JPH1053709A - Emulsion composition and adhesive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an emulsion composition excellent in water resistance and water resistance and an adhesive comprising the same. SOLUTION: An aqueous dispersion of an organic polymer (A) having at least one acid group selected from the group consisting of a carboxyl group, a sulfonic acid group and a phosphoric acid group or a salt thereof, a carboxyl group, a sulfonic acid group and A compound (B) having at least one acid group or a salt thereof selected from the group consisting of a phosphate group and at least two phenolic hydroxyl groups, and a reactivity with the acid group or a salt thereof. An emulsion composition comprising a compound (C) having at least two functional groups.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

SUMMARY OF THE INVENTION The present invention relates to an emulsion composition having excellent water-resistant adhesiveness and water-resistant adhesiveness, and an adhesive comprising the same.

[0002]

2. Description of the Related Art Organic solvent-based adhesives, pressure-sensitive adhesives, paints, coatings, and the like have excellent adhesiveness and adhesion, and are widely used for various purposes. However, such an adhesive using an organic solvent has problems such as air pollution due to the volatilization of the organic solvent, deterioration of the working environment, and the risk of fire. For this reason, the development of emulsion compositions that do not use organic solvents has been actively pursued.

An emulsion composition used as an adhesive or the like is obtained by dispersing an organic polymer in water. However, since such an organic polymer is generally insoluble in water, it is necessary to use a large amount of an emulsifier in order to stably disperse it in water. When an emulsion composition containing a large amount of an emulsifier is used as an adhesive or the like, moisture is easily taken into the interface between the adherend and the dried organic polymer film, and the organic polymer dried film itself tends to have an adhesive property. Adhesion decreases. In particular, when the adherend is a metal, the adhesion is further reduced due to corrosion of the metal.

As a technique for solving such a problem, for example, JP-A-3-21626 discloses that an ionic functional group such as a carboxyl group is introduced into the molecule of a urethane polymer to eliminate the need for an emulsifier. The disclosed urethane emulsion composition is disclosed.

However, the above-mentioned urethane-based emulsion composition has an insufficient effect of suppressing moisture intrusion into the adherend interface and corrosion of the metal adherend surface since acidic groups remain in the urethane polymer film. It is. For this reason, these emulsion compositions cannot be used in fields where water resistance and water resistance are required, such as building materials.

[0006]

SUMMARY OF THE INVENTION In view of the above, it is an object of the present invention to provide an emulsion composition having excellent water resistance and water resistance and an adhesive comprising the same.

[0007]

SUMMARY OF THE INVENTION The present invention provides an aqueous dispersion of an organic polymer (A) having at least one acid group selected from the group consisting of a carboxyl group, a sulfonic acid group and a phosphoric acid group, or a salt thereof. A compound having at least one acid group selected from the group consisting of a carboxyl group, a sulfonic acid group and a phosphoric acid group, or a salt thereof, and at least two phenolic hydroxyl groups; Or an emulsion composition comprising a compound (C) having at least two functional groups reactive with a salt thereof. Hereinafter, the present invention will be described in detail.

The organic polymer (A) used in the present invention has at least one acid group selected from the group consisting of a carboxyl group, a sulfonic acid group and a phosphoric acid group, or a salt thereof. An organic polymer generally used as an adhesive, a paint, a coating agent, or the like is used as a main skeleton, and the main skeleton has at least one acid group selected from the group consisting of a carboxyl group, a sulfonic acid group, and a phosphate group, or The salt has been introduced.

The main skeleton can be broadly classified into a polymer (1) obtained by radical addition polymerization and a polymer (2) obtained by polyaddition. The monomer constituting the polymer (1) is not particularly limited. For example, ethylene; propylene; butylene; isobutylene; butadiene; isoprene; chloroprene; styrene; vinyl chloride; vinylidene chloride; vinyl acetate, vinyl valerate, and caprylic acid Fatty acid vinyl esters such as vinyl; acrylonitrile; methacrylonitrile; acrylic esters such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate; methacrylic esters such as methyl methacrylate, butyl methacrylate, lauryl methacrylate; acrylamide; methacrylamide;
Vinylpyrrolidone; N-vinylmorpholine; N, N-dimethylacrylamide. These may be used alone or in combination of two or more.

As the polymer (1) obtained by the above radical addition polymerization, styrene-butadiene-based copolymer, acrylonitrile-butadiene-based copolymer, chloroprene-based polymer are preferable because of their excellent adhesion to a substrate. Coalescence, vinyl acetate polymer, ethylene-vinyl acetate copolymer,
(Meth) acrylate polymers and the like are preferably used.

[0011] At least one acid group selected from the group consisting of a carboxyl group, a sulfonic acid group and a phosphoric acid group or a salt thereof is introduced into the polymer (1) obtained by the above-mentioned radical addition polymerization. The method for forming the polymer (A) is not particularly limited, and an appropriate method can be adopted. For example, at least one kind of acid group selected from the group consisting of a carboxyl group, a sulfonic acid group and a phosphoric acid group Or a polymer (1) obtained by subjecting a monomer having a salt thereof and a polymerizable unsaturated double bond to the above radical addition polymerization.
And the like.

Among such monomers, those having an acid group are not particularly limited, and examples thereof include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-acryloxyethylsuccinic acid, 2-acryloxyethyl phthalic acid, 2-methacryloxyethyl succinic acid, 2-methacryloxyethyl phthalic acid, 4-acryloxyethyl trimellitic acid, 4-methacryloxyethyl trimellitic acid, caprolactone-modified 2-hydroxyethyl acrylate, Examples include caprolactone-modified 2-hydroxyethyl methacrylate, acryloxyethyl phosphate, methacryloxyethyl phosphate, acryloxyethylsulfonic acid, methacryloxyethylsulfonic acid, and styrenesulfonic acid. These may be used alone or in combination of two or more. Among them, acrylic acid, methacrylic acid, acryloxyethyl phosphate, methacryloxyethyl phosphate, styrenesulfonic acid and the like are preferably used.

Among these monomers, those having a salt of an acid group are not particularly limited. Examples thereof include alkali metal salts such as sodium and potassium of the above-mentioned monomer having an acid group; And ammonium salts such as trimethylamine and triethylamine. These may be used alone or in combination of two or more. Of these, volatile ammonium salts such as ammonium and triethylamine can be removed by scattering when the emulsion composition of the present invention is dried and formed into a film, which lowers the water resistance of the obtained film. Since it is not allowed to be used, it is preferably used.

The polymer (2) obtained by the above polyaddition is not particularly limited, and examples thereof include a urethane polymer obtained from a polyisocyanate and a polyol, a urea polymer obtained from a polyisocyanate and a polyamine, and a polyurea. Examples include an ether-based polymer obtained from an epoxy and a polyol, and a sulfide-based polymer obtained from a polyvinyl compound and a polythiol. Of these, urethane-based polymers and urea-based polymers are preferably used because of their excellent adhesion to the substrate.

The polymer (2) obtained by the above polyaddition
The method of introducing at least one acid group selected from the group consisting of a carboxyl group, a sulfonic acid group and a phosphoric acid group or a salt thereof into the above-mentioned organic polymer (A) is not particularly limited, and is appropriately selected. For example, a carboxyl group, a polyol having at least one acid group selected from the group consisting of a sulfonic acid group and a phosphate group or a salt thereof, a polyamine, a polyvinyl compound,
A method of copolymerizing polythiol or the like when polymerizing the polymer (2) obtained by the above polyaddition can be adopted.

Among these monomers, those having an acid group are not particularly limited. Examples thereof include dimethylol lactic acid, dimethylol propionic acid, dimethylol butyric acid, dimethylol valeric acid, lysine, arginine, and 2,4-diaminobenzoic acid. 3,4-diaminobutanesulfonic acid,
3,6-diamino-2-toluenesulfonic acid, 2,6-
Examples thereof include diaminobenzenesulfonic acid and N- (2-aminoethyl) -2-aminoethylsulfonic acid. These may be used alone or in combination of two or more.

