JP2000080242A - Hardenable emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin-containing hardenable emulsion having an improved pot life in summer, especially a hardenable emulsion also having an excellent balance with various physical properties such as adhesion strength, a heat-resistant creep property and water resistance. SOLUTION: This hardenable emulsion is a multilayer-structured emulsion having a core part and a shell part in which the core part is obtained by emulsion polymerizing a polymerizable monomer mixture having >=80 deg.C Tg of a polymer and <1 g solubility in water at 25 deg.C with an epoxy resin and the shell part is obtained by emulsion polymerizing a polymerizable monomer having >=80 deg.C Tg of a polymer and >=1 g solubility in water at 25 deg.C with more than one kind of a polymerizable monomer mixture selected from a polymerizable monomer having <80 deg.C Tg of a polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a paint, a printing ink, a gas barrier packaging material,
The present invention relates to a curable emulsion containing an epoxy resin, which is suitable for processed paper, fiber processing agents, building materials, and the like.

[0002]

2. Description of the Related Art In recent years, the development of materials that are resource-saving and environmentally friendly has been promoted. In particular, in the field of paints and adhesives using a solvent, there is an active movement to remove the solvent due to VOC regulations due to the discharge of the solvent. Among the materials listed as alternatives to solvent-based materials, aqueous development is being developed. A typical example of the aqueous solution is an emulsion, for example, a thermoplastic acrylic emulsion,
Examples include vinyl acetate emulsion and ethylene vinyl acetate emulsion. However, in applications where high adhesive strength, heat resistance, water resistance, and solvent resistance are required, solvent-based systems must still be used.

On the other hand, attempts have been made to solve the above-mentioned problems by using a thermosetting epoxy resin instead of a conventional thermoplastic emulsion in an aqueous form, or by combining it with a thermoplastic emulsion. . However, an aqueous emulsion containing an epoxy resin is not usually used alone, and its performance is exhibited only when a curing agent is added and cured. In that case, the pot life after mixing the main agent and the curing agent becomes a problem.
Here, the pot life indicates a time during which the initial physical properties immediately after mixing the main agent and the curing agent are maintained,
This is not a problem for thermoplastic emulsions.

A curing agent for curing an epoxy resin at room temperature is as follows:
Many have a pot life of less than an hour. In this case, the problem of the pot life is avoided by limiting the amount of work and the amount of work so that the work is completed within one hour. Conventionally, when a curing agent having a long pot life is selected and used, it is difficult to cure at room temperature, and there is a problem that it is necessary to cure by heating in practice. Therefore, there is a strong demand for a compounding system that maintains the room-temperature curability and extends the pot life.

On the other hand, for example, Japanese Patent Laid-Open No. Sho 59-621
In Japanese Patent Publication No. 4 (JP-A-4), the pot life in a cement mortar system is extended by completely neutralizing a diamine as a curing agent with oxalic acid. In JP-A-6-330011 and JP-A-7-126595, a core-shell emulsified epoxy resin is formed using a specific acrylic polymer.
The pot life is being extended.

[0006] These improvements have solved the problem of the conventional pot life to some extent, but it is said that the balance between the curability at room temperature and the pot life under conditions assumed in summer is insufficient. There was a problem.

[0007]

SUMMARY OF THE INVENTION In view of the above-mentioned problems of the prior art, an object of the present invention is to propose a curable emulsion containing an epoxy resin having an improved pot life. It is an object of the present invention to provide a curable emulsion having an improved pot life under the conditions described above, and further having a good balance with other physical properties such as adhesive strength, heat creep resistance, and water resistance.

[0008]

Means for Solving the Problems The present inventors have conducted various studies to solve the above-mentioned problems, and as a result, have found that the core part is a copolymer containing an epoxy resin and a specific monomer as essential components, and the shell part is a specific radical. It has been found that a multilayer emulsion comprising a copolymer of a polymerizable monomer solves the above problems.

That is, the present invention is a multilayer emulsion having a core portion and a shell portion, wherein the core portion has a glass transition temperature of a polymer of 80 ° C. or more and a solubility in water at 25 ° C. of less than 1 g. Obtained by emulsion polymerization of a radical polymerizable monomer mixture containing the radical polymerizable monomer (A) and an epoxy resin, wherein the shell portion has a glass transition temperature of 80 ° C. or higher and 25 ° C.
The glass transition temperature of the radical polymerizable monomer (B-1) having a solubility in water of 1 g or more and the polymer is 80
It is a curable multilayer emulsion obtained by emulsion-polymerizing a mixture of one or more radical polymerizable monomers selected from the radical polymerizable monomers (B-2) at a temperature lower than 0 ° C.

