JPH08231616A - Curable water-based resin composition - Google Patents

Abstract

PURPOSE: To obtain a curable water-based resin composition having high contact properties and can give a cured film having high-level adhesiveness, heat resistance and water resistance. CONSTITUTION: A curable water-based resin composition comprising water and a water-based resin matrix obtained by emulsion-polymerizing 40-95 pts.wt. radical-polymerizable monomer component essentially consisting of an aromatic unsaturated compound, a 1-12 C alkyl ester of an α,β-unsaturated mono- carboxylic acid and acrylic acid and/or methacrylic acid in the presence of 5-60 pts.wt. epoxy resin and giving a film having a Tg of 20 to -40 deg.C.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a curable aqueous resin composition which exhibits tackiness by being dried at room temperature or by being dried by heating, and has a property of becoming non-tacky with the passage of time. . More specifically, the present invention relates to a curable aqueous resin composition that imparts high adhesive strength immediately after drying and exhibits high heat resistance, water resistance and adhesiveness by being left as it is at room temperature or by heating. .

[0002]

2. Description of the Related Art In recent years, resource-saving and environmentally friendly materials have been developed. Among them, solvent-based chloroprene adhesives are being actively replaced. This chloroprene adhesive has (1) good adhesion (contact property) immediately after solvent drying, (2) high adhesion due to high crystallinity after curing, (3) good heat resistance and water resistance , And so on.

This chloroprene adhesive is made water-based by, for example, emulsifying chloroprene rubber and improving the performance of conventional thermoplastic acrylic emulsions and urethane emulsions. The balance between strength, heat resistance, and water resistance cannot be achieved, and nothing is satisfactory yet. On the other hand, there is an attempt to balance the contact property, the adhesive strength after curing, the heat resistance, and the water resistance by combining with a conventional thermoplastic emulsion alone and with a thermosetting epoxy resin.

[0004]

However, if the emulsion of the epoxy resin is simply blended with the thermoplastic emulsion, the epoxy resin and the remaining polymer component may be separated during storage, or the epoxy resin emulsion may be separated. There is a problem that a large amount of emulsifier used during production affects water resistance. For these,
For example, in JP-A-49-106586, emulsion polymerization is carried out in the presence of an epoxy resin to solve the problem of separation. Further, in JP-A-57-115418, the compatibility of the epoxy resin with an acrylic polymer is improved by partially forming an acryloyl group at the terminal of the epoxy resin, preventing separation during storage and improving performance. Although these problems have solved the conventional problems to a considerable extent, it has been difficult to balance the currently required higher contact properties with the adhesive strength after curing, heat resistance and water resistance.

[0005]

As a result of various studies to solve the above problems, the present inventor selected a combination of an epoxy resin and a polymer obtained from a specific monomer, and focused on the Tg of a film after drying. By doing so, they have found that the above problems can be overcome, and have completed the present invention. That is, in the present invention, (A) C1 to C of (a) an aromatic unsaturated compound and (b) an α, β-unsaturated monocarboxylic acid in the presence of 5 to 60 parts by weight of an epoxy resin.
An aqueous resin composition comprising a resin matrix obtained by emulsion-polymerizing 40 to 95 parts by weight of a radical-polymerizable monomer containing 12 alkyl esters, (c) acrylic acid and / or methacrylic acid as essential components, and water. , Tg of the film obtained from the aqueous resin composition is 20 to -4.
A curable aqueous resin composition having a temperature of 0 ° C. is provided.

The present invention will be described in detail below. The epoxy resin used in the present invention refers to a compound having one or more epoxy groups in one molecule, for example, glycidyl ethers, glycidyl esters, glycidyl amines,
Examples include linear aliphatic epoxides and alicyclic epoxides. Examples of (a) glycidyl ethers include aromatic glycidyl ethers and aliphatic glycidyl ethers.
Examples of aromatic glycidyl ethers include bisphenol diglycidyl ether, phenol novolac polyglycidyl ether, and biphenol diglycidyl ether.