Among such monomers, those having a salt of an acid group are not particularly limited. Examples thereof include alkali metal salts such as sodium and potassium of the above monomers having an acid group; and ammonium salts such as ammonia, trimethylamine and triethylamine. And the like. These may be used alone or in combination of two or more. Of these, volatile ammonium salts such as ammonium and triethylamine can be removed by scattering when the emulsion composition of the present invention is dried and formed into a film, which lowers the water resistance of the obtained film. Since it is not allowed to be used, it is preferably used.

When polymerizing the polymer (1) obtained by the radical addition polymerization or the polymer (2) obtained by the polyaddition, after polymerizing the monomer having an acid group, The acid groups can be converted to salts by adding an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide; an amine such as ammonia, trimethylamine or triethylamine.

In the organic polymer (A), the amount of the acid group or a salt thereof is based on 1 g of the organic polymer (A).
0.02 to 3 mmol are preferred. When the amount is less than 0.02 mmol, the effect of improving the water resistance is insufficient, and the hydrophilicity of the organic polymer (A) is insufficient, so that it is difficult to stably disperse it in water. When the amount exceeds mmol, the hydrophilicity of the organic polymer (A) becomes too large,
The water resistance of the dried film decreases. More preferably, 0.1
~ 2.0 mmol.

The method for producing the aqueous dispersion of the organic polymer (A) is not particularly limited, and any suitable method can be employed. When the organic polymer (A) has a main skeleton of the polymer (1) obtained by the radical addition polymerization, for example, the above-mentioned monomers can be prepared by adding water to the above-mentioned monomer in the presence of an emulsifier or a water-soluble polymer. Emulsion polymerization method in which the above monomers are dispersed in water in the presence of a dispersion stabilizer such as an emulsifier, a water-soluble polymer, or inorganic fine particles to form an oil-soluble radical polymerization. A suspension polymerization method of polymerizing with an initiator;
After polymerization in bulk or in an organic solvent such as alcohol, acetone, or methyl ethyl ketone, a post-dispersion method or the like of dispersing in water can be employed. Among them, the emulsion polymerization method is preferable because the production is relatively simple and the obtained aqueous dispersion of the organic polymer (A) has excellent dispersion stability.

When the organic polymer (A) has the main skeleton of the polymer (2) obtained by the above-mentioned polyaddition, for example, the above-mentioned monomers may be replaced with an emulsifier, a water-soluble polymer or the like. A method of dispersing in water in the presence of a dispersion stabilizer to cause a polyaddition reaction; a post-dispersion method of dispersing in water after the above monomers are subjected to a polyaddition reaction in a bulk or organic solvent. it can. Among them, the post-dispersion method is preferable because the side reaction during the polyaddition reaction is small. Also,
When the organic polymer (A) is a urethane-based polymer, the resulting emulsion composition is excellent in dispersion stability and coatability to a base material, and therefore has a self-emulsifying urethane polymer or urethane. A post-emulsification method in which the prepolymer is dispersed in water is more preferred. Hereinafter, a post-emulsification method of dispersing the urethane polymer or urethane prepolymer having the self-emulsifying property in water will be described in detail.

The self-emulsifying urethane polymer or urethane prepolymer includes a polyisocyanate compound, a polyol compound, a carboxyl group in the molecule,
It is obtained by reacting a compound having at least one acid group selected from the group consisting of a sulfonic acid group and a phosphoric acid group or a salt thereof, and further having at least two active hydrogens capable of reacting with an isocyanate group. Product.

The polyisocyanate compound is not particularly restricted but includes, for example, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,2,4-trimethyl Hexamethylene diisocyanate, 3-isocyanatomethyl-3,5,5-
Trimethylcyclohexyl isocyanate, dicyclohexylmethane-4,4'-diisocyanate, methylcyclohexyl-2,4-diisocyanate, methylcyclohexyl-2,6-diisocyanate, xylylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, tetramethylxylylene Aliphatic diisocyanates such as diisocyanate and transcyclohexane-1,4-diisocyanate; 2,4-toluylene diisocyanate, 2,6-toluylene diisocyanate, diphenylmethane-4,4'-diisocyanate, 1,5-naphthene diisocyanate, tolidine Aromatic diisocyanates such as diisocyanate, tetraalkyldiphenylmethane diisocyanate and paraphenylene diisocyanate And the like. These may be used alone or in combination of two or more.

The polyol compound is not particularly restricted but includes, for example, polyether polyols such as polyethylene glycol and polypropylene glycol; dicarboxylic acids such as adipic acid, sebacic acid, itaconic acid, maleic anhydride, terephthalic acid and isophthalic acid; Polyester diols composed of diols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol, 1,6-hexanediol, tripropylene glycol, neopentyl glycol; polycaprolactone diol; polytetramethylene ether diol; polybutadiene Diol; hydrogenated polybutadiene diol; polycarbonate diol; polythioether diol; polyacrylate diol and the like. These may be used alone or in combination of two or more.

The molecular weight of the above polyol compound is preferably 300 to 20,000 when used alone. If it is less than 300, the obtained dried film becomes too hard, and if it exceeds 20,000, the viscosity of the urethane polymer or urethane prepolymer before water dispersion becomes too high, and the dispersion operation at the time of water dispersion becomes difficult. More preferably, it is 300 to 10,000.
Further, if necessary, the polyol compound having a molecular weight of 300 to 20,000 may be added to the polyol compound having a molecular weight of less than 300, for example, ethylene glycol, 1,4-butanediol, 1,6-
A low molecular weight diol compound such as hexanediol can be used as a mixture.

At least one selected from the group consisting of a carboxyl group, a sulfonic acid group and a phosphoric acid group in the molecule
The compound having at least two active hydrogens capable of reacting with an isocyanate group having at least two kinds of acid groups or salts thereof is not particularly limited. For example, dimethylol lactic acid, dimethylol propionic acid, dimethylol butyric acid, dimethylol valeric acid Lysine, arginine, 2,4-diaminobenzoic acid, 3,4-diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, 2,6-diaminobenzenesulfonic acid, N- (2-aminoethyl ) -2-Aminoethylsulfonic acid and the like. These may be used alone or in combination of two or more. Among them, dimethylol alkanoic acid compounds such as dimethylolpropionic acid, dimethylolbutyric acid, and dimethylolvaleric acid having a structure represented by the following general formula (1) are preferably used.

[0027]

Embedded image (In the formula, R represents an alkyl group having 1 to 20 carbon atoms.)

In the above-mentioned molecule, at least one selected from the group consisting of a carboxyl group, a sulfonic group and a phosphoric group.
The amount of the compound having at least two active hydrogens capable of reacting with an isocyanate group having at least two kinds of acid groups or salts thereof is 0% as the amount of acid groups in 1 g of the obtained urethane polymer or urethane prepolymer. It is preferable to add so as to be 0.1 to 2.0 mmol. If the amount is less than 0.1 mmol, the resulting urethane polymer or urethane prepolymer lacks hydrophilicity and is difficult to stably disperse in water. If the amount exceeds 2.0 mmol, the obtained urethane polymer or urethane The hydrophilicity of the prepolymer becomes too large, and the water resistance of the dried film decreases.

In the above-mentioned molecule, at least one selected from the group consisting of a carboxyl group, a sulfonic group and a phosphoric group.
When a compound having a kind of acid group or a salt thereof and further having at least two active hydrogens capable of reacting with an isocyanate group is used, the acid group in the obtained urethane polymer or urethane prepolymer is completely or partially It is preferable to use a neutralizing agent that neutralizes the urethane in order to stably disperse the obtained urethane polymer or urethane prepolymer in water.