Hereinafter, the present invention will be described in detail. The curable emulsion of the present invention has a multilayer structure composed of a core and a shell. With such a structure, it is possible to improve the pot life and balance with other physical properties. Note that another layer may be provided between the core portion and the shell portion as long as the effects of the present invention are not impaired.

In the polymerization of the core portion of the curable emulsion of the present invention, when the glass transition temperature of the polymer is 80 ° C. or more,
A radically polymerizable monomer (A) having a solubility in water at 5 ° C. of less than 1 g is used. By using the radically polymerizable monomer (A) for the core, the polymer becomes more hydrophobic and a multilayer emulsion can be easily formed. Also, the familiarity with the epoxy resin of the core part is improved. Examples of such a radically polymerizable monomer (A) include, for example, aromatic unsaturated compounds, for example, styrene, α-
Methylstyrene, vinyltoluene and the like can be mentioned. Preferably it is styrene.

The radical polymerizable monomer mixture used in the polymerization of the core may contain a radical polymerizable monomer other than the radical polymerizable monomer (A) in order to control the performance of the core. Such radically polymerizable monomers include α, β-unsaturated monocarboxylic acid alkyl esters, carboxyl group-containing monomers, hydroxyl group-containing monomers, amide group-containing monomers, methylol group-containing monomers, alkoxymethyl group-containing monomers, epoxy group-containing monomers , Polyfunctional monomers, mono- or diesters of α, β-ethylenically unsaturated dicarboxylic acids, vinyl esters, nitrile group-containing monomers, olefins, and chlorine-containing vinyl monomers.

Examples of the alkyl esters of α, β-unsaturated monocarboxylic acids include alkyl esters of acrylic acid or methacrylic acid. Examples of the alkyl ester of acrylic acid or methacrylic acid include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate,
Isobutyl acrylate, hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, methyl methacrylate,
Examples include ethyl methacrylate, propyl methacrylate, isopropyl acrylate, butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, and the like.

Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, maleic acid, fumaric acid,
Examples include itaconic acid and monoalkyl itaconate. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and polyethylene glycol acrylate. Examples of the amide group-containing monomer include acrylamide, methacrylamide, and N, N-. Methylene bisacrylamide, diacetone acrylamide, maleic amide, maleimide and the like, and examples of the methylol group-containing monomer include N-methylol acrylamide, N-methylol methacrylamide, dimethylol acrylamide, dimethylol methacrylamide, and the like. Examples of the methyl group-containing monomer include N-methoxymethyl acrylamide and N-methoxymethyl methacryl. For example, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, methyl glycidyl acrylate, methyl glycidyl methacrylate, etc. may be mentioned as the epoxy group-containing monomer. Examples of the reactive monomer include divinylbenzene, polyoxyethylene diacrylate, polyoxyethylene dimethacrylate, polyoxypropylene diacrylate, polyoxypropylene dimethacrylate, butanediol diacrylate, butanediol dimethacrylate, trimethylolpropane triacrylate, and trimethylol. Propane trimethacrylate, pentaerythritol tetraacrylate, pentaerythri Mono- or diesters of α, β-ethylenically unsaturated dicarboxylic acids include, for example, mono- or dibutyl maleate, mono- or dioctyl fumarate, and vinyl esters include, for example, vinyl acetate, Vinyl propionate, vinyl benzoate, and the like, and the nitrile group-containing monomer include, for example, acrylonitrile, methacrylonitrile, and the like.Olefins include, for example, butadiene and isoprene.The chlorine-containing vinyl monomer includes, for example, vinyl chloride. , Vinylidene chloride, chloroprene and the like.

The radical polymerizable monomers other than the radical polymerizable monomer (A) as described above may be used alone or as a mixture of two or more. Preferably, a combination of an alkyl ester of α, β-unsaturated monocarboxylic acid and a carboxyl group-containing monomer is preferred.
More preferably, examples of the alkyl ester of an α, β-unsaturated monocarboxylic acid include ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. As the carboxyl group-containing monomer, acrylic acid,
Methacrylic acid is exemplified.

In the radical polymerizable monomer mixture used in the polymerization of the core portion, a preferable composition ratio when the radical polymerizable monomer (A), the α, β-unsaturated monocarboxylic acid alkyl ester, and the carboxyl group-containing monomer are used Means that the radical polymerizable monomer (A) is 10% based on the radical polymerizable monomer mixture in the core portion.
８０80 wt%, α-β-unsaturated monocarboxylic acid alkyl ester is 20-95 wt%, and carboxyl group-containing monomer is 0.1-20 wt%.