Examples of the diglycidyl ether of bisphenol include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A and tetrabromobisphenol A.
Examples of such polyglycidyl ethers of phenol novolac include phenol novolacs, cresol novolacs, polyglycidyl ethers of brominated phenol novolacs, and examples of diglycidyl ethers of biphenols include biphenols and tetramethyl. Diglycidyl ether of biphenol may be mentioned. Examples of the aliphatic glycidyl ether include glycidyl ethers such as polyethylene glycol, polypropylene glycol, glycerin and tetramethylene glycol.

Examples of (b) glycidyl esters include aromatic glycidyl esters and alicyclic glycidyl esters. As the aromatic glycidyl ester,
For example, phthalic acid and terephthalic acid. Examples thereof include diglycidyl ester such as isophthalic acid, and examples of the alicyclic glycidyl ester include glycidyl ester such as hexahydrophthalic acid, tetrahydrophthalic acid and dimer acid.

Examples of the (c) glycidyl amines include tetraglycidyl diaminodiphenylmethane, tetraglycidyl metaxylylenediamine, triglycidyl aminophenol and the like. Examples of (d) linear aliphatic epoxides include epoxidized polybutadiene and epoxidized soybean oil. (E) Examples of alicyclic epoxides include 3,4-
Examples thereof include epoxy-6-methylcyclohexylmethylcarboxylate and 3,4-epoxycyclohexylmethylcarboxylate. The epoxy resins may be used alone or in combination of two or more.

From the viewpoint of heat resistance and water resistance, preferred epoxy resins are glycidyl ethers, more preferably bisphenol diglycidyl ethers, and particularly preferably bisphenol A and bisphenol F diglycidyl ethers. The epoxy equivalent of the epoxy resin may be in the range of 100 to 10,000, and is preferably 150 to 3,000, more preferably 170 to 3,000 from the viewpoint of room temperature curability, heat resistance and water resistance.
It is 1,000.

The radically polymerizable monomer used in the present invention includes (a) an aromatic unsaturated compound, (b) a C1 to C12 alkyl ester of an α, β-unsaturated monocarboxylic acid, and (c) acrylic acid and And / or methacrylic acid as an essential component. The aromatic unsaturated compound (a) has a radical polymerizable double bond in the aromatic compound, and examples thereof include styrene, α-methylstyrene and vinyltoluene. C1 of α, β-unsaturated monocarboxylic acid
The C1 to C12 alkyl ester (b) includes, for example, C1 to C12 alkyl esters of acrylic acid or methacrylic acid.

C1 to C of acrylic acid or methacrylic acid
Examples of the alkyl ester of 12 include methyl acrylate, ethyl acrylate, propyl acrylate,
Isopropyl acrylate, butyl acrylate, isobutyl acrylate, hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl acrylate, butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl Examples thereof include methacrylate and lauryl methacrylate.

The combination of the composition of the radically polymerizable monomer and the epoxy resin in the present invention achieves a high degree of balance between contact property and heat resistance for the first time. When the aromatic unsaturated compound (a) is not used, the Tg of the present invention is
A high degree of contact cannot be obtained even when adjusted to the range. In addition, C1 to C1 of α, β-unsaturated monocarboxylic acid
When the alkyl ester (b) of 2 is not used, Tg control becomes difficult and a high contact property cannot be obtained. When an alkyl ester having C of more than 13 is used, high heat resistance cannot be obtained. Further, when acrylic acid and / or methacrylic acid (c) is not used, a high degree of balance between contact property and heat resistance cannot be achieved.

Radical polymerizable monomers (a), (b),
Each of (c) may be used alone, or each may be a mixture of two or more kinds. In the radically polymerizable monomer, preferably, the aromatic unsaturated compound is styrene, the C1 to C12 alkyl ester of the α, β-unsaturated monocarboxylic acid is ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and Butyl acrylate is preferable, and acrylic acid and / or methacrylic acid is methacrylic acid.

