JP3048673B2 - 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 is suitable as an adhesive for wood. About things.

[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. glycidyl - aqueous adhesive formed by blending the ether compound has been proposed (Japanese Patent Publication 55-1954 discloses). 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, these Japanese Patent Publication No. 55-1954 and JP 60-245
The adhesive proposed in the 680 publication shows good adhesive strength in a repeated boiling test and a continuous boiling test in which heat is applied during the test to accelerate the curing, but the room temperature conforms to a practical test. The results of the water resistance test when immersed in water are poor, and there is a problem in practical use.

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, in就, and to provide a suitable aqueous adhesive composition as wood adhesives.

[0006]

Means for Solving the Problems The present invention provides the following chemical formula 1.
General formula

Embedded image (However, in the above formula, R ¹ and R ² are a hydrogen atom, an alkyl
The same group selected from the group consisting of
Is a different group, and R ³ is a hydrogen atom, a halogen atom,
Or an alkyl group or alkenyl which may contain a hydroxyl group
And a group selected from the group consisting of
And at least one of P, Q, R and S is a carbohydrate.
Selected from the group consisting of xyl groups, their esters and their amides
Other groups that are different from the
It is a kill group. Has an acid imide structure in the molecule represented by
An aqueous solution of a multicomponent copolymer or a salt thereof, a 4-functional epoxy compound having a tertiary amino nitrogen atom, the general formula represented by the following Formula 2

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.

The water-soluble polymer constituting the aqueous solution of the water-soluble polymer having an acid imide structure in the molecule used in the present invention includes, for example, a unit (A) based on an α-olefin group in the main chain. ), A unit (B) based on maleic imide or N-substituted maleic imide, and a unit (C) based on unsaturated carboxylic acid or its ester or its amide as constituent components. And specific examples thereof include a multi-component copolymer represented by the following general formula 1 or a salt thereof.

Embedded image (However, in the above formula, R ¹ and R ² are a hydrogen atom, an alkyl
The same group selected from the group consisting of
Is a different group, and R ³ is a hydrogen atom, a halogen atom,
Or an alkyl group or alkenyl which may contain a hydroxyl group
And a group selected from the group consisting of
And at least one of P, Q, R and S is a carbohydrate.
Selected from the group consisting of xyl groups, their esters and their amides
In Barre groups, it differs from other groups are hydrogen atom or an alkyl group. Examples of the α-olefin that can constitute the unit (A) of the above formula include ethylene, propylene, 1-butene, isobutylene, 1-pentene, 1-hexene, and 1-hexene.
Heptin, 2-methyl-1-hexene, 1-octene,
1-nonene, styrene, α-methylstyrene, 1,3-
Butadiene, isoprene and the like are preferred. As the A unit, isobutylene is particularly preferable among them. The term “isobutylene” used herein refers to a return B containing isobutylene.
Also means B. Further, one or more α-olefins may be used. Note that, instead of α-olefin, an unsaturated compound similar to other α-olefin may be used. The N-substituted maleimide which can constitute the unit (B) is obtained by substituting a hydrogen atom bonded to a nitrogen atom constituting the maleimide with an appropriate substituent. alkyl such as ethyl, phenyl, hydroxyalkyl, hydroxyphenyl, Cal
Boxoxyalkyl , carboxyphenyl, primary aminoalkyl, secondary aminoalkyl, tertiary aminoalkyl groups and the like are included. Further, as an unsaturated carboxylic acid or its ester or its amide which can constitute the unit (C), acrylic acid, methacrylic acid, maleic acid,
Maleic anhydride, monomethyl maleate, monohexyl maleate, monobutyl maleate, monohexyl maleate, monooctyl maleate, monostearyl maleate, fumaric acid, monomethyl fumarate, monoethyl fumarate Acid ester, monobutyl fumarate,
Monohexyl fumarate, monooctyl fumarate, monostearyl fumarate, acrylamide, monomethyl acrylamide, monoethyl acrylamide, dimethyl acrylamide , diethyl acrylamide, hydroxyethyl acrylamide, maleic amide, fumaric amide, hydroxyethyl acryle
And the like. The molar ratio of the repeating unit (A) based on the unsaturated compound, the repeating unit (B) based on the maleic imide, and the repeating unit (C) based on the unsaturated carboxylic acid constituting the multicomponent copolymer is generally a molar ratio. A: B + C is 1: 0.8 to 1.2, preferably approximately 1: 1 and B: C is 0.9 to 1.2.
0.3: 0.1 to 0.7, preferably 0.8 to
0.4: 0.2 to 0.6 is preferred. In this case, when the amount of maleic imides is extremely large, it tends to be difficult to obtain a water-soluble adhesive. The degree of polymerization of the multipolymer is 2
About 00 to 10000 is appropriate. The degree of polymerization is 2
If it is extremely smaller than 00, the coating properties and the like tend to decrease and the adhesive performance tends to decrease. Also reverse
, When heavy Godo exceeds 10000, it tends to cause a decrease in adhesive performance with tendency of viscosity similar to the extremely high becomes above coating and the like come to decrease. In the present invention,
The polymerization degree of the multi-component copolymer is preferably in the range of 400 to 5000. If the multi-component copolymer is water-soluble as it is, it can be used as it is. If it is water-insoluble, it is made water-soluble by reacting with a basic compound. Examples of the basic compound used herein include ammonia (aqueous ammonia), ammonium salt compounds, oxides, hydroxides, and carbonate phosphates of alkali metals, alkaline earth metals, and organic amines. One or two or more kinds of alkaline substances are blended. The amount of the basic compound used is such that 30 mol% or more of the carboxyl groups in the copolymer form a salt, and the pH of the adhesive composition obtained by blending the copolymer is in the range of 4 to 10. Is preferred. When the pH is lower than 4, the curing is accelerated by the acid component, and the applicability is remarkably reduced due to thickening or gelling, and the adhesiveness is reduced. Also, p
If H exceeds 10, contamination of wood becomes remarkable and room-temperature curability tends to be poor. Adjustment of the aqueous solution of these multi-component copolymers is carried out simply by mixing with water when the copolymer is water-soluble, but the copolymer becomes water-soluble by reaction with a basic compound. When used, the reaction is carried out by mixing the copolymer with an aqueous solution containing a basic compound. Upon mixing, the mixture may be heated to 60 to 90 ° C. if necessary. The solid content of the aqueous solution is preferably 5 to 50% by weight.