The Tg of the polymer in the core may be set according to the purpose. Here, Tg means a value calculated from all radically polymerizable monomers in the core portion excluding the epoxy resin. Preferably, the temperature is from -50C to 80C. At -50 ° C or higher, there is no problem with the heat resistance of the cured product.
If it does not exceed, there is no problem in the film formability. More preferably-
40 ° C to 50 ° C.

The epoxy resin used in the core of the curable emulsion of the present invention includes, for example, glycidyl ethers, glycidyl esters, glycidylamines, linear aliphatic epoxides, alicyclic epoxides and the like. Glycidyl ethers include aromatic glycidyl ether and aliphatic glycidyl ether.

Examples of the aromatic glycidyl ether include diglycidyl ether of bisphenol, polyglycidyl ether of phenol novolak, and diglycidyl ether of biphenol. Examples of the diglycidyl ether of bisphenol include diglycidyl ethers such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, and tetrabromobisphenol A. Examples of the polyglycidyl ether of phenol novolak include: Examples thereof include polyglycidyl ethers such as phenol novolak, cresol novolak, and brominated phenol novolak. Examples of the diglycidyl ether of biphenol include diglycidyl ether of biphenol and tetramethylbiphenol.

Examples of the aliphatic glycidyl ether include glycidyl ethers such as polyethylene glycol, polypropylene glycol, glycerin and tetramethylene glycol. As glycidyl esters,
Aromatic glycidyl esters, alicyclic glycidyl esters and the like can be mentioned. Examples of the aromatic glycidyl ester include phthalic acid and terephthalic acid. Examples include diglycidyl esters such as isophthalic acid, and examples of alicyclic glycidyl esters include glycidyl esters such as hexahydrophthalic acid, tetrahydrophthalic acid, and dimer acid.

The glycidylamines include, for example, tetraglycidyldiaminodiphenylmethane, tetraglycidyl meta-xylylenediamine, triglycidylaminophenol and the like. Examples of linear aliphatic epoxides include epoxidized polybutadiene and epoxidized soybean oil, and examples of alicyclic epoxides include 3,4 epoxy-6-methylcyclohexylmethyl carboxylate and 3,4 epoxycyclohexylmethyl carboxylate. Rates and the like.

The epoxy resin may be obtained by partially reacting the terminals of the epoxy resin with a monobasic acid such as acrylic acid or methacrylic acid. Epoxy resins may be used alone or in combination of two or more. Preferred epoxy resins are glycidyl ethers from the viewpoint of heat resistance and water resistance,
More preferred are diglycidyl ethers of bisphenol, and particularly preferred are diglycidyl ethers of biphenol A and biphenol F. The epoxy equivalent of the epoxy resin may be in the range of 100 to 10000, and is preferably 150 to 3000, more preferably 170 to 1000, from the viewpoint of room temperature curability, heat resistance and water resistance.

In the curable emulsion of the present invention, the composition ratio of the epoxy resin and the radical polymerizable monomer mixture used in the core portion is such that the radical polymerizable monomer mixture is 40 to 95% by weight based on 5 to 60% by weight of the epoxy resin. %. When the epoxy resin content is 5% by weight or more, there is no problem in heat resistance and water resistance, and when it does not exceed 60% by weight, there is no problem in initial adhesion. More preferably, the radical polymerizable monomer is 45 to 90% by weight based on 10 to 55% by weight of the epoxy resin.

The core of the curable emulsion of the present invention comprises:
For example, it can be obtained as follows. For example, an epoxy resin and a radical polymerizable monomer mixture containing a radical polymerizable monomer (A) as essential components are uniformly dissolved in advance by sufficiently stirring at room temperature or under heating, and a surfactant and a dispersant are added thereto. Then, a protective colloid, a water-soluble polymer, etc., water and a radical polymerization initiator are added to form an emulsified dispersion, followed by polymerization.

In addition to this method, for example, a method in which an epoxy resin and a radical polymerizable monomer mixture are separately emulsified and dispersed and subjected to polymerization, a method in which only the epoxy resin is emulsified and dispersed and the radical polymerizable monomer is directly polymerized, and the like can be mentioned. The polymerization initiator can be added together with the emulsified dispersion or separately. The curable emulsion of the present invention has a shell portion.