If desired, radical-polymerizable monomers other than the radical-polymerizable monomer which is an essential component of the present invention may be combined. For example, a hydroxyl group-containing monomer such as 2
-Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate,
Hydroxypropyl methacrylate, polyethylene glycol acrylate; amide group-containing monomers such as acrylamide, methacrylamide, N, N-methylenebisacrylamide, diacetone acrylamide, maleic acid amide, maleimide;

Methylol group-containing monomers such as N-methylolacrylamide, N-methylolmethacrylamide, dimethylolacrylamide, dimethylolmethacrylamide; alkoxymethyl group-containing monomers such as N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N -Butoxymethyl acrylamide, N-butoxymethyl methacrylamide;

Epoxy group-containing monomers such as glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, methyl glycidyl acrylate, methyl glycidyl methacrylate; polyfunctional monomers such as divinylbenzene, polyoxyethylene diacrylate, polyoxyethylene dimethacrylate, polyoxypropylene. Diacrylate, polyoxypropylene dimethacrylate, butanediol diacrylate, butanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate;

Mono- or diesters of α, β-ethylenically unsaturated dicarboxylic acids such as mono- or dibutyl maleate, mono- or dioctyl fumarate; vinyl esters such as vinyl acetate, vinyl propionate; unsaturated nitriles such as acrylonitrile, methacryl Ronitrile; unsaturated carboxylic acids such as maleic acid, fumaric acid,
Itaconic acid, monoalkyl itaconate; olefin,
For example, butadiene, isoprene; chlorine-containing vinyl monomers such as vinyl chloride, vinylidene chloride, chloroprene;

In the present invention, the ratio of the epoxy resin to the radical-polymerizable monomer is 5 to 60 parts by weight, preferably 10 to 55 parts by weight, more preferably 20 parts by weight.
~ 50 parts by weight of radically polymerizable monomer is 40 ~
95 parts by weight, preferably 45 to 90 parts by weight, more preferably 50 to 80 parts by weight. If the amount of the epoxy resin is less than 5 parts by weight, the heat resistance and water resistance will be poor, and if it exceeds 60 parts by weight, the contact property will be poor.

The Tg of the film obtained from the aqueous resin composition of the present invention is 20 to -40 ° C, preferably 5 to -30.
C., more preferably 0 to -25.degree. If the Tg exceeds 20 ° C, the contact property will be insufficient not only at room temperature but also when dried by heating, resulting in poor adhesion,
If the temperature is lower than 40 ° C, the adhesive strength will be insufficient. The film obtained from the composition of the present invention is preferably in a state where the vinyl polymer (B) from the specific radically polymerizable monomer and the uncured epoxy resin (A) are compatible with each other. That is, the Tg of the film due to compatibilization is not only the cause of the vinyl polymer (B) but also the amount of the dissolved epoxy resin (A),
It also depends on the molecular weight.

For example, Tg of vinyl polymer (B) itself
Even if the Tg is set high, when the amount of the epoxy resin (A) added is large, the Tg of the film is
Will fall. The reverse is also possible. Therefore, the composition ratio of the radical-polymerizable monomer is determined depending on where the Tg of the film under the compatibility with the epoxy resin is set. However, there is an optimum range of the radical-polymerizable monomer in terms of the cotant property, the heat resistance after curing the epoxy resin, and the water resistance.

C1 of (a) aromatic unsaturated compound and (b) α, β-unsaturated monocarboxylic acid which are essential components of the present invention.
To C12 alkyl ester, and (c) acrylic acid and / or methacrylic acid, the composition ratio of (a) aromatic unsaturated compound is 20 to 80% by weight, preferably 25 to 7
0% by weight, (b) C1 of α, β-unsaturated monocarboxylic acid
To C12 alkyl ester is 20 to 80% by weight, preferably 25 to 80% by weight, and (c) acrylic acid and / or methacrylic acid is 0.1 to 20% by weight, preferably 0.5 to 10% by weight. .

