance is poor, on the other hand, if it exceeds 100 parts by weight, the pot life becomes short and it is economically disadvantageous.

[0013] The composition of the present invention may optionally contain
Solvents such as toluene, butyl acetate and carbitol, plasticizers such as phthalic acid esters, extenders or fillers such as clay, talc, calcium carbonate, mica, and silicic acid powder, white pigments such as titanium white and coloring Pigment, dye, polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, starch, sizing agent or viscosity agent such as dextrin, dispersant, wetting agent, defoaming agent such as silcon oil, An antifreezing agent such as ethylene glycol, an antiseptic / antifungal agent, a rust inhibitor, and the like may be appropriately added.

[0014]

Next, the present invention will be described based on production examples, examples and comparative examples. Production Example 1. Stirrer, reflux condenser, thermometer, nitrogen inlet tube and dropper
After charging 398 parts (weight, the same applies hereinafter) of deionized water and 40 parts of an anionic surfactant (25% by weight aqueous solution) in a 1-liter separable flask equipped with The temperature rose. 48 parts of acrylic acid, 57 parts of methyl methacrylate and 111 parts of butyl acrylate,
A polymerizable monomer mixture consisting of 184 parts of styrene was added to a 40 part flask, and the mixture was stirred for 15 minutes.
4.6 parts of a 5% by weight aqueous hydrogen peroxide solution and 4.2 parts of a 3% by weight aqueous L-ascorbic acid solution were added to initiate polymerization. From 15 minutes after the start of the polymerization, the remaining polymerizable monomer mixture was dropped uniformly over 90 minutes. During this time, 41 parts of a 1.75% by weight aqueous hydrogen peroxide solution and 37 parts of a 3% by weight aqueous L-ascorbic acid solution were divided and dropped into the flask every 10 minutes until the dropping of the polymerizable monomer mixture was completed. After dropping, the mixture was aged for 1 hour and cooled to obtain an emulsion having a nonvolatile content of 44.5% by weight. Next, 31.8 parts of a 16.6% by weight aqueous solution of ethyleneimine was added to 150 parts of the emulsion with stirring, and the mixture was reacted at 50 ° C. for 2 hours.
An amino group-containing acrylic emulsion having an amino hydrogen equivalent of 3000 g · Solid / eq was obtained.

Production Example 2 A stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube, and a dropper
398 g of deionized water and an anionic surfactant (25% by weight)
Aqueous solution) at 68 ° C. while introducing nitrogen.
The temperature rose. Acrylic acid 60 parts, methyl methacrylate 5
40 parts of a polymerizable monomer mixture consisting of 3 parts, 103 parts of butyl acrylate and 184 parts of styrene was added to a flask, stirred for 15 minutes, and then 4.6 parts of 1.75% by weight of hydrogen peroxide solution. And a 3% by weight aqueous L-ascorbic acid solution 4.2
Was added to initiate polymerization. From 15 minutes after the start of the polymerization, the remaining polymerizable monomer mixture was dropped uniformly over 90 minutes. During this time, 41 parts of 1.75 wt% hydrogen peroxide solution and 3 parts
37 parts by weight of an aqueous L-ascorbic acid solution was divided and dropped into the flask every 10 minutes until the dropping of the polymerizable monomer mixture was completed. After dropping, the mixture was aged for 1 hour and cooled to obtain an emulsion having a nonvolatile content of 44.5% by weight. Next, 31.8 parts of an aqueous solution of 18.8% by weight of ethyleneimine was added to 150 parts of this emulsion while stirring, and the reaction was carried out at 50 ° C. for 2 hours.
An aminoethyl group-containing emulsion of 00 g · Solid / eq was obtained.

