JPH11302531A - Aqueous resin composition and adhesive - Google Patents

Abstract

(57) [Problem] To provide an aqueous resin composition which gives a film excellent in water resistance, solvent resistance, heat resistance, durability, aging resistance and adhesion to a substrate. SOLUTION: (A) An emulsion in which a polymer in which a polyurethane unit and a polyvinyl alcohol unit are bonded by a structural unit represented by the following general formula (I) is dispersed in water: (B) an aziridine group, an epoxy group, An aqueous resin composition comprising a compound having two or more functional groups selected from an oxazoline group, an oxazine group, and an isocyanate group in a molecule. Embedded image

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention cures in a short time even at room temperature, and exhibits excellent properties such as excellent water resistance, solvent resistance, heat resistance, durability, aging resistance and adhesion to a substrate. The present invention relates to an aqueous resin composition and an adhesive capable of forming a film having the same.

[0002]

2. Description of the Related Art Conventionally, polyurethane has been used as a resin to fill the boundary field between rubber and plastics by taking advantage of its excellent mechanical properties, abrasion resistance, chemical resistance, adhesiveness, etc., as a resin and a coating agent. , And has permeated a wide range of application fields such as artificial leather. Among them, aqueous polyurethane has been rapidly developed to meet social needs such as environmental conservation, resource saving and safety. High-performance aqueous polyurethanes have emerged due to advances in the technology of emulsifying and dispersing urethane resins in water, the technology of self-emulsifying and dispersing by ionomerization, and the technology of increasing the molecular weight in water. It has reached a comparable level and has been put to practical use in various application fields. However, the emulsifiers and ionic groups required for aqueous conversion often impair the inherent properties of the polyurethane resin, for example, solvent resistance and heat resistance.Furthermore, aqueous polyurethane and various aqueous emulsions are blended. In many cases, there is a problem with miscibility. These improvements have been considerably improved depending on the selection of the emulsifier, the type of ionic group to be introduced, and the like, but in reality, they have not yet reached a satisfactory level.

[0003]

Under such circumstances, the present invention provides excellent water resistance, solvent resistance, heat resistance, durability, aging resistance, and base materials which do not have the above-mentioned problems. The purpose of the present invention is to provide a polyurethane-based aqueous resin composition and an adhesive having the following adhesiveness.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to develop an aqueous resin composition and an adhesive having the above-mentioned preferable properties. As a result, (A) a polyurethane unit and a polyvinyl alcohol unit are as follows: An emulsion in which a polymer bonded by a structural unit represented by the general formula (I) is dispersed in water; and (B) an aziridine group, an epoxy group,
It has been found that an aqueous resin composition comprising a compound having two or more functional groups selected from oxazoline groups or oxazine groups and isocyanate groups in a molecule is an aqueous resin composition and an adhesive having desired performance. .

[0005]

Embedded image

[0006]

Further, in the case where the polymer constituting the emulsion (A) is an aqueous resin composition or an adhesive containing a carboxyl group in at least one of the polyurethane unit and the polyvinyl alcohol unit, It has been found that a high level of performance is exhibited. Also,
Even when one or more aqueous emulsions selected from vinyl acetate-based resin emulsions, (meth) acrylate-based emulsions, and diene-based resin emulsions are blended, they have high blending stability and are suitable for the purpose of the present invention. I also found that. The present invention has been completed based on such findings.

[0007] The emulsion of the present invention in which a polymer in which a polyurethane unit and a polyvinyl alcohol unit are bonded by the structural unit represented by the above general formula (I) is dispersed in water is generally used. It can be obtained by reacting a urethane prepolymer having two or more groups with a polyvinyl alcohol polymer having a primary or secondary amino group in the molecule. The urethane prepolymer having two or more isocyanate groups in the molecule constituting the polymer (A) of the present invention is generally obtained by increasing the chain of an organic diisocyanate and an organic compound having two active hydrogen atoms. Can be

Here, various organic compounds having two active hydrogen atoms can be mentioned, and polyesters, polyacetals, polyethers, polyamides and polyesteramides having a hydroxyl group can be mentioned as high molecular weight compounds. Examples of low molecular weight compounds include various glycols, diamines, amino alcohols, and water. When a carboxyl group is introduced into a polyurethane unit, an organic compound having both a carboxyl group and the above two active hydrogens in the molecule at the same time, for example, dimethylolpropionic acid is usually used. When the polyurethane unit contains a carboxyl group, the dispersion stability of the emulsion is improved, and higher performance is imparted. Further, as the organic diisocyanate, all aromatic and aliphatic diisocyanates can be used. As a suitable diisocyanate, butane-1,4-diisocyanate,
6-hexane diisocyanate, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate- (1,4), 1-methylcyclohexane-2,4-diisocyanate, 1-methylcyclohexane-2,6-
Examples thereof include diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluylene diisocyanate, 2,6-toluylene diisocyanate, and 4,4′-diphenylmethane diisocyanate.