The T of the film obtained from the composition of the invention
g is a differential scanning calorimeter, and the heating rate is from -100 ° C to 1
It can be measured at 0 ° C / min. The inflection point of the obtained data is Tg
If there are two or more inflection points, the inflection point on the high temperature side is T
g. When measuring Tg, a sample obtained by drying an aqueous resin composition at room temperature or by heating must be used. However, in the case of drying by heating, excessive heating is T
Since it involves a change in g, it is necessary to carry out the process as quickly as possible.

The emulsion polymerization applied to the specific radically polymerizable monomer of the present invention is carried out by a conventionally known polymerization technique, that is, in the presence of a radically polymerizable monomer, a radical polymerization initiator, water and a surfactant. In the case of the present invention, for example, the epoxy resin and the radical-polymerizable monomer are uniformly dissolved in advance by sufficiently stirring at room temperature or under heating, and a surfactant, a dispersant, a protective colloid, a water-soluble polymer are added thereto. And the like and water and a radical polymerization initiator are added to form an emulsion dispersion, and then polymerization is performed.

Other than this method, for example, a method of separately emulsifying and dispersing an epoxy resin and a radical-polymerizable monomer for polymerization, a method of emulsifying and dispersing only an epoxy resin and directly polymerizing the radical-polymerizable monomer, and the like can be mentioned. Also, the method of adding the polymerization initiator may be added together with the emulsion dispersion or separately. Even if the radically polymerizable monomer and the epoxy resin react during emulsion polymerization,
You don't have to. It is better not to react.

The surfactant used is ionic,
Nonionic surfactants are mentioned, and examples of the ionic surfactants include anionic, cationic and amphoteric. Examples of the anionic surfactant include fatty acids, sulfuric acid ester salts of higher alcohols, sulfuric acid ester salts of liquid fatty oil, aliphatic amine and aliphatic amide sulfates,
Phosphate ester of aliphatic alcohol, sulfonate of dibasic fatty acid ester, sulfonate of aliphatic amide,
Examples thereof include alkyl allyl sulfonates and formalin condensed naphthalene sulfonates.

Examples of the cationic surfactant include primary amine salts, secondary amine salts, tertiary amine salts, quaternary ammonium salts, pyridinium salts and the like. Examples of the amphoteric surfactant include carboxylic acid salt type, sulfuric acid ester salt type, sulfonic acid salt type, and phosphoric acid ester salt. Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ester, sorbitan alkyl ester, polyoxyethylene sorbitan alkyl ester and the like.

In addition to the non-reactive surfactants listed above, reactive surfactants can also be used.
As the reactive surfactant, those having a radically polymerizable functional group in one molecule and one or more functional groups selected from a sulfonic acid group, a sulfonate ester group, a sulfonate group, and a sulfonate ester group. Or those having a radical-polymerizable functional group in one molecule and having polyoxyethylene, polyoxypropylene, polyoxyethylene-polyoxypropylene composite type alkyl ether or alcohol, and the like. These surfactants may be used alone or in combination of two or more.

Examples of the dispersant, protective colloid and water-soluble polymer include polyphosphate, polyacrylate, styrene-acrylic acid copolymer salt, styrene-methacrylic acid copolymer salt and water-soluble acrylic acid ester copolymer. Examples thereof include polymer salts, water-soluble methacrylic acid ester copolymer salts, polyvinyl alcohol, polyacrylamide, polymethacrylamide, and polyacrylamide copolymers.

As the polymerization initiator, a water-soluble or oil-soluble polymerization initiator can be used. Examples of the water-soluble polymerization initiator include persulfates, peroxides, water-soluble azobis compounds, and peroxide-reducing agent redox compounds. Examples of the persulfate include ammonium persulfate, potassium persulfate, sodium persulfate, and the like, and examples of the peroxide include hydrogen peroxide, t-butyl hydroperoxide, and the like.
Examples thereof include t-butyl peroxymaleic acid and succinic acid peroxide. Examples of the water-soluble azobis compound include 2,2′-azobis (N-hydroxyethylisobutyramide), 2,2′-azobis (2-amidinopropane) dihydrogen chloride, 4,4′-azobis (4-cyanopentanoic acid) ) And the like.