Production Example 3 A stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube, and a dropper
398 g of deionized water and an anionic surfactant (25% by weight)
Aqueous solution) at 68 ° C. while introducing nitrogen.
The temperature rose. Acrylic acid 32 parts, methyl methacrylate 6
40 parts of a polymerizable monomer mixture consisting of 2 parts, 122 parts of butyl acrylate and 184 parts of styrene was added to a flask and stirred for 15 minutes, and then 4.6 parts of 1.75% by weight hydrogen peroxide solution. And a 3% by weight aqueous L-ascorbic acid solution 4.2
Was added to initiate polymerization. From 15 minutes after the start of the polymerization, the remaining polymerizable monomer mixture was dropped uniformly over 90 minutes. During this time, 41 parts of 1.75 wt% hydrogen peroxide solution and 3 parts
37 parts by weight of an aqueous L-ascorbic acid solution was divided and dropped into the flask every 10 minutes until the dropping of the polymerizable monomer mixture was completed. After dropping, the mixture was aged for 1 hour and cooled to obtain an emulsion having a nonvolatile content of 44.5% by weight. Next, 24.8 parts of an aqueous solution of 12.9% by weight of ethyleneimine was added to 150 parts of the emulsion while stirring, and the mixture was reacted at 50 ° C. for 2 hours to obtain a nonvolatile content of 40% by weight and an amino hydrogen equivalent of 50%.
An aminoethyl group-containing emulsion of 00 g · Solid / eq was obtained.

Example 1, Comparative Example 1 Water 15 was added to 15 parts by weight of a polyvinyl alcohol polymer having a carboxyl group (trade name: KM-618, manufactured by Kuraray Co., Ltd.).
The mixture was stirred at 85 to 90 ° C. for 2 hours to obtain a carboxyl group-containing polyvinyl alcohol polymer aqueous solution (A-1). 84 parts by weight of the aqueous solution of the polyvinyl alcohol polymer having a carboxyl group (A-1) was mixed with heavy calcium carbonate (Toyo Fine Chemical Co., Ltd.)
Product name: Whiten P-30) 90 parts by weight, Production Example 1
-Containing acrylic emulsion resin 9 prepared in
0 parts by weight and 21 parts by weight of water were added and sufficiently stirred to obtain a uniform aqueous dispersion composition (B-1) having a solid content of 49%. To 100 parts of the above aqueous dispersion composition (B-1), various epoxy compounds are added as follows, in an amount such that the number of epoxy groups is the same as the number present in the adhesive of the present invention, and The mixture was stirred to prepare the adhesive.

The above aqueous dispersion composition (B-1) 100
N, N, N ', N'-tetraglycidyl-1, a tetrafunctional epoxy compound having a tertiary amino nitrogen atom
A composition containing 5 parts of 3-xylenediamine (trade name; TETRAD-X, manufactured by Mitsubishi Gas Chemical Company, Ltd.) is defined as a composition (C-1). The above aqueous dispersion composition (B-1)
1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, a tetrafunctional epoxy compound having a tertiary amino nitrogen atom in 100 parts TETRAD-C
A composition obtained by mixing 5 parts of Mitsubishi Gas Chemical Co., Ltd.) is referred to as a composition (C-2). The above aqueous dispersion composition (B-1)
100 parts of bisphenol A diglycidyl ether type epoxy resin (trade name: ADEKARESIN EP-41)
A composition obtained by mixing 90 parts of Asahi Denka Kogyo Co., Ltd.) is referred to as composition (C-3). The above aqueous dispersion composition (B-
1) 100 parts of glycerin triglycidyl ether type epoxy resin (trade name: Denacol EX-314)
A composition containing 6.9 parts of Nagase Sangyo Co., Ltd.) is defined as a composition (C-4). The above aqueous dispersion composition (B-1)
100 parts of bisphenol F diglycidyl ether type epoxy resin (EPO / TOHTO YDF-1)
The composition (C-5) was prepared by blending 8.1 parts of No. 70 Toto Resin Chemical Co., Ltd.). 100 parts of the above aqueous dispersion composition (B-1) is mixed with a phenol-volac glycidyl ether type epoxy resin (EPO • TOHTO).
YDPN-638 manufactured by Toto Resin Chemical Co., Ltd.) 8.6
What blended the part is set as the composition (C-6).

Using these compositions, a birch material with a thickness of 10 m / m was used as an adherend under the following bonding conditions. Coating amount 250 g / m ² Deposit within 5 minutes Pressing 10 kg / cm ³ × 16 hours (20 ° C) Curing 7 days (20 ° C)

The normal strength, the water resistance and the boiling water resistance of the obtained adhesive material between birch and birch are shown in JIS K below.
The measurement was carried out in accordance with-6852 "Testing method of adhesive shear strength of adhesive." Normal strength: Measured at 20 ° C., 65% RH Water resistant strength: Measured in a state of being left in water at 20 ° C. for 3 days and kept wet Boiling water strength: 60 ± 3 after immersion in boiling water for 4 hours
After drying at a temperature of ° C. for 20 hours, further immersing in boiling water for 4 hours, immersing in water for 1 hour, the measurement results are shown in Table 1 below in a wet state.