The neutralizing agent is not particularly restricted but includes, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; and tertiary amines such as trimethylamine and triethylamine. Of these, volatile tertiary amines are preferably used since the resulting coating can be prevented from lowering in water resistance by being scattered and removed during drying.

Further, in order to improve the dispersion stability, it has a cationic hydrophilic group such as an ammonium group or a nonionic hydrophilic group such as polyoxyethylene, and further has an active hydrogen capable of reacting with isocyanate. May be used in combination. In this case, the amount of the hydrophilic group is such that the molecule has at least one acid group selected from the group consisting of a carboxyl group, a sulfonic acid group and a phosphate group or a salt thereof, Together with the amount of the acid group or a salt thereof in the compound having at least two active hydrogens capable of reacting with a group, 0.1 to 0.1 g / g of the obtained urethane polymer or urethane prepolymer
2.0 mmol is preferred. If the amount is less than 0.1 mmol, the resulting urethane polymer or urethane prepolymer lacks hydrophilicity and is difficult to stably disperse in water. If the amount exceeds 2.0 mmol, the obtained urethane polymer or urethane The hydrophilicity of the prepolymer becomes too large, and the water resistance of the dried film decreases.

The polyisocyanate compound, the polyol compound, and a carboxyl group in the molecule,
A compound having at least one acid group selected from the group consisting of a sulfonic acid group and a phosphoric acid group or a salt thereof, and further reacting a compound having at least two active hydrogens capable of reacting with an isocyanate group to form a self-emulsifying compound; The method for obtaining the urethane polymer or urethane prepolymer is not particularly limited, and examples thereof include bulk polymerization and solution polymerization.

In either case of the above bulk polymerization or the above solution polymerization, the reaction temperature is preferably from 50 to 150 ° C. The solvent used in the case of performing the solution polymerization is not particularly limited, for example, acetone, methyl ethyl ketone, tetrahydrofuran, inert to isocyanate groups such as methyl acetate, highly miscible with water,
Further, those having a boiling point of 100 ° C. or less are preferred. 10
When a solvent having a boiling point higher than 0 ° C. is used, it is difficult to remove only the solvent from the obtained emulsion composition to the outside in the step after water dispersion.

When the self-emulsifying urethane polymer or urethane prepolymer is reacted, a catalyst such as an amine compound or an organometallic compound may be used for the purpose of adjusting the reaction rate. The amine compound is not particularly limited and includes, for example, triethylamine, N, N,
N ', N'-tetramethylethylenediamine, tetramethylguanidine, triethylenediamine, dimethylaminoethanol, bis (2-dimethylaminoethyl) ether and the like can be mentioned. These may be used alone,
More than one species may be used in combination.

The organometallic compound is not particularly restricted but includes, for example, stannas octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dimaleate, phenylmercuric acid propionate, lead octenoate and the like. These may be used alone or in combination of two or more.

The polyisocyanate compound, the polyol compound, and a carboxyl group in the molecule
A compound having at least one acid group selected from the group consisting of a sulfonic acid group and a phosphoric acid group or a salt thereof, and further reacting a compound having at least two active hydrogens capable of reacting with an isocyanate group. The compounding amount of the component is not particularly limited, but it is possible to mix the component such that the equivalent ratio of the isocyanate group is excessive with respect to the active hydrogen capable of reacting with the isocyanate group. It is preferable because a prepolymer can be obtained. By using a urethane prepolymer having an isocyanate group at the end, the viscosity becomes low, so that it is easy to disperse in water.After dispersing in water, the chain is extended by a chain extender starting from the terminal isocyanate group to increase the molecular weight. By doing so, various physical property designs can be made advantageous.

The method of dispersing the obtained urethane polymer, urethane prepolymer or their organic solvent solution in water is not particularly limited. For example, (1) an acetone method of dispersing a urethane polymer organic solvent solution in water,
(2) A prepolymer mixing method of self-emulsifying a urethane prepolymer having an isocyanate group at a terminal and then chain-extending the same; A block isocyanate method of blocking and extending the chain, (4) a melt dispersion method of dispersing a urethane prepolymer having a terminal buret group by heating in molten water, converting the urethane prepolymer to formol with methylaldehyde and extending the chain, and the like can be used.

When dispersed in water, acetone, methyl ethyl ketone, tetrahydrofuran, ethyl acetate, ethyl acetate, and the like are used so that the viscosity of the urethane polymer, urethane prepolymer or their organic solvent solution having self-emulsifiability is 50,000 cP or less. It is preferable to adjust with a hydrophilic organic solvent such as -methylpyrrolidone. 50,000c
If it exceeds P, problems such as aggregation will occur.

The above-mentioned dispersion is carried out, for example, by adding water gradually to a urethane polymer, a urethane prepolymer or an organic solution thereof having the above-mentioned self-emulsifying property while applying a mechanical shearing force. Meanwhile, a batch method such as a method of gradually adding a urethane polymer, a urethane prepolymer having a self-emulsifying property or an organic solution thereof; various kinds of continuous emulsification such as a rotor-stator method, a line mill method, a static mixer method, and a vibration method It can be carried out by a continuous method of quantitatively supplying and dispersing water and the urethane polymer, urethane prepolymer or their organic solutions having self-emulsifiability to a disperser, and the like.

When the urethane prepolymer having an isocyanate group at the terminal is dispersed in water, the urethane prepolymer is chain-chained with a compound having two active hydrogens capable of reacting with the isocyanate group after or simultaneously with the dispersion step. Can be extended. The compound having two active hydrogens capable of reacting with the isocyanate group is not particularly limited, and examples thereof include ethylenediamine and 1,4.
-Butanediamine, 1,6-hexamethylenediamine,
3-aminomethyl-3,5,5-trimethylcyclohexylamine, 1,3-bis (aminomethyl) cyclohexane, xylylenediamine, piperazine, 2,5-dimethylpiperazine, 4,4'-dicyclohexylmethanediamine, 3, Diamino compounds such as 3'-dimethyl-4,4'-dicyclohexylmethanediamine; and diol compounds such as ethylene glycol, propylene glycol, 1,4-butanediol, and 1,6-hexanediol.

The amount of the compound having two active hydrogens capable of reacting with the isocyanate group is as follows.
It is preferable that the amount is equal to or less than the equivalent of the isocyanate group serving as a chain extension starting point in the urethane prepolymer having an isocyanate group at the terminal. When the isocyanate group is added in excess of the equivalent, the molecular weight of the obtained urethane polymer is reduced by chain extension, and the cohesive force of the dried film of the obtained emulsion composition is reduced.
Since the compound having two active hydrogens capable of reacting with the isocyanate group has higher nucleophilicity to the isocyanate group than water existing as a dispersion medium, the reaction proceeds in preference to water existing as a dispersion medium. .

The urethane prepolymer having an isocyanate group at the terminal can be extended with water. In this case, water as a dispersion medium present during the above-mentioned dispersion step also serves as a chain extender. In this reaction, the amine generated by the reaction of water with the isocyanate group in the urethane prepolymer having an isocyanate group at the terminal always reacts with a new isocyanate group, so that the amount of water is excessive. However, the amount of water involved in the chain extension reaction does not exceed the equivalent of isocyanate groups.

When synthesizing the urethane polymer or urethane prepolymer having self-emulsifiability or dispersing the urethane polymer or urethane prepolymer in water, the hydrophilic organic solvent added as necessary may be heated,
Using a means such as reduced pressure or reduced pressure heating, the resulting urethane polymer can be removed outside the aqueous dispersion of the aqueous dispersion.
When a large amount of the hydrophilic organic solvent remains in the aqueous dispersion of the urethane polymer, the solvent resistance and the heat resistance of the dried film of the finally obtained emulsion composition are reduced, and Deteriorate working environment.