Examples of the peroxide-reducing agent redox system include the above-mentioned peroxides such as sodium bisulfite, sodium thiosulfate, sodium hydroxymethanesulfinate, L-ascorbic acid, and salts thereof, cuprous salts, and Examples include addition of reducing agents such as iron salts. Examples of oil-soluble polymerization initiators include peroxides and oil-soluble azobis compounds, and examples of peroxides include benzoyl peroxide, lauroyl peroxide, butyl peroxide, cumene hydroperoxide and the like. ,

Examples of the oil-soluble azobis compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile and 2,2'-azobis-2,4-dimethylvalero. Examples include nitrile and the like.
In the emulsion polymerization of the present invention, if necessary, a pH adjusting agent such as sodium hydrogen phosphate or sodium hydrogen carbonate, a molecular weight adjusting agent such as t-dodecyl mercaptan, n-dodecyl mercaptan or a low molecular halogen compound, a chelating agent, a plasticizer Agents, organic solvents and the like can be added before, during or after the emulsion polymerization.

The polymerization temperature is, for example, 0 to 100 ° C., especially 30.
The temperature is preferably ˜90 ° C., and the reaction is carried out in an inert atmosphere under normal pressure or, if necessary, under pressure. When the aqueous resin composition of the present invention is used for, for example, an adhesive or a paint, it may be used as it is, but a curing agent may be added as necessary to cure the epoxy resin contained therein.

Examples of the curing agent include polyamine type, acid anhydride type, phenol resin, polymercaptan, Lewis acid complex and the like. Examples of the polyamine-based curing agent include aliphatic polyamines, alicyclic polyamines, aromatic polyamines, polyamides and tertiary amines. Examples of the aliphatic polyamines include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and these. And modified products thereof.

Examples of the alicyclic polyamine include isophoronediamine, menthanediamine, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) 2,
4,810-tetraoxaspiro (5,5) undecane adduct, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclohexyl) methane, and modified products thereof may be mentioned. Examples of aromatic polyamines include m-xylylenediamine, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, and modified products thereof.

Examples of polyamides include condensation products of dicarboxylic acids such as dimer acid and the above polyamines. Examples of the tertiary amine include dimethylbenzylamine, dimethylaminomethylphenol, 2,4,6-
Tertiary amino group-containing compounds such as trisdimethylaminomethylphenol, modified products thereof, imidazole, 2
Examples include imidazole compounds such as -methylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole, and modified products thereof. Other polyamines include dicyandiimide and adipic acid dihydrazide.

Examples of the acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and modified products thereof, which are monofunctional. Examples of bifunctional compounds include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, and modified products thereof. Examples of the phenol resin include novolac type phenol resin and resol type phenol resin.

Examples of polymercaptans include condensates of thioglycolic acid and polyhydric alcohols and polysulfides. Examples of the Lewis acid complex include an amine complex of boron trifluoride. These curing agents may be used alone or in combination of two or more. A polyamine curing agent is preferable, and an alicyclic polyamine curing agent or an alicyclic polyamine curing agent is more preferable. The addition amount of the polyamine-based curing agent is preferably equivalent to the epoxy group contained.

When the aqueous resin composition of the present invention is cured by using a curing agent, for example, (a) when it is applied as an adhesive, a method of mixing both before applying to an adherend may be used. It is also possible to apply the aqueous resin composition of the present invention to one adherend, apply a curing agent to the other adherend, and mix the coated surfaces of both adherends by overlapping.
(C) It is also possible to use a method in which the aqueous resin composition of the present invention is applied to one of the adherends, then a curing agent is further applied, and then the other adherend is overlaid and mixed. . In particular, the latter two methods have the advantage that they can be used regardless of the pot life.