[0021]

TABLE 1 normal state resistance water resistance boiling real (C-1) 178 (100 ) 81 (0) 60 (0) facilities Example (C-2) 188 (100 ) 83 (0) 63 (0) ratio (C-3) 158 (87) 15 (0) 30 (0) Comparison (C-4) 162 (83) 43 (0) 29 (0) Example (C-5) 134 (0) 10 (0) 0 (0) (C-6) 137 (0) 00 However, the unit of the numerical value in the table is kg / cm ³ , and the number in parentheses indicates the percentage of wood fracture. The same applies to the following table. From Table 1 above, the composition comprising an aqueous solution of a polyvinyl alcohol polymer having a carboxyl group and an amino group-containing acrylic emulsion or an aqueous acrylic resin having active hydrogen has a tertiary amino nitrogen atom. A mixture of N, N, N ', N'-tetraglycidyl-1,3-xylenediamine and 1,3-bis (NN-diglycidylaminomethyl) cyclohexane, which are tetrafunctional epoxy compounds. (C-1) and (C-1)
-2) It can be seen that only the adhesive shows good adhesive strength in water resistance and boiling water resistance.

Comparative Example 2 Isobutylene-maleic anhydride-maleic acid imide copolymer (Isovalene 304, trade name of Kuraray Co., Ltd., copolymerization molar ratio 1: 0.5: 0.5, hereinafter abbreviated as acid imide copolymer) To 50 parts by weight, 20 parts by weight of industrial 25% aqueous ammonia and 70 parts by weight of water were added, and the mixture was stirred at 85 to 90 ° C. for 2 hours to obtain an acid imide copolymer aqueous solution (A-2). Aqueous solution of the above acid imide copolymer (A-2) 84
90 parts by weight of heavy calcium carbonate (trade name: Whiten P-30, manufactured by Toyo Fine Chemical Co., Ltd.), and amino group-containing acrylic emulsion produced in Production Example 1
90 parts by weight of the resin and 21 parts by weight of water were added and sufficiently stirred to obtain a uniform aqueous dispersion composition (B-2). N, N, N ', N'- is a tetrafunctional epoxy compound having a tertiary amino nitrogen atom in 100 parts of the aqueous dispersion composition (B-2).
A composition (C-7) was prepared by mixing 5 parts of tetraglycidyl-1,3-xylenediamine (trade name: TETRAD-X, manufactured by Mitsubishi Gas Chemical Co., Ltd.). 250 g / m ² of an adhesive was applied to a veneer, a hippopotamus, and a cypress wood veneer, and allowed to stand at 40 × 95% RH for 16 hours, and then visually observed for contamination. The results are shown in Table 2 in comparison with the composition (C-1) of the present invention.

Comparative Example 3 Heavy calcium carbonate (Toyo Fine Chemical Co., Ltd.) was added to 84 parts by weight of the above acid imide copolymer aqueous solution (A-2).
90 parts by weight of styrene-butadiene copolymer latex (trade name: KS-207, manufactured by Sumitomo Nogatack Co., Ltd.) and 21 parts by weight of water and sufficiently stirred, and the mixture was stirred thoroughly to obtain a uniform aqueous dispersion composition. A product (B-3) was obtained. N, a tetrafunctional epoxy compound having a tertiary amino nitrogen atom in 100 parts of the above aqueous dispersion composition (B-3).
A composition (C-8) was prepared by mixing 5 parts of N, N ', N'-tetraglycidyl-1,3-xylenediamine (trade name: TETRAD-X, manufactured by Mitsubishi Gas Chemical Company, Ltd.). The contamination state was visually observed in the same manner as in Comparative Example 2. Table 2 shows the results.