Compound (B) used in the present invention
Is a compound having at least one acid group selected from the group consisting of a carboxyl group, a sulfonic acid group and a phosphoric acid group or a salt thereof, and at least two phenolic hydroxyl groups. Such substances are not particularly limited, and include, for example, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid,
6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2,3,4-trihydroxybenzoic acid, 2,4,6-trihydroxybenzoic acid, 3,4,5- Trihydroxybenzoic acid, 3,4
-Dihydroxy-5-[(3,4,5-trihydroxybenzoyl) oxy] benzoic acid, 2,2'-methylenebis (3,4,5-trihydroxybenzoic acid), 3,3 '
-Methylenebis (6-hydroxybenzoic acid), 3,5-
Dihydroxy-4-methylbenzoic acid, 2,4-dihydroxy-6-methylbenzoic acid, 2,5-dihydroxyphenylacetic acid, 3,4-dihydroxyphenylacetic acid, 3,4
-Dihydroxyphenylpropionic acid, 2,6-dihydroxyterephthalic acid, 1,4-bis (carboxymethyl) -2,5-dihydroxybenzene, 3,4-dihydroxymandelic acid, 1,4-dihydroxy-2-naphthalenecarboxylic acid 3,5-dihydroxy-2-naphthalenecarboxylic acid, 3,7-dihydroxy-2-naphthalenecarboxylic acid, 4,4'-methylenebis (3-hydroxy-2-naphthalenecarboxylic acid), 2,5-dihydroxybenzenesulfone Acid, 2,5-dihydroxy-1,4-
Benzenedisulfonic acid, 4,5-dihydroxy-1,3
-Benzenedisulfonic acid, 6,7-dihydroxy-2-
Naphthalenesulfonic acid, 4,5-dihydroxy-2,7
-Naphthalenedisulfonic acid, 3,6-dihydroxy-
2,7-naphthalenedisulfonic acid and the like can be mentioned.

Among them, 2,3,4-trihydroxybenzoic acid, 2,4,6-trihydroxybenzoic acid,
4,5-trihydroxybenzoic acid, 3,4-dihydroxy-5-[(3,4,5-trihydroxybenzoyl)
Oxy] benzoic acid, 2,2'-methylenebis (3,4
5-trihydroxybenzoic acid) and the like are preferably used.

Further, alkali metal salts such as sodium and potassium; and ammonium salts such as ammonia, trimethylamine and triethylamine. Of these, volatile ammonium salts such as ammonium and triethylamine can be removed by scattering when the emulsion composition of the present invention is dried and formed into a film, which lowers the water resistance of the obtained film. Since it is not allowed to be used, it is preferably used.

In the present invention, the amount of the compound (B) is preferably 0.1 to 30 parts by weight based on 100 parts by weight of the organic polymer (A). If the amount is less than 0.1 part by weight, the effect of improving the water-resistant adhesive strength is small, and if it exceeds 30 parts by weight, the physical properties such as the strength of the obtained film are significantly reduced. More preferably, it is 0.5 to 20 parts by weight.

The method for adding the compound (B) is not particularly limited. For example, the compound (B) is diluted with a hydrophilic solvent or water and then directly added to the aqueous dispersion of the organic polymer (A). A method of adding; a method of mixing the compound (B) with the organic polymer (A) before being dispersed in water, and then dispersing the mixture in water; a method of adding the compound (B) to the organic polymer ( After mixing with the monomer or prepolymer as the raw material of A), a method of dispersing this mixture in water can be adopted.

Compound (C) used in the present invention
Is a compound having at least two functional groups reactive with the acid group or the salt thereof of the organic polymer (A) and the compound (B). The functional group is not particularly limited as long as it is a functional group capable of reacting with the acid group or a salt thereof to form a chemical bond.
Examples include an epoxy group, an aziridine group, an oxazoline group, an isocyanate group, a carbodiimide group, and a hydrazine group. Specific examples of the compound (C) include the following compounds known as so-called crosslinking agents.

(1) Hexamethylene diisocyanate
(HDI), trimer of HDI, isophorone diisocyanate
(IPDI), trimer of IPDI, xylylene disulfide
Socyanate (XDI), trimer of XDI, diphenyl
Methane diisocyanate (MDI), 1,4-cyclohexane
Xanbis (methyl isocyanate) (H₆XDI),
H ₆XDI trimer, 4,4-methylenebis (cyclo
Xyl isocyanate) (H₁₂MDI), H₁₂MDI's
Trimers; trimethylol-based diisocyanates
Lopan, polyester polyol, polyethylene glyco
Modified products such as polypropylene and polypropylene glycol
Isocyanate compounds.

(2) Trimethylolpropane-tri-3
-[(1-aziridinyl) propionate)], diphenylmethane-bis-4,4'-N, N'-diethyleneurea, tetramethylolmethane-tri-β-aziridinylpropionate, N, N'-toluene- Aziridine compounds such as 2,4-bis- (1-aziridinecarboxamide) and N, N'-hexamethylene-1,6-bis- (1-aziridinecarboxamide).

(3) Propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, resorcin diglycidyl ether, neopentyl glycol Diglycidyl ether, sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, 1,6-hexanediol diglycidyl ether,
Polytetramethylene glycol diglycidyl ether,
Epoxy compounds such as cresol novolak type epoxy emulsion and modified bisphenol A type epoxy emulsion.

(4) Oxazoline group-containing monomers such as phenylenebis-2-oxazoline, 2,2 '-(1,3-phenylene) bis-2-oxazoline, 2-isopropenyl-2-oxazoline and other monomers An oxazoline-based compound such as an oxazoline-based reactive polymer obtained by copolymerizing (5) A carbodiimide compound represented by the following general formula (2).

[0054]

Embedded image

In the above general formula (2), R ¹ and R ² are the same or different and are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aryl group having 6 to 16 carbon atoms. Represents an aralkyl group. More specifically, examples include a propyl group, a cyclohexyl group, a p-toluoyl group and the like.

(6) Hydrazine compounds such as adipic dihydrazide, sebacic dihydrazide, dodecandiohydrazide, isophthalic dihydrazide, and 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin.

Of these, aziridines, epoxies, isocyanates, oxazolines and carbodiimides are preferred. More preferably, aziridine-based, epoxy-based ones dissolved in water, water-dispersed,
Or, it is self-emulsifying. These may be used alone or in combination of two or more.

In the present invention, the amount of the compound (C) to be added is preferably 0.1 to 30 parts by weight based on 100 parts by weight of the organic polymer (A). If the amount is less than 0.1 part by weight, the effect of improving the water-resistant adhesive strength is small, and if it exceeds 30 parts by weight, the physical properties such as the strength of the obtained film are significantly reduced. More preferably, it is 0.5 to 20 parts by weight.

The emulsion composition of the present invention may further contain, depending on the purpose, a crosslinking agent, an elastomer, a synthetic resin, a plasticizer, an aqueous dispersion of a synthetic resin, an aqueous solution of a water-soluble resin, an aqueous solution of an alkali-soluble resin, or an aqueous dispersion of a tackifying resin. Modifiers such as bodies, pigments, inorganic fillers, coupling agents, stabilizers, thickeners, defoamers, fungicides, rust inhibitors, emulsifiers and the like may be added.

The crosslinking agent is not particularly limited, and examples thereof include metal-based crosslinking agents such as aluminum acetylacetonate and zirconium acetylacetonate. The amount of the cross-linking agent to be added depends on the amount of the organic polymer (A) 10
0.1 to 20 parts by weight relative to 0 parts by weight is preferred.