The aqueous resin composition of the present invention may be cured by evaporating water at room temperature or by heating and then proceeding at room temperature, or by heating. In addition, the adherends may be stuck together without volatilizing water, and curing may proceed at room temperature or heating. When the aqueous resin composition of the present invention is used for an adhesive, a tackifier and a rubber component may be added if necessary. Examples of the tackifier include natural tackifiers such as rosin, rosin derivative, terpene resin, and terpene derivative, petroleum resin, styrene resin, coumarone indene resin, phenol resin, xylene resin, etc. Examples of synthetic tackifiers include: These tackifiers are preferably added in the form of an aqueous dispersion or an aqueous solution.

Examples of the rubber component include liquid nitrile rubber and silicone rubber. Further, an amino resin such as a melamine resin, a urea resin or a benzoguanamine resin may be added to further improve the curing performance. In addition, germicide, antiseptic, antifoaming agent, plasticizer, flow regulator, thickener, pH adjuster, surfactant, coloring pigment, extender pigment,
A rust preventive pigment or the like may be added. The water-based resin composition of the present invention can be used not only in adhesives and pressure-sensitive adhesives, but also in paints, printing inks, gas barrier packaging materials, processed papers, fiber processing agents, building materials and the like.

As the adhesive, for example, wood, plywood, particle board, gypsum board, metal such as iron and aluminum, plastic film, plastic foam, non-woven fabric of plastic, leather, cotton, linen cloth, glass fiber, glass cloth. Adhesion such as FRP.

Examples of the field of adhesives include tapes, labels, wallpaper, flooring materials and the like. Examples of the paint field include concrete, wood, metal, floor polish and the like. Examples of the fiber processing agent include non-woven fabric, carpet, electric flocked cloth, laminated cloth, tire cord and the like. Examples of building materials include sealing materials, latex cement, and waterproof materials.

[0044]

EXAMPLES Examples of the present invention will be described below, but these do not limit the scope of the present invention. Parts are based on weight unless otherwise specified. (Examples 1 to 14) (1) <Preparation of emulsion> In 1000 parts of the mixture of the radical-polymerizable monomer and the epoxy resin shown in Table 1, Emulgen 950 [manufactured by Kao Corporation,
25% of polyoxyethylene nonyl phenyl ether]
Aqueous solution 80 parts, Rebenol WZ [Kao Corporation, polyoxyethylene nonyl phenyl ether sodium sulfate]
Of 40% of 25% aqueous solution, 2 parts of ammonium persulfate and 430 parts of distilled water were added and stirred with a homomixer to prepare a pre-emulsion.

Separately, add 400 ml of distilled water to a flask equipped with a stirrer.
Part, 20 parts of 25% aqueous solution of Emulgen 950 was charged,
The temperature is raised to 80 ° C. and 1 part of ammonium persulfate dissolved in 50 parts of water is added. Add the pre-emulsion
Continuous dripping over time. Then, a solution prepared by dissolving 0.5 part of ammonium persulfate in 50 parts of water was added, and the polymerization was continued at the same temperature for 1 hour. After that, cool down to below 30 ℃, and
Adjust the pH to 7 with 5% concentrated ammonia water
A 0% emulsion was obtained. Table 1 also shows the viscosity after polymerization and the Tg after emulsion drying.

(Comparative Examples 1 to 6) Emulsion polymerization was performed on the mixture of the radically polymerizable monomer and epoxy resin shown in Table 2 by the same method as in Examples to obtain emulsions. The viscosity after polymerization and the Tg after drying the emulsion are also shown in Table 2. (2) <Evaluation method and evaluation results> (a) Blending with curing agent Commercially available curing agent Ancamine 2075 (ACI Japan Limit) was added to the emulsions obtained in Examples 1 to 14 and Comparative Examples 1 to 6. Modified alicyclic polyamine manufactured by Ted; 40 phr added to epoxy resin), Ancamine 1769
(ACI Japan Limited, modified aliphatic polyamine, addition amount: 25 phr relative to epoxy resin), 2
-Methylimidazole (addition amount 5 for epoxy resin)
(phr) was mixed with stirring at the ratios shown in Tables 3 and 4 to obtain a blended product.