The radical polymerizable monomer that can be used in the polymerization of the shell portion includes a polymer having a glass transition temperature of 80.
A radical polymerizable monomer (B-1) having a solubility in water of 1 g or more at 25 ° C. or higher at 25 ° C. or higher, and a radical polymerizable monomer (B-2) having a glass transition temperature of less than 80 ° C.
At least one or more radically polymerizable monomers selected from A radical polymerizable monomer (B-
By using 1) and (B-2), the polymer becomes more hydrophilic, and the multilayer emulsion of the present invention can be easily formed. In addition, the compatibility with the epoxy resin becomes poor, and the epoxy resin hardly migrates to the shell portion.

In the polymerization of the shell part, it is preferable not to use a radical polymerizable monomer other than the radical polymerizable monomer (B-1) and the radical polymerizable monomer (B-2). Examples of the radically polymerizable monomer (B-1) include alkyl esters of α, β-unsaturated monocarboxylic acids,
Examples include amide group-containing monomers, nitrile group-containing monomers, carboxyl group-containing monomers, and the like.

Specifically, examples of the alkyl ester of an α, β-unsaturated monocarboxylic acid include methyl methacrylate and the like, examples of the amide group-containing monomer include acrylamide, and examples of the nitrile group-containing monomer include Acrylonitrile and the like can be mentioned, and examples of the carboxyl group-containing monomer include acrylic acid and methacrylic acid.

Preferred are methyl methacrylate, acrylamide and methacrylic acid. Examples of the radical polymerizable monomer (B-2) include alkyl esters of α, β-unsaturated monocarboxylic acids, monomers containing hydroxyl groups, monomers containing epoxy groups, mono- or diesters of α, β-ethylenically unsaturated dicarboxylic acids, Examples include vinyl esters, olefins, and chlorine-containing vinyl monomers.

Specifically, the above-mentioned example is used. Preferred are ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate. In the radical polymerizable monomer (B-1) used in the polymerization of the shell portion, for example, preferred examples include the case where an α, β-unsaturated monocarboxylic acid alkyl ester, a carboxyl group-containing monomer, and an amide group-containing monomer are used. The composition ratio is such that the alkyl ester of α, β-unsaturated monocarboxylic acid is 5 to 80% by weight,
The carboxyl group-containing monomer is 0.1 to 20% by weight, and the amide group-containing monomer is 0.1 to 10% by weight.

The radical polymerizable monomer (B-2)
For example, when the α, β-unsaturated monocarboxylic acid alkyl ester is used, the content is 10 to 95% by weight. The compositions (B-1) and (B-2) are based on the radical polymerizable monomer mixture used in the polymerization of the shell portion. The Tg of the polymer in the shell may be set according to the purpose. Here, Tg means a calculated value from all radically polymerizable monomers used in the polymerization of the shell portion. Preferably, the temperature is from -50C to 80C. -5
At 0 ° C. or higher, there is no problem in heat resistance of the cured product, and at 80 ° C. or lower, there is no problem in film formability. More preferably from -40 ° C to 50
° C.

The weight ratio of the core part to the shell part is 50 to
The shell part is 50 to 5 parts by weight with respect to 95 parts by weight. When the core is 50 parts by weight or more, there is no problem in heat resistance, and when the core is 95 parts by weight or less, there is no problem in pot life. The curable emulsion of the present invention is obtained, for example, as follows. First,
The radical polymerizable monomer mixture / epoxy resin in the core portion is emulsion-polymerized, and then the radical polymerizable monomer mixture in the shell portion is emulsion-polymerized.

Further, as a polymerization method, a phase inversion method in which the shell portion is polymerized at first and then the core portion is polymerized may be used. Emulsion polymerization of the core portion and the shell portion may be carried out in the presence of a radically polymerizable monomer, a radical polymerization initiator, water and a surfactant according to a standard method. Surfactants that can be used in emulsion polymerization include ionic and nonionic surfactants, and ionic surfactants include anionic and
Cationic and amphoteric.

Examples of the anionic surfactant include a fatty acid, a sulfate of a higher alcohol, a sulfate of a liquid fatty oil, a sulfate of an aliphatic amine and an aliphatic amide, a phosphate of an aliphatic alcohol, and a dibasic acid. Sulfonates of fatty acid esters, sulfonates of aliphatic amides, alkylallyl sulfonates, formalin condensed naphthalene sulfonates, and the like. Examples of the cationic surfactant include primary amine salts and secondary amine salts. , Tertiary amine salts, quaternary ammonium salts, pyridinium salts and the like, and examples of the amphoteric surfactants include carboxylate type, sulfate type, sulfonate type and phosphate ester salt.

Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ester, sorbitan alkyl ester, and polyoxyethylene sorbitan alkyl ester.
In addition to the non-reactive surfactants mentioned above, reactive surfactants can also be used. The reactive surfactant has a radically polymerizable functional group in one molecule and a sulfonic acid group, a sulfonic acid ester group, a sulfonic acid group, one having one or more functional groups selected from sulfonic acid ester groups, Alternatively, it has a radical polymerizable functional group in one molecule and has a polyoxyethylene, polyoxypropylene, polyoxyethylene polyoxypropylene composite type alkyl ether or alcohol. These surfactants may be used alone or in combination of two or more.

Examples of the dispersant, protective colloid, and water-soluble polymer include polyphosphate, polyacrylate, styrene-maleic acid copolymer salt, styrene-acrylic acid copolymer salt, and styrene-methacrylic acid copolymer. Salt, water-soluble acrylate copolymer salt, water-soluble methacrylate copolymer salt, polyvinyl alcohol, polyacrylamide, polymethacrylamide, polyacrylamide copolymer, polymethacrylamide copolymer and the like.

As the polymerization initiator, a water-soluble or oil-soluble polymerization initiator can be used. Examples of the water-soluble polymerization initiator include persulfate, peroxide, a water-soluble azobis compound, a redox system of a peroxide-reducing agent, and the like.As the persulfate, for example, ammonium persulfate, potassium persulfate,
Examples of peroxides include hydrogen peroxide, t-butyl hydroperoxide, t-butyl peroxide and the like.
-Butylperoxymaleic acid, succinic peroxide, and water-soluble azobis compounds such as 2,2
2'-azobis (N-hydroxyethylisobutylamide), 2,2'-azobis (2-amidinopropane) 2
Hydrogen chloride, 4,4′-azobis (4-cyanopentanoic acid) and the like can be mentioned. As the redox system of the peroxide-reducing agent, for example, the above-mentioned peroxide can be added to sodium hydrogen sulfite, sodium thiosulfate, hydroxymethanesulfine Addition of reducing agents such as sodium acid, L-ascorbic acid, and salts thereof, cuprous salts, and ferrous salts. Examples of the oil-soluble polymerization initiator include peroxides and oil-soluble azobis compounds, and examples of the peroxide include dibutyl peroxide, benzoyl peroxide, lauroyl peroxide, and cumene hydroperoxide. Examples of oil-soluble azobis compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile,
2,2′-azobis-2,4-dimethylvaleronitrile and the like.

In the polymerization of the curable emulsion of the present invention, if necessary, a pH adjuster such as sodium hydrogen phosphate or sodium hydrogen carbonate, t-dodecyl mercaptan, n
-A molecular weight modifier such as dodecyl mercaptan or a low molecular weight halogen compound, a chelating agent, a plasticizer, an organic solvent and the like can be added at any time before, during or after emulsion polymerization. The polymerization can be carried out at a temperature of 0 to 100 ° C, particularly preferably 30 to 90 ° C. The polymerization is carried out in an inert atmosphere under normal pressure or, if necessary, under pressure.

The curable emulsion of the present invention may further contain other latexes, for example, acrylic latex, styrene butadiene latex, chloroprene latex, urethane latex, ethylene vinyl acetate latex, vinyl acetate latex, etc., as required for improving the performance. It may be added, and a tackifier or rubber component may be further added.Also, in order to further improve the curing performance, melamine resin, urea resin, amino resin such as benzoguanamine resin and resol type or novolak type phenol resin May be added. Further, a bactericide, a preservative, an antifoaming agent, a plasticizer, a flow regulator, a thickener, a pH regulator, a surfactant, a coloring pigment, an extender pigment, an antirust pigment, and the like may be added. Further, in order to balance pot life and room temperature curability, an inorganic acid, a low molecular organic acid, a carboxylic acid polymer, or the like may be added.

Examples of the pigment include barium hydroxide,
Magnesium hydroxide, aluminum hydroxide, silicon oxide, titanium oxide, calcium sulfate, barium sulfate, calcium carbonate, basic zinc carbonate, basic lead carbonate, silica sand, clay, talc, silica compounds, titanium dioxide, antimony trioxide, etc. No. Examples of tackifiers include rosin-based, rosin derivative-based, terpene resin-based, and natural tackifiers such as terpene derivative-based, petroleum resin-based, styrene resin-based, coumarone indene resin-based, phenolic resin-based, and xylene resin-based And a synthetic resin-based tackifier. These tackifiers are preferably added in the form of an aqueous dispersion or an aqueous solution. Examples of the rubber component include liquid nitrile rubber and silicone rubber.