The above elastomer is not particularly restricted but includes, for example, styrene-butadiene rubber, butadiene rubber, isoprene rubber, acrylonitrile-butadiene rubber, chloroprene rubber, butyl rubber, styrene thermoplastic elastomer, olefin thermoplastic elastomer,
Synthetic rubbers such as urethane-based thermoplastic elastomers and polyester-based thermoplastic elastomers, and natural rubbers are exemplified. These may be used alone or in combination of two or more. The amount of the elastomer added is preferably 0.1 to 300 parts by weight based on 100 parts by weight of the organic polymer (A).

The synthetic resin is not particularly restricted but includes, for example, (meth) acrylic, epoxy, vinyl acetate, vinyl acetate-ethylene copolymer, ethylene-ethyl acrylate copolymer, ethylene- (meth) Examples include acrylic acid copolymers, vinyl chlorides, phenoxys, and styrenes. These may be used alone or in combination of two or more. The amount of the synthetic resin is 0.1 to 300 parts by weight based on 100 parts by weight of the organic polymer (A).
Parts by weight are preferred.

The plasticizer is not particularly restricted but includes, for example, phthalic esters such as diethyl phthalate, dibutyl phthalate and dioctyl phthalate; tributyl phosphate, triphenyl phosphate, tris (β-chloropropyl) phosphate and the like. Fatty acid esters such as butyl oleate, dibutyl adipate, di-n-hexyl adipate and dibutyl sebacate; dihydric alcohol esters such as diethylene glycol dibenzoate; butyl acetyl ricinoleate and tributyl acetyl citrate Oxyacid esters and the like. These may be used alone or in combination of two or more. The added amount of the plasticizer is preferably 0.5 to 100 parts by weight based on 100 parts by weight of the organic polymer (A).

The synthetic resin aqueous dispersion is not particularly restricted but includes, for example, emulsions and latexes of vinyl acetate, vinyl acetate-ethylene copolymer, acrylic, urethane, vinyl, elastomer and the like. . These may be used alone or in combination of two or more. The addition amount of the synthetic resin aqueous dispersion is preferably 5 to 200 parts by weight (solid content) based on 100 parts by weight of the organic polymer (A).

The aqueous solution of the water-soluble resin or the aqueous solution of the alkali-soluble resin is not particularly limited. Examples thereof include polyvinyl alcohol, polyacrylic acid, sodium polyacrylate, polyvinylpyrrolidone, polyvinyl methyl ether, polyethylene glycol, and the like. Polypropylene glycol type, polyacryl ad type, polyethylene imine type, polymaleic acid type copolymer, isobutylene-maleic anhydride type copolymer, methylcellulose type, ethylcellulose type, carboxyethylcellulose type, hydroxyethylcellulose type, hydroxypropylcellulose type, Water-soluble alkyd resin, starch type, oxidized starch type, carboxyl starch type, dialdehyde starch type, dextrin type, cationic starch type, pullulan type, dextran type, a Biagomu systems include polyalginic sodium-based or the like. These may be used alone or in combination of two or more. The amount of the water-soluble or alkali-soluble resin water bath added may be the same as that of the organic polymer (A).
The amount is preferably 1 to 200 parts by weight (solid content) based on 100 parts by weight.

The aqueous dispersion of the tackifying resin is not particularly restricted but includes, for example, gum rosin, tall oil rosin, wood rosin, polymerized rosin, hydrogenated rosin, disproportionated rosin, rosin ester, hydrogenated rosin ester, disproportionation. Rosin-based resins such as rosin ester, rosin-modified phenolic resin, and maleic acid-modified rosin resin; terpene resins; phenolic resins; alkylphenol resins; terpene phenolic resins; xylene resins; ketone resins; aliphatic petroleum resins; Water dispersions such as alicyclic petroleum resins; coumarone resins; and styrene resins. These may be used alone or in combination of two or more. The amount of the aqueous dispersion of the tackifier resin is determined based on the amount of the organic polymer (A) 1
It is preferably from 5 to 150 parts by weight (solid content) based on 00 parts by weight.

The above-mentioned pigments are not particularly restricted but include, for example, mica-like iron oxide, lead white, lead red, graphite, silver vermilion, ultramarine, navy blue, cobalt oxide, titanium dioxide, titanium dioxide-coated mica, strontium chromate, titanium yellow ,
Inorganic pigments such as titanium black, zinc chromate, iron black, molybdenum red, molybdenum white, litharge, and liptone; azo pigments, dye lakes, anthraquinone-based, phthalocyanine-based organic dyes and the like; These may be used alone or in combination of two or more. The amount of the pigment to be added is preferably 0.1 to 200 parts by weight based on 100 parts by weight of the organic polymer (A).

The inorganic filler is not particularly restricted but includes, for example, oxides such as silica, alumina, titania, zirconia, zinc oxide, magnesium oxide and iron oxide;
Carbonates such as calcium carbonate, magnesium carbonate and zinc carbonate; silicates such as aluminum silicate, magnesium silicate, calcium silicate, kaolin, clay, talc, mica, zeolite and sericite; aluminum hydroxide, magnesium hydroxide Hydroxides and the like; sulfates and sulfites such as calcium sulfate, barium sulfate and calcium sulfite; nitrides such as boron nitride and silicon nitride; titanates such as potassium titanate and barium titanate; Dawsonite; carbon black; silicon carbide and the like. These may be used alone or in combination of two or more. The addition amount of the inorganic filler is preferably 1 to 200 parts by weight based on 100 parts by weight of the organic polymer (A).

The coupling agent is not particularly restricted but includes, for example, silane coupling agents and titanate coupling agents. The silane coupling agent is not particularly limited, and examples thereof include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and N- (Β-aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-
And mercaptopropyltrimethoxysilane.

The titanate coupling agent is not particularly restricted but includes, for example, isopropyl triisostearoyl titanate, isopropyl tri-n-dodecylbenzenesulfonyl titanate, tetraoctyl bis (dioctyl phosphite) titanate bis (dioctyl pyrophosphate) ethylene Titanate, isopropyl trioctanoyl titanate, isopropyl tri (N-
Aminoethyl-aminoethyl) titanate, isopropyl tri (dioctyl phosphate) titanate and the like. The amount of the coupling agent to be added is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the organic polymer (A).

The stabilizer is not particularly restricted but includes, for example, antioxidants, ultraviolet absorbers, ultraviolet stabilizers and the like. The antioxidant is not particularly limited, and examples thereof include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, and 2,6-di-t-butyl-4.
Monophenols such as ethylphenol; 2,2'-
Methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-
Butylphenol), 4,4'-butylidenebis (3-
Bisphenols such as methyl-6-t-butylphenol); 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4 6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis-
[Methylene-3- (3 ', 5'-di-t-butyl-4'
-Hydroxyphenyl) propionate] High molecular phenols such as methane; sulfuric such as dilauryl 3,3'-thiodipropionate and distearyl 3,3'-thiodipropionate; triphenylphosphite, diphenylisodecylphospho Phosphorus, such as phyto, phenyldiisodecyl phosphite, and tris (2,4-di-t-butylphenyl) phosphite.

The above-mentioned ultraviolet absorber is not particularly restricted but includes, for example, phenyl salicylate and pt-salicylic acid.
Salicylic acids such as butylphenyl; benzophenones such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone System, 2-
Benzotriazoles such as (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole; And cyanoacrylates such as ethylhexyl-2-cyano-3,3'-diphenylacrylate and ethyl-2-cyano-3,3'-diphenylacrylate.

The ultraviolet stabilizer is not particularly restricted but includes, for example, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,2, succinate)
Hindered amines such as 6,6-tetramethyl-4-piperidyl); 2,4-di-t-butylphenyl-3,5
And benzoate compounds such as -di-t-butyl-4-hydroxybenzoate. These stabilizers may be used alone or in combination of two or more. The amount of the stabilizer added is preferably 0.01 to 20 parts by weight based on 100 parts by weight of the organic polymer (A).