The urethane prepolymer having two or more isocyanate groups in the molecule can be obtained by increasing the chain of the organic diisocyanate and the organic compound having two active hydrogen atoms. The organic compound having active hydrogen atoms is stirred with a temperature of about 40 to 120 ° C, preferably 60 to 120 ° C.
Manufactured by heating to 0 ° C. If desired, a catalyst can be used for this reaction, in which case temperatures below 40 ° C. are sufficient. The reaction is heated for a time sufficient for all the active hydrogen in the raw material to react, and the reaction is preferably carried out in the presence of a solvent, but if the prepolymer is a liquid at the processing temperature, these reactions may take place. Conditions are not necessarily required. As the solvent, those in which the reaction raw materials are dissolved are preferable, and ketones and esters, aliphatic hydrocarbon compounds such as heptane and octane, and aromatic hydrocarbon compounds such as benzene and toluene are used. Further, the amount of the organic diisocyanate and the organic compound having two active hydrogen atoms in this reaction is
The equivalent ratio of NCO / active hydrogen is preferably 1.2 / 1 to 3/1, and more preferably 1.5 / 1 to 2.5 / 1. Outside this range, gelation of the prepolymer may occur.

The polymer (A) of the present invention is usually prepared by reacting the urethane prepolymer having two or more isocyanate groups in the molecule with a polyvinyl alcohol polymer having a primary or secondary amino group in the molecule. Although it is obtained, the polyvinyl alcohol having a primary or secondary amino group constituting the polymer of (A) of the present invention is not particularly limited as long as it is a polyvinyl alcohol-based polymer containing a primary or secondary amino group in the molecule. Absent. The polyvinyl alcohol-based polymer having this functional group can be obtained by various methods. For example, 1. Ethylenic unsaturated having a primary amino group or a secondary amino group such as vinylformamide, vinylacetamide, and methylvinylacetamide A method of copolymerizing a monomer or an ethylenically unsaturated monomer having a functional group capable of forming a primary amino group or a secondary amino group by hydrolysis or the like with vinyl acetate, followed by saponification, After an addition reaction of a mercaptan having an amino group such as aminothiophenol with NaOH or the like as a catalyst, to a side chain epoxy group of a polymer comprising a vinyl acetate and a monomer having an epoxy group such as allyl glucidyl ether, Saponification method, 3. having a functional group capable of reacting with the hydroxyl group of polyvinyl alcohol in the molecule, and Alternatively a compound having a secondary amino group obtained by the method such as reacting a polyvinyl alcohol polymer. Also, there is a method of polymerizing an ethylenically unsaturated monomer having a primary amino group or a secondary amino group in the presence of a polyvinyl alcohol polymer having a mercapto group. Is obtained.

The polyvinyl alcohol having a primary or secondary amino group constituting the polymer (A) of the present invention has an effect of the present invention even if the molecule has a functional group other than the primary or secondary amino group in the molecule. As long as it is not impaired. Such other monomer units include ethylene, isobutylene, acrylonitrile, methacrylonitrile,
Acrylic acid, methacrylic acid, (anhydrous) fumaric acid, (anhydride) maleic acid, (anhydride) itaconic acid, allylsulfonic acid, methallylsulfonic acid, vinylsulfonic acid, acrylamide-2-methylpropanesulfonic acid, methacrylamide-2 -Methylpropanesulfonic acid, sulfopropyl acrylate, sulfopropyl methacrylate and their alkali salts, acrylamide, methacrylamide, trimethyl- (3-acrylamido-3-dimethylpropyl) -ammonium chloride, ethyl vinyl ether,
Examples thereof include butyl vinyl ether, N-vinylpyrrolidone, vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, vinylidene fluoride, and tetrafluoroethylene. Among these, when a monomer having a carboxyl group is used, the dispersion stability of the emulsion is improved, and higher performance is imparted. Further, those having a functional group at the terminal obtained by polymerizing a vinyl ester monomer such as vinyl acetate in the presence of a thiol compound such as thiolacetic acid or mercaptopropionic acid may be used.