Examples of the inorganic acid and the low molecular weight organic acid include the following. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid and the like. As the low molecular weight organic acid, refers to a compound having a molecular weight of less than 1000 having one or more carboxyl groups in one molecule, for example, monobasic acid formic acid, acetic acid, propionic acid, butyric acid, etc., polybasic acid oxalic acid, malon Acid, succinic acid, glutaric acid, adipic acid,
Examples include the aromatic carboxylic acids such as benzoic acid, terephthalic acid, isophthalic acid and phthalic acid, such as citric acid, and the unsaturated carboxylic acids mentioned above.

The carboxylic acid polymer refers to, for example, a polymer having a carboxyl group, and can be obtained, for example, by polymerizing an unsaturated carboxylic acid having a carboxyl group. Examples of unsaturated carboxylic acids include, for example, monobasic acids and polybasic acids; examples of monobasic acids include acrylic acid and methacrylic acid; examples of polybasic acids include maleic acid, fumaric acid, and itacone Acids.
When polymerizing the unsaturated carboxylic acid, a radical polymerizable monomer may be combined as needed. As the radical polymerizable monomer, for example, an aromatic unsaturated compound,
α, β unsaturated carboxylic acid alkyl esters, vinyl esters, unsaturated nitriles, olefins and the like.

The curable emulsion of the present invention uses a curing agent for an epoxy resin in order to obtain a cured crosslinked product when used. Examples of the curing agent include linear aliphatic polyamines, polyamides, alicyclic polyamines, aromatic polyamines, tertiary amines, aminophenol compounds, and the like, and modified products thereof. Examples of the linear aliphatic polyamine include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, and modified products thereof.

Examples of the polyamide include a condensate of a dicarboxylic acid such as dimer acid and the above-mentioned linear aliphatic polyamine. Examples of the alicyclic polyamine include mensendiamine, isophoronediamine, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) 2,
Examples thereof include 4,8,10-tetraoxaspiro (5,5) undecane adduct, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclohexyl) methane, and modified products thereof.

Examples of the aromatic polyamine include m-xylylenediamine, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, and modified products thereof. Other polyamines include dicyandiamide, adipic dihydrazide and the like.

Examples of the tertiary amine include tertiary amino group-containing compounds such as dimethylbenzylamine and the like, modified products thereof, imidazole, 2-methylimidazole,
Examples thereof include imidazole compounds such as ethyl-4-methylimidazole and 2-phenylimidazole, and modified products thereof. An aminophenol compound refers to a phenol compound having an amino group.
And phenolic OH groups. For example, 2-aminophenol, 4
-Aminophenol, 4-dimethylaminophenol,
2,4,6-trisdimethylaminomethylphenol,
Dimethylaminomethylphenol and the like.

Preferred are linear aliphatic polyamines, polyamides, alicyclic polyamines, tertiary amines and aminophenol compounds, and more preferred are alicyclic polyamines, tertiary amines and aminophenol compounds. The alicyclic polyamines include isophorone diamine and modified products thereof, the tertiary amines include 2-methylimidazole and modified products thereof, and the aminophenol compounds include 2,4,6-trisdimethylaminomethylphenol. Can be

These curing agents may be used alone or in combination of two or more. Other curing agents for epoxy resins that may be used include acid anhydrides, polymercaptan, and the like. Examples of the acid anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, Examples thereof include hydrophthalic acid, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and modified products thereof. Examples of the polymercaptan include condensates of thioglycolic acid and a polyhydric alcohol and polysulfides.

The amount of the curing agent for the epoxy resin is determined according to the curability and the physical properties of the curing agent. The curing agent is added to 100 parts by weight (solid content) of the curable emulsion of the present invention.
It is 1 to 100 parts by weight. When the amount is 0.1 part by weight or more, the heat resistance and water resistance are good, and when it does not exceed 100 parts by weight, the initial adhesiveness becomes good. Preferably, the compounding amount of the curing agent is 0.5 to 50 parts by weight.

As a method of using the curable emulsion of the present invention, for example, a curable emulsion and a curing agent are mixed,
Thereafter, a method of applying to one adherend and laminating, or a method of applying a composition obtained by mixing a curable emulsion and a curing agent on both sides of lamination and laminating the same is exemplified. Separately, a method of applying a part of the components, for example, only the curable emulsion to one adherend, further applying a curing agent, for example, and then laminating and bonding the other adherend, followed by curing. Alternatively, a method may be used in which a curable emulsion and a curing agent are simultaneously applied to one adherend, and then the other adherend is overlaid and bonded, followed by curing. Further, a method in which a curable emulsion is applied to one adherend, a curing agent is applied to the other adherend, and then laminated and bonded, followed by curing may be used.