The emulsifier is not particularly restricted but includes, for example, anionic emulsifiers such as sodium lauryl sulfate, sodium dodecylbenzenesulfonate, ammonium lauryl sulfate and ammonium dodecylbenzenesulfonate; nonionic emulsifiers such as polyethylene glycol alkylphenyl ether; No. The amount of the emulsifier added is 0.01 to 2 parts by weight per 100 parts by weight of the organic polymer (A).
0 parts by weight is preferred.

The method for adding the above-mentioned modifier is not particularly limited. For example, a method in which the above-mentioned modifier is diluted or dispersed in a hydrophilic solvent or water and then added directly to the emulsion composition of the present invention; A method of mixing the modifier with the organic polymer (A) before being dispersed in water, and then dispersing the mixture in water; after mixing with a monomer or prepolymer that is a raw material of the organic polymer (A), A method of dispersing this mixture in water can be adopted.

The emulsion composition of the present invention comprises an adhesive,
It can be suitably used as an adhesive, a paint, a coating agent and the like. In this case, the viscosity of the emulsion composition of the present invention is 100,000 cP or less, and the solid concentration is preferably 20 to 75% by weight, but may be adjusted to an appropriate viscosity and concentration as needed. .

The method for applying the emulsion composition of the present invention is not particularly limited, and for example, a method using a spray, a roll coater, a flow coater, a brush or the like can be adopted. In addition, the emulsion composition of the present invention is used without or after forced drying after application, but is preferably force-dried from the viewpoint of productivity. In this case, the drying temperature is from 30 ° C to 150 ° C.
C. and drying time are preferably 20 minutes or less.

The emulsion composition of the present invention can be particularly suitably used as an adhesive. The adhesive comprising the emulsion composition of the present invention is used by applying it to at least one of the adherends to be adhered. The coating amount is a solid content per one surface of the adherend, and is 10 to 300
g / cm ² is preferred. Further, if necessary, when bonding the adherends to each other or after the bonding, the pressure-bonding may be performed using a roll press, a hydraulic press, a turnbuckle, or the like. In this case, the pressing temperature is from room temperature to 150
° C, crimping time is 20 minutes or less, crimping pressure is 0.01 ~
200 kg / cm ² is preferred.

The adherend on which the adhesive comprising the emulsion composition of the present invention can be used is not particularly limited, and examples thereof include metals, plastics, inorganic materials, wood, and paper. In particular, it exhibits excellent water resistance and water resistance. The adhesive obtained by using the adhesive comprising the emulsion composition of the present invention,
For example, it can be suitably used as a door, a partition, an outer wall material, a top plate of a desk, a packaging film or sheet for food and the like.

The present invention 2 is an emulsion composition comprising a polytannic acid (D) in place of the compound (B). The polytannic acid (D) is produced, for example, by the method disclosed in JP-A-61-4775. Specifically, a hydrolyzable tannic acid represented by the following formula (3), a monovalent or divalent or higher phenol other than tannic acid, and one kind of aldehyde or ketone are added in the presence of an acid catalyst. It can be obtained by condensation.

[0081]

Embedded image

In the present invention 2, the blending amount of the polytannic acid (D) is preferably 0.1 to 30 parts by weight based on 100 parts by weight of the organic polymer (A). If the amount is less than 0.1 part by weight, the effect of improving the water-resistant adhesive strength is small, and if it exceeds 30 parts by weight, the physical properties such as the strength of the obtained film are significantly reduced. More preferably, it is 0.5 to 20 parts by weight.

The method for adding the polytannic acid (D) is not particularly limited. For example, after the polytannic acid (D) is diluted with a hydrophilic solvent, the aqueous dispersion of the organic polymer (A) is directly added. A method of adding the above-mentioned polytannic acid (D), which has been hydrophilically modified by an appropriate method, to an aqueous dispersion of the organic polymer (A); Is mixed with the organic polymer (A) before dispersing in water, and then dispersing the mixture in water; the polytannic acid (D) and a monomer or a raw material of the organic polymer (A) or After mixing with the prepolymer, a method of dispersing this mixture in water can be employed.

The method for modifying the polytannic acid (D) hydrophilically is not particularly limited, and for example, a method of forming a complex with a water-soluble polymer such as a water-soluble acrylic resin can be employed. In the case of diluting the polytannic acid (D) with water by these methods, the amount of the water-soluble polymer must be controlled so as not to impair the water-resistant adhesiveness of the emulsion composition obtained.

The present invention 3 includes, in place of the compound (B), a group consisting of tannic acid, a compound having a mercapto group and a carboxyl group or a salt thereof, and a compound having at least two phosphate groups or a salt thereof. An emulsion composition containing at least one compound (E) selected from the group consisting of:

The above-mentioned tannic acid is mainly composed of a compound having a complex structure in which glucose represented by the above formula (3) and gallic acid, di-gallic acid, tri-gallic acid, etc. are bonded in a depsidic manner. And a mixture having, as accessory components, gallic acid, trigallic acid and the like.

The compound having a mercapto group and a carboxyl group or a salt thereof is not particularly limited, and examples thereof include thioglycolic acid, mercaptopropionic acid, mercaptobutyric acid, mercaptocyclohexanecarboxylic acid, mercaptophenylacetic acid, and mercaptobenzoic acid. Preferably, these compounds and their carboxylate salts are water-soluble. Among them, mercaptoacetic acid and mercaptopropionic acid are preferably used.

The compound having at least two phosphate groups or salts thereof is not particularly restricted but includes, for example, phytic acid, D-fructose-1,6-diphosphate, uridine-5'-diphosphate, uridine-5. '-Triphosphate, 5'-inosinic acid triphosphate and the like. Among them, phytic acid is preferably used.

As the above compound (E), alkali metal salts of these compounds such as sodium and potassium; and ammonium salts such as ammonia, trimethylamine and triethylamine can also be used. Of these, volatile ammonium salts such as ammonium and triethylamine can be removed by scattering when the emulsion composition of the present invention is dried and formed into a film, which lowers the water resistance of the obtained film. Since it is not allowed to be used, it is preferably used.

In the present invention 3, the compounding amount of the compound (E) is preferably 0.05 to 30 parts by weight based on 100 parts by weight of the organic polymer (A). If the amount is less than 0.05 part by weight, the effect of improving the water-resistant adhesive strength is small, and if it exceeds 30 parts by weight, the physical properties such as the strength of the obtained film are significantly reduced. More preferably, it is 0.1 to 20 parts by weight.

The method for adding the compound (E) is not particularly limited. For example, the compound (E) may be dissolved in a hydrophilic solvent or water, or may be directly dissolved without dissolving the compound (E). A method of adding the compound (E) to the organic polymer (A) before being dispersed in water, and then dispersing the mixture in water; After mixing with the monomer or prepolymer which is a raw material of the polymer (A), a method of dispersing the mixture in water can be adopted, and the above compound (E) is dissolved in a hydrophilic solvent or water because of easy operation. A method of dissolving and directly adding to the aqueous dispersion of the organic polymer (A) is preferably used. When the compound (E) is used by dissolving it in a hydrophilic solvent or water, the hydrogen ion concentration index (pH) of the solution is set to 6. by volatile amines such as ammonia, trimethylamine and triethylamine.
It is preferable to adjust to a range of 0 to 9.5.

In the emulsion composition of the present invention 1, the phenolic hydroxyl group of the compound (B) forms a strong chelate bond to a metal. Similarly, the present invention 2
In the above emulsion composition, the phenolic hydroxyl group of the polytannic acid (D) forms a strong chelate bond to a metal. In the emulsion composition of the present invention 3, when tannic acid is used among the compounds (E), the phenolic hydroxyl group of tannic acid forms a strong chelate bond to the metal, and the mercapto group and the carboxyl group or When a compound having a salt thereof is used, a mercapto group forms a strong chelate bond to a metal, and when a compound having at least two phosphate groups or salts thereof is used, a phosphate group or a salt thereof is used. Forms a strong chelate bond to the metal.