(B) <Evaluation of Adhesion Performance> The above-mentioned compounded product was evaluated for adhesion performance by the method shown below. The results are shown in Tables 5-6. (Coating / adhesion) The viscosity of the compounded product is 100 Ps with the thickener.
After that, it is applied to a plywood and a 1-inch wide No. 9 canvas using a wire bar # 75, and dried at 20 ° C. for 20 minutes. After that, the dry surfaces of the blended products are pasted together,
A 4.5 kg roller was reciprocated twice.

(Initial Bonding Strength) 180 ° peel strength was measured by a Tensilon tensile tester using a sample that was left at 20 ° C. for 1 hour after being laminated. 2.0 kg / inc
It is judged that h or more is acceptable. Pulling speed is 50mm / m
in. (Adhesive Strength After Curing) Using a sample that was left at 20 ° C. for 7 days after bonding, 180 ° peel strength was measured with a Tensilon tensile tester. It is judged to be acceptable when it is 4.0 kg / inch or more. The pulling speed was 50 mm / min.

(Heat resistance) A sample, which was left at 20 ° C. for 7 days after being laminated, was pulled in a 90 ° direction by a 400 g weight in an atmosphere at 80 ° C., and if the weight did not drop after standing for 24 hours, it was judged as a pass. In the case, it was judged as a failure. The weight was attached to the canvas side. (Water resistance) A sample that had been laminated and left to stand at 20 ° C for 7 days was immersed in distilled water for 1 day, and then the 180 ° peel strength was immediately measured with a Tensilon tensile tester. 2.0
It is judged to be acceptable if it is kg / inch or more. The pulling speed was 50 mm / min.

[0050]

[Table 1]

(Note): Epoxy resin A: Araldite AER manufactured by Asahi Chiba Co., Ltd.
260 bisphenol A type, epoxy equivalent 190 epoxy resin B: Asahi Chiba Co., Ltd., Araldite AER
280 Bisphenol A type, epoxy equivalent 280 Epoxy resin C: Asahi Ciba Co., Ltd., Araldite AER
6071 bisphenol A type, epoxy equivalent 450 epoxy resin D: DOW CHEMICAL JAPAN CO., LTD. E. FIG.
N. 438 Phenol novolac type, Exequivalent 180 St: Styrene, MMA: Methyl Methacrylate, E
A: ethyl acrylate, n-BA: n-butyl acrylate, 2-EHA: 2-ethylhexyl acrylate, MAA: methacrylic acid, HEMA: hydroxyethyl methacrylate.

[0052]

[Table 2]

[0053]

[Table 3]

[0054]

[Table 4]

[0055]

[Table 5]

[0056]

[Table 6]

[0057]

The aqueous resin composition obtained from the present invention is
As it is a matrix composition of a polymer obtained from a specific monomer composition and an epoxy resin, it has a high degree of contact properties, and the curing of the epoxy resin proceeds smoothly at room temperature, so the adhesive strength after curing and heat resistance It has a high level of properties and water resistance, and can have the same performance as solvent-based chloroprene adhesives.

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display area C08L 33/06 LJG C08L 33/06 LJG

Claims (1)

[Claims] 1. In the presence of 5 to 60 parts by weight of (A) epoxy resin, (B) (a) aromatic unsaturated compound, (b) α,
A C1-C12 alkyl ester of β-unsaturated monocarboxylic acid, and (c) an aqueous resin matrix obtained by emulsion-polymerizing 40 to 95 parts by weight of a radical-polymerizable monomer containing acrylic acid and / or methacrylic acid as essential components. A curable aqueous resin composition comprising an aqueous resin composition containing water, wherein a film obtained from the aqueous resin composition has a Tg of 20 to -40 ° C.