The method of applying the adhesive is arbitrary and not limited. For example, spray coating, roll coater coating, curtain flow coating, comb ironing, brush coating and the like can be mentioned. At the time of applying the adhesive, the adherend may or may not be heated. The time until application after application is arbitrary, for example, at 20 to 180 ° C. for 1 second to 60 minutes. The volatilization of water may not be complete.

After bonding, heating may or may not be performed. When heating, the temperature is 30 to 180 ° C., and the heating time may be selected from 1 second to 24 hours. After bonding, curing may be performed at room temperature or by heating. Curing can be performed at 10 to 180 ° C. for 1 minute to 2 weeks. The curable emulsion of the present invention is an adhesive,
It can be used not only for adhesives but also for paints, printing inks, gas barrier packaging materials, processed paper, textile processing agents, building materials, and the like. As the adhesive, for example, wood, plywood, particle board, gypsum board, iron, metals such as aluminum,
Plastic film, plastic foam, non-woven fabric of plastic, leather, cotton, linen cloth, glass fiber,
Adhesion of glass cloth, FRP, and the like can be given. The adhesive field includes, for example, tapes, labels, wallpapers, flooring materials, and the like, and the coating field includes, for example, concrete, wood, metal, floor polish, and the like, and the fiber processing agents include, for example, nonwoven fabrics, carpets, and electric flocking cloths. , A laminated cloth, a tire cord, and the like, and examples of the building material include a sealing material, latex cement, a waterproofing material, and the like.

[0053]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described with reference to embodiments. Parts are by weight unless otherwise specified. The physical properties of the composition were evaluated as follows. (1) Evaluation of pot life Each formulation comprising the curable emulsion of the present invention and the curing agents described in Table 3 was prepared, and immediately thereafter, and at 35 ° C for 2 hours.
After 4 hours, the viscosity is measured, and the rate of change of the measured value is determined. The viscosity was measured at 25 ° C. using a B-type viscometer. A change rate of 100% or less is determined to be acceptable.

Immediately after the preparation of the composition, and after leaving it at 35 ° C. for 24 hours, the adhesive strength and heat creep described below are evaluated. (2) Adhesive strength After adjusting the viscosity of the composition to 100 Ps with a thickener (ADEKANOL UH420, manufactured by Asahi Denka Co., Ltd.), it was applied to a 1-inch wide No. 9 canvas using a wire bar # 75. Dry at 20 ° C. for 20 minutes. Thereafter, the surfaces on which the composition has been dried are adhered, and a 4.5 kg roller is reciprocated once.

Using a sample which had been pasted for 1 hour at 20 ° C. after lamination and a sample which had been cured for 7 days at 20 ° C. after lamination, the 180 ° peel strength was measured with a Tensilon tensile tester. 1 hour after the sample
A pass of 0 kg / inch or more was judged to be acceptable (initial adhesive strength). 4.0 kg / inch for a sample cured for 7 days
The above is judged to be acceptable (curing adhesive strength). In Table 4, the case where the bonding was strong and the portion other than the bonding surface was broken was indicated as "material breakage".

The pulling speed was 50 mm / min. (3) Heat creep resistance The samples prepared for the evaluation of the adhesive strength were bonded and then cured at 20 ° C. for 7 days.
° One side of the canvas was fixed in the same manner as the peel strength measurement, and a weight of 300 g was applied to the other canvas to apply a force in the direction of gravity.

After standing for 24 hours, if the weight did not drop, it was judged as pass, and if it dropped, it was judged as reject. In the heat creep test, a test piece having an adhesion length of 10 cm was used. (4) Water resistance After the samples prepared in the evaluation of the adhesive strength were bonded and cured at 20 ° C. for 7 days, and then immersed in distilled water for 1 day, the peel strength was immediately measured with a Tensilon tensile tester. . 3.0 kg / inch or more is judged to be acceptable.
The pulling speed was 50 mm / min.