The primary or secondary amino group content of the polyvinyl alcohol polymer having a primary or secondary amino group in the molecule constituting the polymer (A) of the present invention is as follows:
There is no particular limitation, and a suitable range varies depending on the degree of polymerization and the like.
10 mol% is more preferred. When the content of the primary or secondary amino group is less than 0.1 mol%, the reactivity with the urethane prepolymer having two or more isocyanate groups in the molecule for obtaining the polymer of the present invention is reduced,
On the other hand, if it exceeds 15 mol%, gelation may occur during the process of obtaining the polymer of the present invention, which is not preferred in some cases. The saponification degree of the polyvinyl alcohol-based polymer is preferably 50 mol% or more, more preferably 60 mol% or more, and even more preferably 70 mol% or more. The degree of polymerization is preferably in the range of 50 to 4000, and 10
0 to 2000 is more preferable.

The polymer (A) of the present invention is usually obtained by reacting a urethane prepolymer having two or more isocyanate groups in the molecule with a polyvinyl alcohol polymer having a primary or secondary amino group in the molecule. In this case, the ratio of the urethane prepolymer to the polyvinyl alcohol-based polymer is usually 0.2 to 20 parts by weight, preferably 0.5 to 15 parts by weight of the polyvinyl alcohol-based weight per 100 parts by weight of the urethane prepolymer. Parts by weight. This reaction is generally performed while vigorously stirring an aqueous solution of a urethane prepolymer having two or more isocyanate groups in a molecule dissolved in an organic solvent and a polyvinyl alcohol-based polymer having a primary or secondary amino group in the molecule. This is performed by mixing and emulsifying. The mixing method is not particularly limited, and various methods can be adopted. At this time, for the purpose of increasing emulsifying properties and reactivity, conventionally known anionic, cationic, nonionic, amphoteric surfactants and diol compounds or diamine compounds having a carboxyl group, a sulfonic acid group or the like in the molecule. Can be added to the system. When it is necessary to increase the chain of the urethane prepolymer, it is generally carried out by adding a chain extender to the urethane prepolymer in the above-mentioned emulsified state. Examples of the chain extender include compounds having at least two functional groups including active hydrogen, such as water, hydrazine, primary and secondary diamines,
Amino alcohols, amino acids, hydroxy acids, glycols and the like are used, and the amount thereof is preferably about 1 to 1.3 equivalents per equivalent of the isocyanate of the urethane prepolymer.

In general, according to the above method, a polyurethane unit and a polyvinyl alcohol unit are represented by the general formula (I)
A polymer of the present invention (A) linked by a structural unit represented by the following formula is obtained. Further, generally, the polymer of the present invention obtained by the above method is emulsified in an organic solvent / water emulsion dispersion. The emulsion is obtained by distilling or stripping the organic solvent at a temperature of 30 to 80 ° C. and replacing the dispersion medium with an aqueous phase. At this time, it is preferable to remove the solvent under reduced pressure.

The polymer emulsion (A) of the present invention is generally obtained by the above method, and the particle size of the polymer emulsion is 0.02 to 2.5 μm, preferably 0.02 to 2.5 μm.
Various conditions are adjusted so that the average particle diameter is 5 to 1.5 μm. The solid content of the polymer emulsion (A) is usually adjusted to 20 to 65% by weight.

The aqueous resin composition and the adhesive of the present invention comprise:
The above (A) and (B) are compounds having two or more functional groups selected from an aziridine group, an epoxy group, an oxazoline group or an oxazine group and an isocyanate group in a molecule. Compounds having two or more aziridine groups in the molecule include 2,4,6-tris (1′-aziridinyl)-
1,3,5-triazine, ω-aziridinylpropionic acid-2,2′-dihydroxymethyl-butanol-triester, 4,4′-bis (ethyleneiminocarbonylamino) diphenylmethane and the like.