Further, in the emulsion composition of the present invention 1, a strong chemical bond is formed between the organic polymer (A) and the compound (C), and the compound (B) and the compound (B) are formed. A strong chemical bond is also formed with C). In the emulsion composition of the present invention 2, it is considered that the polytannic acid (D) and the compound (C) have some strong interaction, and the organic polymer (A)
A strong chemical bond is formed between the compound and the compound (C). In the emulsion composition of the third aspect of the invention, a strong chemical bond is formed between the organic polymer (A) and the compound (C), and when tannic acid is used as the compound (E), It is considered that a strong chemical bond is formed between gallic acid or the like, which is a sub-component in tannic acid, and the compound (C), and has a strong interaction with the main component of tannic acid. When a compound having a mercapto group and a carboxyl group or a salt thereof or a compound having at least two phosphate groups or a salt thereof is used as the compound (E), the compound and the compound (C) may be A strong chemical bond is formed.

Furthermore, in any of the emulsion compositions of the present invention 1, 2 and 3 of the present invention, the compound (C) blocks an acid group in the organic polymer (A) which does not participate in chelate formation. Therefore, surface corrosion of the metal adherend is less likely to occur. Therefore, even when a metal material is used as the adherend, excellent water-resistant adhesiveness can be exhibited.

[0095]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Examples 1 to 16 and Comparative Examples 1 to 14 In Examples and Comparative Examples, the following polymers and compounds were used. ( Polymer A-1) Preparation of Carboxyl Group-Containing Urethane Polymer Aqueous Dispersion Polycaprolactone polyol (Placcel L220A
L, OH number 57, number average molecular weight 2000, manufactured by Daicel Chemical Industries, Ltd.) 100 parts by weight, isophorone diisocyanate 3
0.8 parts by weight and 5.5 dimethylolpropionic acid
Parts by weight (molar ratio of isocyanate group / hydroxyl group = 1.5)
, A mixed solution obtained by adding 34.1 parts by weight of methyl ethyl ketone was stirred and subjected to boiling point polymerization until the content of isocyanate groups became 2.3% by weight or less. To this were added 4.2 parts by weight of triethylamine as a neutralizing agent and 56.8 parts by weight of methyl ethyl ketone for viscosity adjustment.

Next, 200 parts by weight of the above reaction mixture was vigorously stirred at room temperature, 300 parts by weight of water was added thereto, and immediately thereafter, 24.4 parts by weight of a 10% by weight aqueous solution of ethylenediamine was added. . Thereafter, the mixture was further stirred for 1 hour at room temperature, and then the pressure was reduced to remove the solvent.
By weight, an aqueous dispersion of a carboxyl group-containing urethane polymer was obtained. This was designated as polymer A-1.

( Polymer A-2) Preparation of Carboxyl Group-Containing Urethane Polymer Aqueous Dispersion Polypropylene glycol polyol (Nissan Uniol D-2000, OH value 58, number average molecular weight 200)
0, manufactured by NOF Corporation, 100 parts by weight, 31.2 parts by weight of isophorone diisocyanate, 5.6 parts by weight of dimethylolpropionic acid (molar ratio of isocyanate group / hydroxyl group = 1.5), and 34.2 parts by weight of methyl ethyl ketone The resulting mixed solution was stirred and subjected to boiling polymerization until the isocyanate group content became 2.3% by weight or less. To this were added 4.2 parts by weight of triethylamine as a neutralizing agent and 57.0 parts by weight of methyl ethyl ketone for adjusting the viscosity.

Next, 200 parts by weight of the above reaction mixture was vigorously stirred at room temperature, 300 parts by weight of water was added thereto, and immediately thereafter, 24.6 parts by weight of a 10% by weight aqueous solution of ethylenediamine was added. . Thereafter, the mixture was further stirred for 1 hour at room temperature, and then the pressure was reduced to remove the solvent.
By weight, an aqueous dispersion of a carboxyl group-containing urethane polymer was obtained. This was designated as polymer A-2.

( Polymer A-3) Preparation of Carboxyl Group-Containing Urethane Polymer Aqueous Dispersion Polypropylene glycol diol (Nissan Uniol D-2000, OH value 58, number average molecular weight 2000,
100 parts by weight, manufactured by NOF Corporation, 43.1 parts by weight of isophorone diisocyanate, and 6.1 parts by weight of dimethylolpropionic acid (DMPA, equivalent ratio of (isocyanate group / hydroxyl group) = 2.0), Trimet technical A product obtained by adding 37.3 parts by weight of methyl ethyl ketone to the mixture was stirred and subjected to boiling polymerization until the content of isocyanate groups became 4.3% by weight or less. Here, 4.6 parts by weight of triethylamine as a neutralizing agent, 62.1 parts by weight of methyl ethyl ketone for viscosity adjustment, and a novolak type alkylphenol resin having a softening point of 150 ° C. (CK)
90 parts by weight (solid content: 45 parts by weight) of M-2400, 50% by weight methyl ethyl ketone solution (manufactured by Showa Polymer Co., Ltd.) were added.

Next, 200 parts by weight of the above reaction mixture was vigorously stirred at room temperature, 350 parts by weight of water was added thereto, and immediately thereafter, 27.5 parts by weight of a 20% by weight aqueous ethylenediamine solution (solid content) 5.5 parts by weight).
Thereafter, the mixture was further stirred at room temperature for 1 hour, and then the solvent was removed under reduced pressure to obtain a carboxyl group-containing urethane polymer aqueous dispersion having a solid content concentration of 40% by weight. This was designated as polymer A-3.

( Polymer A-4) Preparation of Aqueous Dispersion of Acrylic Polymer Containing Sulfonic Acid Group 60 parts by weight of butyl acrylate, 17 parts by weight of styrene, 20 parts by weight of vinyl acetate, and 3 parts by weight of styrene sulfonic acid The mixture was dispersed in 30 parts by weight of water in which 2 parts by weight of ammonium lauryl sulfate and 1 part by weight of polyoxyethylene nonylphenyl ether (Neugen EA140, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) were dissolved as an emulsifier to prepare an emulsion monomer liquid. did. The emulsified monomer solution was heated to 70 ° C. while stirring in a separable flask, and added dropwise over 3 hours to 70 parts by weight of water in which 0.1 part by weight of ammonium persulfate was dissolved as an initiator. Heat to 80 ° C and add 3
Emulsion polymerization was carried out for hours, and after cooling, the pH was adjusted to 7 with aqueous ammonia.
To obtain a sulfonic acid group-containing acrylic polymer aqueous dispersion having a solid content of 50% by weight. This was designated as polymer A-4.

(Polymer A-5) An aqueous dispersion of a carboxyl group-containing acrylic polymer (Polytron U154, solid content concentration 60% by weight, manufactured by Asahi Kasei Corporation) was designated as Polymer A-5.

(Polymer A-6) An aqueous dispersion of carboxyl group-containing vinyl acetate-ethylene copolymer (Sumikaflex 910, solid content concentration 55% by weight, manufactured by Sumitomo Chemical Co., Ltd.) was used as polymer A-6. did.

( Polymer a-1) Preparation of aqueous dispersion of urethane polymer containing no acid group Polypropylene glycol polyol (Nissan Uniol D-2000, OH value 58, number average molecular weight 200)
0, manufactured by NOF Corporation), 100 parts by weight, 3.7 parts by weight of 1,4-butanediol, and 31.2 parts by weight of isophorone diisocyanate (molar ratio of isocyanate group / hydroxyl group =
A mixed solution obtained by adding 34.2 parts by weight of methyl ethyl ketone to 1.5) was stirred and subjected to boiling polymerization until the isocyanate group content became 2.3% by weight or less. To this was added 57.0 parts by weight of methyl ethyl ketone for adjusting the viscosity.