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 ( 2 ).
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. Arylene such as alkylenediphenylene, sulfonyldiarylene, alkylenedioxy, or 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.

The amino group-containing acrylic emulsion having active hydrogen used in the present invention is, for example, an amino group-containing emulsion having active hydrogen obtained by modifying a carboxyl group-containing acrylic emulsion with alkyleneimine. The acrylic emulsion containing a carboxyl group is, specifically, a monomer (E) 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 (E) are optionally used.
Monomers that can be copolymerized with the same, specifically, monomers (F) (meth) acrylamide, N-methylol (meth) acrylamide, 2-hydroxyethyl (meth) acrylate,
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 (E), and preferably is 2.
5 to 15% by weight. In addition, the emulsion containing these carboxyl groups during the emulsion polymerization described above,
A monomer having two or more copolymerizable unsaturated groups in one molecule in advance, 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.

The amino group-containing aqueous acrylic resin having a modified active hydrogen used in the present invention includes a carboxyl group-containing aqueous acrylic resin modified with an alkyleneimine and having an active hydrogen-containing amino group-containing aqueous acrylic resin.
An acrylic resin is exemplified. The aqueous acrylic resin containing a carboxyl group specifically refers to one or a mixture of two or more carboxyl group-containing unsaturated monomers of the monomer (E) described for the emulsion containing a carboxyl group. And an aqueous resin obtained by solution polymerization of a monomer (E) and, if necessary, one or a mixture of two or more monomers selected from the group of copolymerizable monomers (F). Yes, or even if the polymer obtained by solution polymerization is not water-soluble, the polymer may be a basic substance such as ammonia, trimethylamine, triethylamine, amine compounds such as monoethanolamine, sodium hydroxide,
An aqueous resin obtained by neutralizing with a basic substance such as potassium hydroxide. Further, carboxyl group-containing poval,
Including lignin, rosin, etc.