Compounds having two or more epoxy groups in the molecule include bisphenol A diglycidyl ether,
Bisphenol A diβ methyl glycidyl ether, bisphenol F diglycidyl ether, tetrahydroxyphenylmethane tetraglycidyl ether, resorcinol diglycidyl ether, brominated bisphenol A
Diglycidyl ether, chlorinated bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, diglycidyl ether of bisphenol A alkylene oxide adduct, novolak glycidyl ether, polyalkylene glycol diglycidyl ether, glycerin triglycidyl ether, pentaerythritol di Glycidyl ether type such as glycidyl ether and epoxy urethane resin; Glycidyl ether / ester type such as P-oxybenzoic acid glycidyl ether / ester; diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate Glycidyl ester type such as, diglycidyl acrylate, diglycidyl dimer; Glycidyl aniline, tetraglycidyl diaminodiphenylmethane, triglycidyl isocyanurate, glycidyl amine type, such as triglycidyl aminophenol; epoxidized polybutadiene, linear aliphatic epoxy resins such as epoxidized soybean oil; 3,4 epoxy -
6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexane) carboxylate, bis (3,4-epoxy-6methylcyclohexylmethyl) adipate, vinylcyclohexene Examples include alicyclic epoxy resins such as diepoxide, dicyclopentadiene oxide, bis (2,3-epoxycyclopentyl) ether, and limonenedioxide, and polyamide epichlorohydrin.

Compounds having two or more oxazoline groups or oxazine groups in the molecule include 2,2'-ethylenebis (2-oxazoline), 2,2'-p-phenylenebis (2-oxazoline), Unsaturated oxazolines or oxazine compounds such as 2'-ethylenebis (2-oxazine), 2,2'-p-phenylenebis (2-oxazine), 2-vinyl-2-oxazoline, 2-isopropenyl-2-oxazoline and others And a polymer obtained by polymerization of an unsaturated compound of the formula (I).

Compounds having two or more isocyanate groups in the molecule include butane-1,4-diisocyanate, 1,6-hexane diisocyanate, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate- (1,4), 1-methylcyclohexane-
2,4-diisocyanate, 1-methylcyclohexane-2,6-diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate,
Examples thereof include 2,4-toluylene diisocyanate, 2,6-toluylene diisocyanate, and 4,4′-diphenylmethane diisocyanate.

In the aqueous resin composition and the adhesive of the present invention, (A) a polymer in which a polyurethane unit and a polyvinyl alcohol unit are bonded by a structural unit represented by the above general formula (I) is dispersed in water. The blending amount of the emulsion and (B) a compound having two or more functional groups selected from an aziridine group, an epoxy group, an oxazoline group or an oxazine group and an isocyanate group in a molecule is 100 parts by weight of (A) in terms of solid content. (B) 0.1-70
Part is preferable, and (B) 0.2 to 50 parts is more preferable.
Outside of this range, there are problems such as insufficient curing and embrittlement of the coating.

The aqueous resin composition and the adhesive of the present invention comprise:
In addition to the above (A) and (B), an aqueous emulsion can be blended as required. Examples of the aqueous emulsion that can be blended include conventionally known vinyl acetate polymer emulsions, vinyl acetate- (meth) acrylate copolymer emulsions, ethylene-vinyl acetate copolymer emulsions, and ethylene-vinyl acetate- (meth) acrylic acid. Ester copolymer emulsion, ethylene-vinyl chloride copolymer emulsion, ethylene-vinyl acetate-vinyl chloride copolymer emulsion, ethylene-vinyl acetate-
Tertiary carboxylic acid vinyl ester copolymer emulsion, (meth) acrylate (co) polymer emulsion, styrene- (meth) acrylate copolymer emulsion, styrene-butadiene copolymer emulsion, styrene- (meth) Vinyl acetate resin emulsions such as acrylate-butadiene copolymer emulsions, (meth) acrylate emulsions,
Diene resin emulsions are exemplified. The effect of the present invention can be further improved by using a carboxyl group introduced into these aqueous emulsions by copolymerization or the like. (A)
The amount of the aqueous emulsion to be added to (A) and (B) is not particularly limited, but is generally preferably 2,000 parts by weight or less in terms of solid content based on 100 parts by weight of (A).
1500 parts by weight or less is more preferable. If the aqueous emulsion is blended outside this range, the effects of the present invention may not be sufficiently exhibited.

If necessary, the aqueous resin composition and the adhesive of the present invention may contain a conventionally known urethane dispersion. In addition, if necessary,
Various organic solvents such as toluene, perclene, dichlorobenzene, trichlorobenzene, starch, modified starch, oxidized starch, sodium alginate, carboxymethylcellulose, methylcellulose, in order to adjust the drying property, setting property, viscosity, film forming property, etc. Hydroxymethyl cellulose, maleic anhydride / isobutene copolymer,
Maleic anhydride / styrene copolymer, maleic anhydride /
Water-soluble polymers such as methyl vinyl ether copolymer and thermosetting resins such as urea / formalin resin, urea / melamine / folimarin resin, phenol / folimarin resin,
In addition, clay, kaolin, talc, calcium carbonate,
Fillers such as wood flour, bulking agents such as flour, reaction accelerators such as boric acid and aluminum sulfate, pigments such as titanium oxide and others, defoamers, dispersants, antifreeze agents, preservatives, rust inhibitors, etc. Can also be added as appropriate.