[0024]

[Table 2]

Example 2 84 parts by weight of the aqueous solution of the polyvinyl alcohol polymer having a carboxyl group (A-1) used in Example 1 was mixed with heavy calcium carbonate (trade name: Whiten manufactured by Toyo Fine Chemical Co., Ltd.). P-30) 90 parts by weight, 90 parts by weight of the amino group-containing acrylic emulsion produced in Production Example 2, water 21
The weight part was added and sufficiently stirred to obtain a uniform aqueous dispersion composition (B-4) having a solid content of 49%. This aqueous dispersion composition (B-
4) 100 parts by weight of 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane 2 parts by weight,
Composition (C-9) was prepared. In 84 parts by weight of the aqueous solution of the polyvinyl alcohol polymer having a carboxyl group (A-1) used in Example 1, heavy calcium carbonate (trade name: Whiten P-3 manufactured by Toyo Fine Chemical Co., Ltd.) was added.
0) 90 parts by weight, amino group-containing a
90 parts by weight of krill emulsion and 21 parts by weight of water were added, and the mixture was sufficiently stirred to obtain a uniform aqueous dispersion of 49% solid content (B-
5) was obtained. 100 parts by weight of this aqueous dispersion composition (B-5) was mixed with 8 parts by weight of 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane to obtain a composition (C-1)
0) was prepared. The normal strength, the water resistance and the boiling water resistance were measured in the same manner as in Example 1 in accordance with JIS K-6852 “Testing method for adhesive shear strength of adhesive”. Table 3 shows the results.

[0026]

Table 3 Composition Normal water resistance boiling (C-9) 172 (100) 79 (0) 68 (0) ( C-10) 168 (100) 72 (0) 71 (0)

Example 3 The aqueous dispersion composition (C-1) obtained in Example 1 was allowed to stand in an atmosphere of a temperature of 20 ° C. and a humidity of 65%, and immediately thereafter, one hour later, After 8 hours and 24 hours, Example 1
In the same manner as above, normal strength, water resistance and boiling water resistance,
It was measured in accordance with JIS K-6852 "Testing method for adhesive shear strength of adhesive." Table 4 shows the results. still,
For comparison, an aqueous polymer-isocyanate adhesive (trade name: P-eye Bond 127, 100 parts, curing agent 15
(Manufactured by Oka Shinko Co., Ltd.) was used to examine the adhesive performance due to the change over time after mixing the curing agent.

[0028]

[Table 4] Table 4

[0029]

According to the present invention, not only the drawbacks of the prior art but also the boiling at a time when heat is applied and curing is accelerated, as well as at room temperature water suitable for practical tests Even when immersed in water, it shows good adhesive strength and can obtain good water resistance test results, especially exhibiting high water resistance, heat resistance and durability by cold pressing, and furthermore, with respect to wood pollution without even a curing agent, there is no decrease in the bonding performance over time, it is possible to provide a suitable aqueous adhesive compositions inter alia, as a wood adhesive.

──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Koji Nagaoka 141-1 Chidori-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture Inside the Nippon Shokubai Chemical Co., Ltd. 14-1 Machi Kawasaki Laboratory, Nippon Shokubai Chemical Industry Co., Ltd. (72) Masaharu Iwasaki 6-10-5 Higashi-Mukojima, Sumida-ku, Tokyo (72) Inventor Ichiro Fujii 28-28 Totsuka Sakaicho, Kawaguchi City, Saitama Prefecture 1 (72) Inventor Masaru Fujimoto 1-1-18-1, Hama, Kawaguchi-shi, Saitama (56) References JP-A-3-45678 (JP, A) JP-A-2-69587 (JP, A) JP-A-60 -245680 (JP, A) JP-A-3-287684 (JP, A) JP-A-4-264182 (JP, A) JP-A-49-28629 (JP, A) (58) Fields investigated (Int. . ^7, DB name) C09J 1/00 - 201/10 CA (STN ) REGISTRY (STN) WPI / L (QUESTEL)

Claims (1)

(57) [Claims] 1. An aqueous solution of a polyvinyl alcohol polymer having a carboxyl group in the molecule and a tetrafunctional epoxy compound having a tertiary amino nitrogen atom, wherein the epoxy compound is represented by the following general formula: 1) (Where D represents an alkylene group having 1 to 10 carbon atoms, an arylene group, an alkylenedioxy group or a sulfonyl group) represented by the following formula: Amino group-containing acrylic emulsion having
Amino group-containing water having a John or active hydrogen acrylate
Water-based adhesive composition comprising a resin as an essential component.