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. These carboxyl group-containing acrylic emulsions or aqueous acrylic resins are modified with alkylene imines, and the active hydrogen-containing amino group-containing acrylic emulsions or aqueous
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 water-soluble polymer having an acid imide structure in the molecule and the amino group-containing acrylic having active hydrogen. 1 to 100 parts by weight in total with the solid content of the emulsion or aqueous acrylic resin
To 100 parts by weight, preferably 4 to 65 parts by weight, and if it is less than 1 part by weight, water resistance becomes poor, while
When the amount exceeds 0 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.
To give an amino group-containing A acrylic emulsion of an amino hydrogen equivalent 3000g · Solid / eq.

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 and Comparative Example 1 Isobutylene-maleic anhydride-maleic acid imide copolymer (Isovan 304, trade name of Kuraray Co., Ltd., copolymer molar ratio 1: 0.5: 0.5, hereinafter referred to as acid imide copolymer) 50 parts by weight of a polymer), 20 parts by weight of 25% by weight aqueous ammonia for industrial use, and 70 parts by weight of water were mixed, and the mixture was stirred at 85 to 90 ° C. for 2 hours to give an acid imide copolymer aqueous solution (A- 1) was obtained. Aqueous solution of the above acid imide copolymer (A-1) 84
90 parts by weight of heavy calcium carbonate (trade name: Whiten P-30, manufactured by Toyo Fine Chemical Co., Ltd.), 90 parts by weight of the amino group-containing acrylic emulsion produced in Production Example 1, and 21 parts by weight of water were added to parts by weight. The mixture was stirred to obtain a uniform aqueous dispersion composition (B-1) having a solid content of 55% by weight. To 100 parts of the above aqueous dispersion composition (B-1), various epoxy compounds are added in an amount such that the number of epoxy groups is the same as the number present in the adhesive of the present invention, as follows:
With good stirring, the adhesive was adjusted.

That is, the aqueous dispersion composition (B-
1) N, N, N ', N'-tetraglycidyl-1,3-xylenediamine, a tetrafunctional epoxy compound having a tertiary amino nitrogen atom in 100 parts (trade name: TETR)
AD-X 5 parts of Mitsubishi Gas Chemical Co., Ltd.) is used as a composition (C-1). 4 having a tertiary amino nitrogen atom in 100 parts of the above aqueous dispersion composition (B-1)
Functional epoxy compound, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane TE
A composition prepared by mixing 5 parts of TRAD-C (manufactured by Mitsubishi Gas Chemical Co., Ltd.) is referred to as a composition (C-2). A mixture of 100 parts of the aqueous dispersion composition (B-1) and 90 parts of a bisphenol A diglycidyl ether type epoxy resin (trade name: Adekaresin EP-4100 manufactured by Asahi Denka Kogyo KK). This is referred to as a composition (C-3). To 100 parts of the above aqueous dispersion composition (B-1), 6.9 parts of a glycerin triglycidyl ether type epoxy resin (trade name: Denacol EX-314, manufactured by Nagase & Co., Ltd.) was blended. This is referred to as composition (C-4). Bisphenol F diglycidyl ether type epoxy resin (EPO • TOHTO) was added to 100 parts of the aqueous dispersion composition (B-1).
YDF-170 manufactured by Toto Resin Chemical Co., Ltd.) 8.1
The composition (C-5) was prepared by mixing the components. 100 parts of the above aqueous dispersion composition (B-1) was mixed with 100 parts of a phenol-novolak glycidyl ether type epoxy resin (EPO).
・ TOHTO YDPN-638 Toto Resin Chemical Co., Ltd.
The composition (C-6) was prepared by mixing 8.6 parts of the same.

Using these compositions, bonding was carried out under the following bonding conditions, using a birch wood material of 10 m / m thickness as an adherend. Coating amount 250 g / m ² Deposit within 5 minutes Pressing 10 kg / cm ² × 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, and the measurement results in a wet state are shown in Table 1 below.