The composition of the present invention is used for applications such as adhesives, glass fiber sizing agents, inks and paints. Among them, industrial fibers, leather, interior decoration, apparel, flooring (wood, concrete, floor polish), coatings for plastic parts, etc., packages (wrapping paper, etc.), laminations (film / foil, fibers, etc.),
It is effectively used as an adhesive for general industrial use (PVC sheet / wood material, PVC sheet / metal, metal / wood).

The method of using the composition of the present invention as an adhesive is not particularly limited, but is usually applied to a substrate by a method such as a roll coater, nozzle (spray) coating, dipping, or brush coating. I do. In addition, for the bonding operation, the temperature is usually around room temperature and there is no problem, but a heating operation may be added for the purpose of shortening the bonding time, improving the adhesiveness and the curability, By doing so, performance can be further improved.

[0025]

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the following Examples and Comparative Examples, “parts” and “%” mean on a weight basis unless otherwise specified.

Production of Polymer Emulsion Consisting of Polyurethane Unit and Polyvinyl Alcohol Unit Production Example 1 Polyester diol obtained from adipic acid and ethylene glycol and tolylene diisocyanate were NCO / O
After copolymerizing primary amino group-containing polyvinyl alcohol (vinyl formamide and vinyl acetate) with 100 parts by weight of an acetone solution (solid content concentration: 30%) of a urethane prepolymer obtained by reacting at an H molar ratio of 2/1, Polyvinyl alcohol obtained by saponification: polymerization degree 350, saponification degree 98.
5 mol%, primary amino group content 1.5 mol%).
5 parts and nonionic surfactant (Newpole PE-6)
A solution prepared by dissolving 0.4 part of (8, manufactured by Sanyo Chemical) in 15 parts of water was added at 30 ° C. with rapid stirring. Next, 60 parts of water was added through a homogenizer to obtain a stable polymer dispersion. Further, acetone was distilled off at 50 ° C. under reduced pressure to obtain a polymer emulsion having a solid content of 38% and an average particle diameter of 0.2 μm.

Production Example 2 Polyester diol obtained from adipic acid and ethylene glycol, dimethylolpropionic acid and tolylene diisocyanate, NCO / OH molar ratio = 2/1, polyesterdiol / dimethylolpropionic acid molar ratio = 1/0. After copolymerizing a primary amino group-containing polyvinyl alcohol (allyl glycidyl ether and vinyl acetate) with 100 parts by weight of an acetone solution (solid content concentration: 30%) of the urethane prepolymer obtained by the reaction at step 01, 2-aminothiophenol Was added by using NaOH as a catalyst and saponified, and 3 parts of poly (vinyl alcohol) were dissolved in 15 parts of water. This was added at 30 ° C. with rapid stirring. Next, 60 parts of water was added through a homogenizer to obtain a stable polymer dispersion. Further, acetone was distilled off at 50 ° C. under reduced pressure to obtain a polymer emulsion having a solid content of 37% and an average particle diameter of 0.3 μm.

Production Example 3 Polypropylene glycol alcohol, dimethylolpropionic acid and tolylene diisocyanate were mixed with NCO /
OH molar ratio = 2/1, polypropylene glycol allether / dimethylolpropionic acid molar ratio = 1 / 0.02
100 parts by weight of an acetone solution (solid content concentration: 30%) of a urethane prepolymer obtained by the reaction described in (1), a secondary amino group-containing polyvinyl alcohol (methyl vinylacetamide and vinyl acetate are copolymerized and then saponified. Polyvinyl alcohol: degree of polymerization 750, degree of saponification 87.
A solution prepared by dissolving 5 parts of 5 mol% and a secondary amino group content of 2.5 mol% in 15 parts of water was added at 30 ° C. with rapid stirring. Next, 60 parts of water was added through a homogenizer to obtain a stable polymer dispersion. Furthermore, under reduced pressure,
Acetone was distilled off at 50 ° C. to obtain a polymer emulsion having a solid content of 38% and an average particle diameter of 0.3 μm.