Next, while vigorously stirring 200 parts by weight of the above reaction mixture at room temperature, 380 parts by weight of a 1.3% by weight aqueous solution of a henonionic emulsifier (Newcol 210, manufactured by Nippon Emulsifier Co.) was added. Immediately thereafter, 23.0 parts by weight of a 10% by weight aqueous solution of ethylenediamine was added. Thereafter, the mixture was further stirred at room temperature for 1 hour, and then the pressure was reduced to remove the solvent, thereby obtaining an aqueous urethane polymer dispersion having a solid content of 35% by weight and containing no acid group. This was designated as polymer a-1.

( Polymer a-2) Preparation of Aqueous Acrylic Polymer Dispersion Containing No Acid Group A mixture of 60 parts by weight of butyl acrylate, 20 parts by weight of styrene and 20 parts by weight of vinyl acetate was treated with lauryl as an emulsifier. 2 parts by weight of ammonium sulfate and polyoxyethylene nonylphenyl ether (Neugen EA140,
1 part by weight of Daiichi Kogyo Seiyaku Co., Ltd.) was dispersed in 30 parts by weight of water to prepare an emulsion monomer liquid. This emulsified monomer liquid is stirred at 70 ° C. in a separable flask.
, And added dropwise over 3 hours to 70 parts by weight of water in which 0.1 part by weight of ammonium persulfate was dissolved as an initiator.
The emulsion polymerization was further carried out by heating to 80 ° C. for 3 hours, and after cooling, the pH was adjusted to 7 with aqueous ammonia to obtain an aqueous acrylic polymer-free dispersion having a solid content of 50% by weight. . This was designated as polymer a-2.

(Polymer a-3) Aqueous dispersion of vinyl acetate-ethylene copolymer containing no acid group (Sumikaflex 401, solid content concentration 55% by weight, manufactured by Sumitomo Chemical Co., Ltd.)
Was designated as a polymer a-3.

(Compound B-1) An aqueous solution of an acid group-containing polyphenol (25% aqueous solution of triethylamine salt of 3,4,5-trihydroxybenzoic acid) was used as Compound B-1.

(Compound b-1) An acid group-containing monophenol aqueous solution (25% aqueous solution of triethylamine salt of 4-hydroxybenzoic acid) was used as compound b-1.

(Compound C-1) An aqueous dispersion of an aziridine-based crosslinking agent (chemitite DZ-22E, solid content concentration 25% by weight, manufactured by Nippon Shokubai Co., Ltd.) was used as Compound C-1.

(Compound C-2) An aqueous dispersion of an epoxy crosslinking agent (50% by weight aqueous solution of Denacol EX-512, manufactured by Nagase Kasei Kogyo Co., Ltd.) was used as Compound C-2.

(Compound C-3) An aqueous dispersion of a carbodiimide-based crosslinking agent (Yukalink XL-25SE, solid content: 50% by weight, manufactured by Union Carbide) was prepared by adding Compound C-
It was set to 3.

(Compound C-4) An aqueous isocyanate-based crosslinking agent dispersion (SBU-isocyanate 0772, 25% by weight aqueous dispersion, manufactured by Sumitomo Bayer Urethane Co., Ltd.) was used as Compound C-4.

(Compound D-1) Polytannic acid resin solution (K polymer L8, solid content concentration 42% by weight, (mixed solution of isopropanol and N-butanol), manufactured by Teica)
Was designated as Compound D-1.

(Compound E-1) Tannic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in water and adjusted to pH 7.7 and a solid content of 20% by weight with the addition of 25% by weight aqueous ammonia. This was designated as compound E-1.

(Compound E-2) An aqueous solution of ammonium thioglycolate (pH 6.8, active ingredient 50% by weight, manufactured by Yodo Chemical Co., Ltd.) was used as Compound E-2.

(Compound E-3) Water and triethylamine were added to an aqueous solution of phytic acid (solid content: 50% by weight, manufactured by Wako Pure Chemical Industries, Ltd.) to give a pH of 7.1 and a solid content of 21% by weight.
Was adjusted. This was designated as compound E-3.

Emulsion compositions were prepared in the amounts shown in Tables 1, 2 and 3, and the normal adhesive strength and the water resistant adhesive strength of the obtained emulsion compositions were evaluated by the following methods. The results are shown in Tables 1, 2 and 3. In the tables, the amounts are expressed in parts by weight in terms of solid content. The tackifier resin is a phenol resin emulsion (B
KUA2370, solid content concentration 45% by weight, manufactured by Showa Union Gosei Co., Ltd.).

Evaluation Method (1) Normal Adhesion The obtained emulsion composition was applied to canvas and a cold-rolled steel plate (width 25 mm, length 125 mm, thickness 0.8 mm) using a brush. The amount of coating was 100 g / m ² for canvas, and for steel sheets,
The solid content was 40 g / m ² . After drying in an air drying oven at 80 ° C. for 4 minutes, a canvas and a steel plate were roll-pressed (pressure 60 kg / 25 mm) to prepare a test piece. The obtained test piece was cured for one week under the condition of 23 ° C., and then subjected to a 90 ° C. peel test at a pulling speed of 50 mm / min and 23 ° C.

(2) Water-Resistant Adhesive Strength A test piece prepared in the evaluation of normal-state adhesive strength was immersed in water at 50 ° C. for 24 hours to wipe off moisture, and then subjected to a pulling speed of 5%.
A 90 ° C peel test was performed at 0 mm / min and 23 ° C.

[0122]

[Table 1]

[0123]

[Table 2]

[0124]

[Table 3]

As is evident from Tables 1, 2 and 3, the emulsion compositions of the examples according to the present invention show little decrease in adhesiveness to normal adhesive strength even after immersion in warm water, and have excellent water-resistant adhesiveness. Is shown.

[0126]

EFFECT OF THE INVENTION Since the emulsion composition of the present invention has the above-described constitution, it has excellent water resistance and water resistance,
In particular, it has excellent water-resistant adhesion to a metal adherend. Therefore, it can be suitably used as an adhesive, a pressure-sensitive adhesive, a paint, a coating agent, and the like in a field where water resistance and water adhesion such as building materials are required.

Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location C08K 5/13 C08K 5/13 5/42 5/42 5/52 5/52 C08L 61/04 C08L 61/04 C09J 161/04 C09J 161/04 163/00 163/00 175/04 175/04 201/06 201/06 // C09D 5/02 C09D 5/02

Claims (4)

[Claims] 1. An aqueous dispersion of an organic polymer (A) having at least one acid group selected from the group consisting of a carboxyl group, a sulfonic acid group and a phosphoric acid group or a salt thereof, a carboxyl group and a sulfonic acid group A compound (B) having at least one acid group or a salt thereof selected from the group consisting of and a phosphoric acid group and at least two phenolic hydroxyl groups, and a compound having a reactivity with the acid group or a salt thereof An emulsion composition comprising a compound (C) having at least two functional groups having the formula: 2. An aqueous dispersion of the organic polymer (A) having at least one acid group selected from the group consisting of a carboxyl group, a sulfonic acid group and a phosphate group, or a salt thereof, and the acid group or a salt thereof. An emulsion composition comprising: a compound (C) having at least two functional groups reactive with a compound (C); and polytannic acid (D). 3. An aqueous dispersion of the organic polymer (A) having at least one acid group selected from the group consisting of a carboxyl group, a sulfonic acid group and a phosphate group, or a salt thereof, and the acid group or a salt thereof. A compound (C) having at least two functional groups reactive with tannic acid,
An emulsion composition comprising at least one compound (E) selected from the group consisting of a compound having a mercapto group and a carboxyl group or a salt thereof and a compound having at least two phosphate groups or a salt thereof. Stuff. 4. An adhesive comprising the emulsion composition according to claim 1, 2 or 3.