[0021]

TABLE 1 normal state resistance water resistance boiled actual C-1 175 (100) 99 (63) 82 (77) facilities Example C-2 205 (63) 101 (23) 87 (72) specific C-3 69 (0) 00 Comparison C-4 174 (3) 64 (0) 15 (0) Example C-5 131 (3) 11 (0) 34 (0) C-6 162 (30) 2 (0) 13 ( 0) Numerical units are kg / cm ² , and the values in parentheses indicate the percentage of wood fracture. The same applies to the following table. From Table 1 above, a composition comprising an aqueous solution of a water-soluble polymer having an acid imide structure in the molecule and an amino group-containing acrylic emulsion having an active hydrogen or an aqueous acrylic resin was added with a tertiary amino nitrogen. N, a tetrafunctional epoxy compound having atoms,
(C-1) of Example of the present invention, which comprises N, N ', N'-tetraglycidyl-1,3-xylenediamine and 1,3-bis (NN-diglycidylaminomethyl) cyclohexane. And (C-2) that only the adhesive shows good adhesive strength in water resistance and boiling water resistance.

Comparative Example 2 An aqueous solution of an acid imide copolymer (A) prepared in the same manner as in Example 1
-1) 84 parts by weight of calcium bicarbonate (Toyo Phi
Manufactured by N Chemical Co., Ltd.WhitetonP-30) 90 parts by weight
And water 21 weight and styrene-butadiene copolymer latek
Add 90 parts by weight of resin (SBR), stir well and disperse in water
A liquid composition was obtained. To 100 parts by weight of this aqueous dispersion, N, N,
N ', N'-tetraglycidyl-1,3-xylene diurea
Min (trade name: TETRAD-X Mitsubishi Gas Chemical Co., Ltd.)
5 parts) (commercially available from Co., Ltd.) to obtain a composition (C-7). Furthermore, the ratio
For comparison, one of the currently water-resistant adhesive compositions
Aqueous polymer-isocyanate-based resistance commonly used
Adhesive (127100 parts of P-I Bond, trade name, curing agent
15 parts Oka Promotion Co., Ltd.) Composition (C-8)
The adhesive performance was examined. Use these compositionsExample 1
In the same way as above, birch wood of 10 m / m thicknessBonding
AndExample 1Normal strength, water resistance and boiling resistance
Boiling strength is determined by JIS K-6852 “Press-shearing adhesive bonding
Strength test ". The results are shown in Table 2 below.

[0023]

[Table 2] Comparative example Normal water resistant boiling (C-7) SBR 175 79 80 (57) (0) (65) (C-8) Aqueous polymer / 175 72 67 isocyanate (90) (0) (20)

Comparative Example 3 Isobutylene-maleic anhydride copolymer (copolymerization molar ratio 1: 1, average degree of polymerization: 600 powder, Kuraray Isoprene Chemical Co., Ltd. product name: Isoban 06) 50 parts by weight, water 70 parts by weight, The mixture was mixed at a ratio of 27 parts by weight of 25% aqueous ammonia and stirred at 85 to 90 ° C. for 2 hours to prepare a uniform aqueous solution of isobutylene-maleic anhydride copolymer (A-2). 84 parts by weight of this aqueous solution was mixed with heavy calcium carbonate (trade name: Whiten P-30, manufactured by Toyo Fine Chemical Co., Ltd.)
90 parts by weight, 90 parts by weight of the amino-containing acrylic emulsion prepared in Production Example 1, 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' was added to 100 parts of the above aqueous dispersion composition (B-2).
-A composition containing 5 parts of tetraglycidyl-1,3-xylenediamine is referred to as a composition (C-9). In the same manner as in Example 1 , normal strength, water resistance and boiling resistance were measured according to JIS.
It was measured according to K-6852 "Adhesive Compression Shear Bond Strength Test". The results are as follows: Normal 189 (100) Water resistant 58 (0) Boiling resistant 52 (0)

Example 2 Aqueous solution of acid imide copolymer (A-1) used in Example 1
84 parts by weight of calcium bicarbonate (manufactured by Toyo Fine Chemical Co. Whiton P-30) 90 parts by weight of water 21
The weight and 90 parts by weight of the amino group-containing acrylic emulsion resin produced in Production Example 2 were added and sufficiently stirred to obtain a uniform aqueous dispersion composition (B-3) having a solid content of 55%. N, N, N ', N'-tetraglycidyl-1,3-xylenediamine (trade name: TE) was added to 100 parts by weight of the aqueous dispersion composition.
2 parts of TRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.) to prepare a composition (C-10). As the amino group-containing acrylic emulsion resin , the resin prepared in Production Example 3 was used, and N, N, N ', N'-tetraglycidyl-1,3-xylenediamine was used in an amount of 8 parts by weight. Similarly, a composition (C-11) was obtained. Real
In the same manner as in Example 1 , the normal strength, water resistance and boiling resistance were measured in accordance with JIS K-6852 "Adhesive compression shear strength test". The results are as shown in Table 3 below.