Production Example 4 Polyester diol obtained from adipic acid and ethylene glycol and tolylene diisocyanate were subjected to NCO / O
100 parts by weight of an acetone solution (solid content: 30%) of a urethane prepolymer obtained by reacting at an H molar ratio of 2/1 was added to a polyvinyl alcohol containing a primary amino group and a carboxyl group (vinyl formamide and maleic anhydride). And polyvinyl acetate copolymerized and then saponified to obtain polyvinyl alcohol: a degree of polymerization of 300, a degree of saponification of 98.5 mol%,
2 parts of a primary amino group content of 1.5 mol% and maleic anhydride unit of 1.0 mol%) and 0.3 part of a nonionic surfactant (Newpol PE-68, manufactured by Sanyo Chemical Co., Ltd.) in 15 parts The solution dissolved in water was added at 30 ° C. with rapid stirring. Next, 60 parts of water was added through a homogenizer to obtain a stable polymer dispersion. Further, acetone was distilled off at 50 ° C. under reduced pressure, and the solid content concentration was 37%, and the average particle size was 0.1.
A 5 μm polymer emulsion was obtained.

Comparative Production Example 1 A polymer emulsion was obtained in the same manner as in Production Example 1 except that no primary amino group-containing polyvinyl alcohol was used.

Examples 1 to 8, Comparative Examples 1 to 3 Polymer emulsions (A) obtained by the above production examples
Was mixed with the compound (B) shown in Table 1 to prepare an aqueous dispersion, and a film having an average film thickness of 300 μm was prepared at 20 ° C. and 65% RH, and the following tests were performed. (Water resistance and solvent resistance of the film) The film was punched out into a circular shape with a diameter of 25 mm, and the film was immersed in various solvents (water, toluene, ethyl acetate) at 20 ° C for 16 hours to measure the elution rate (% by weight) of the film. did. Table 1 shows the results.

Examples 9 to 14, Comparative Examples 4 to 5 Polymer emulsions (A) obtained by the above production examples
Was mixed with the compound (B) shown in Table 2 and an aqueous emulsion to prepare an aqueous dispersion, which was used to bond a soft PVC sheet and Rawan plywood to conduct an adhesion test shown below. Table 3 shows the results. (Adhesion conditions) Adherend: Soft PVC sheet 1 mm thick / Lauan plywood (Type # 1; 5.5 mm thick) Coating amount: 10 g / 30 × 30 cm Curing: After applying and bonding, lightly pressing with a rubber hand roller, 3 Curing at 20 ° C and 65% RH for a day (Test conditions) Normal strength: Cut to inch width and peel 180 degrees as it is (200 mm / min) Water resistance strength: After 24 hours immersion in water, peel 180 degrees wet (200 mm / min) Heat resistance creep: 80 ° C, 95% RH, 90 degree angle, 1k
Length peeled by g load

[0033]

[Table 1]

[0034]

[Table 2]

[0035]

[Table 3]

[0036]

The aqueous resin composition of the present invention gives a film excellent in water resistance, solvent resistance, heat resistance, durability, aging resistance and adhesion to a substrate. Accordingly, the aqueous resin composition of the present invention can be used as a coating agent for industrial fibers, leather, interior decoration, apparel, flooring (wood, concrete, floor polish), plastic parts, etc., package (wrapping paper etc.), lamination (film) / Foil, fiber, etc.),
Adhesives for general industry (PVC sheet / wood, PVC sheet / metal, metal / wood), etc., and can be widely and effectively used in application fields such as glass fiber sizing agents, inks, and paints.

Claims (5)

[Claims] 1. An emulsion comprising (A) a polymer in which a polyurethane unit and a polyvinyl alcohol unit are bonded by a structural unit represented by the following general formula (I), and (B) an aziridine group and an epoxy group. , An aqueous resin composition comprising a compound having two or more functional groups selected from oxazoline groups, oxazine groups, and isocyanate groups in the molecule. Embedded image 2. The aqueous resin composition according to claim 1, wherein the polymer constituting the emulsion (A) contains a carboxyl group in its polyurethane unit. 3. The aqueous resin composition according to claim 1, wherein the polymer constituting the emulsion (A) contains a carboxyl group in the polyvinyl alcohol unit. 4. The aqueous resin composition according to claim 1, wherein one or more aqueous emulsions selected from a vinyl acetate resin emulsion, a (meth) acrylate ester emulsion, and a diene resin emulsion are blended. . 5. An adhesive comprising the aqueous resin composition according to claim 1.