[0026]

Table 3 Composition Normal water resistance Water resistance (C-10) 198 (100) 97 (85) 81 (93) (C-11) 172 (100) 96 (83) 86 (88)

Comparative Example 4 An aqueous solution of an acid imide copolymer (A) prepared in the same manner as in Example 1
-1) To 84 parts by weight, 90 parts by weight of calcium bicarbonate (Whiteton P-30 manufactured by Toyo Fine Chemical Co., Ltd.), 21 parts by weight of water, and a styrene / acrylic acid alkyl ester copolymer (trade name: Acronal YJ-2720D Mitsubishi) 90 parts by weight of Yuka Birdish Co., Ltd.) were added and sufficiently stirred to obtain an aqueous dispersion composition. This aqueous dispersion 100
N, N, N ', N'-tetraglycidyl-1,
5 parts of 3-xylenediamine (trade name; TETRAD-X, manufactured by Mitsubishi Gas Chemical Company, Inc.) are blended into a composition (C-1).
2) was obtained. Using this composition, a 10 m / m thick birch wood material was adhered in the same manner as in Example 1, and the normal strength, water resistance and boiling resistance were measured in the same manner as in Example-1.
It was measured according to K-6852 "Adhesive Compression Shear Bond Strength Test". The results are shown in Table 4 below.

[0028]

[Table 4] Composition 4 Normal condition Water resistance and boiling resistance (C-12) 117 (19) 50 (0) 25 (3)

[0029]

As described above, according to the present invention, the disadvantages of the prior art are eliminated, and not only during boiling and continuous boiling in which heat is applied and curing is accelerated, but also practical tests are performed immediately. Even when immersed in water at room temperature, it shows good adhesive strength and can obtain good water resistance test results.
High water resistance with cold-pressure clamping, exhibits heat resistance and durability, it is possible to provide a suitable aqueous adhesive compositions inter alia, as a wood adhesive.

────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C09J 133/26 C09J 133/26 135/00 135/00 (72) Inventor Koji Nagaoka 14-1 Chidoricho, Kawasaki-ku, Kawasaki-shi, Kawasaki-shi, Kanagawa Prefecture. No. Nippon Shokubai Kagaku Kogyo Co., Ltd., Kawasaki Research Laboratory (72) Inventor Kazumoto Akazaki 14-1, Chidori-cho, Kawasaki-ku, Kawasaki City, Kanagawa Prefecture Nippon Shokubai Chemical Industry Co., Ltd. 6-10-5 Higashi-Mukojima, Ward (72) Inventor Ichiro Fujii 28-1 Totsuka Sakaimachi, Kawaguchi City, Saitama Prefecture (72) Inventor Masaru Fujimoto 1-1-18-1, Hama, Kawaguchi City, Saitama Prefecture (56) References Special JP-A-60-245680 (JP, A) JP-A-4-72371 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09J 1/00-201/10 CA (STN) REGISTRY (STN) WPI / L (QUA STEL)

Claims (1)

(57) [Claims] 1. A general formula represented by the following chemical formula 1. (However, in the above formula, R ¹ and R ² are a hydrogen atom, an alkyl
The same group selected from the group consisting of
Is a different group, and R ³ is a hydrogen atom, a halogen atom,
Or an alkyl group or alkenyl which may contain a hydroxyl group
And a group selected from the group consisting of
And at least one of P, Q, R and S is a carbohydrate.
Selected from the group consisting of xyl groups, their esters and their amides
In Barre groups, it differs from other groups is a hydrogen atom or Al
It is a kill group. Has an acid imide structure in the molecule represented by
An aqueous solution of a multicomponent copolymer or a salt thereof, a 4-functional epoxy compound having a tertiary amino nitrogen atom, the general formula represented by the following chemical formula 2 ## STR2 ## (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
Water-based adhesive composition comprising a resin as an essential component.