[Production Examples 1 to 9] Polyoxyethylene nonylphenyl ether (trade name: Emulgen) was added to a mixture of a radical polymerizable monomer and an epoxy resin for the core layer (denoted as C in the table) shown in Production Example 1 in Table 1. 950, Kao Corporation
64 parts of a 25% aqueous solution of sodium polyoxyethylene nonylphenyl ether sulfate (trade name: Revenol WZ, manufactured by Kao Corporation), 1.6 parts of ammonium persulfate, and 344 parts of distilled water. The mixture was stirred with a homomixer to prepare a pre-emulsion 1.

Separately, add 400 distilled water to a flask equipped with a stirrer.
Parts, 20 parts of a 25% aqueous solution of Emulgen 950,
The temperature is raised to 80 ° C., and a solution prepared by dissolving 1 part of ammonium persulfate in 50 parts of water is added. To this, the pre-emulsion 1 is continuously dropped over 3 hours. After curing, cure for 30 minutes.
Next, the shell layer shown in Production Example 1 of Table 1 (described as S in the table)
Polyoxyethylene nonyl phenyl ether (trade name: Emulgen 95)
0, 16 parts of 25% aqueous solution of Kao Corporation; 25% aqueous solution of sodium polyoxyethylene nonylphenyl ether sulfate (trade name: Revenol WZ, manufactured by Kao Corporation) 8
, 0.4 parts of ammonium persulfate and 56 parts of distilled water were added, and the mixture was stirred with a homomixer to prepare a pre-emulsion 2.

The pre-emulsion 2 is dropped continuously over 1 hour, following the curing after the drop of the pre-emulsion 1. After dripping 3
After curing for 0 minutes, add 0.5 parts of ammonium persulfate to 5 parts of water.
A solution dissolved in 0 parts was added, and polymerization was continued at the same temperature for 1 hour. Thereafter, the temperature was cooled to 30 ° C. or lower, and the pH was adjusted to 7 with 25% ammonia water to obtain an epoxy-modified acrylic emulsion having a solid content of 50% and a core-shell ratio of 8/2 (weight ratio).

In Production Examples 2 to 9, emulsions were obtained in the same manner as in Production Example 1 except for the monomer compositions shown in Tables 1 and 2. In Production Examples 3 and 4, the ratio of the amount of the added monomer changes in the first and second stages of the polymerization due to the change in the core-shell ratio. Therefore, Emulgen 9
50, Levenol WZ, ammonium persulfate, and distilled water were blended by increasing or decreasing the amount used in Production Example 1 in accordance with the core-shell ratio (C / S) of the amount of the added monomer.

[Production Example 10] A 25% aqueous solution of polyoxyethylene nonylphenyl ether (trade name: Emulgen 950, manufactured by Kao Corporation) was added to a mixture of the radical polymerizable monomer and the epoxy resin shown in Production Example 10 in Table 2. 80 copies,
Sodium polyoxyethylene nonyl phenyl ether sulfate (trade name: Revenol WZ, manufactured by Kao Corporation) 25
% Aqueous solution 40 parts, ammonium persulfate 2 parts, distilled water 40
0 parts was added and stirred with a homomixer to obtain a pre-emulsion 3
Was prepared.

Separately, 400 distilled water was placed in a flask equipped with a stirrer.
Parts, 20 parts of a 25% aqueous solution of Emulgen 950,
The temperature is raised to 80 ° C., and a solution prepared by dissolving 1 part of ammonium persulfate in 50 parts of water is added. To this, the pre-emulsion 3 is continuously dropped over 4 hours. After curing, cure for 30 minutes.
Thereafter, a solution prepared by dissolving 0.5 part of ammonium persulfate in 50 parts of water was added, and polymerization was continued at the same temperature for 1 hour. Then, it is cooled to 30 ° C or less, and p
H was adjusted to 7 to obtain an epoxy-modified acrylic emulsion having a solid content of 50%.

[0064]

Examples 1 to 10 The formulations shown in Table 3 were prepared using the emulsions obtained in Production Examples 1 to 7. During compounding, the curing agent was dissolved in water and then added to the emulsion. Table 4 shows the evaluation results.

[0065]

Comparative Examples 1-4 The formulations shown in Table 5 were prepared using the emulsions obtained in Production Examples 8-10, and the evaluation results are shown in Table 6. Mixing and evaluation were performed in the same manner as in the examples.

[0066]

[Table 1]

[0067]

[Table 2]

[0068]

[Table 3]

[0069]

[Table 4]

[0070]

[Table 5]

[0071]

[Table 6]

[0072]

As described above, a curable emulsion containing an epoxy resin having an improved pot life can be obtained. In particular, the pot life under high temperature conditions assuming the summer is improved. Further, a curable emulsion having an excellent balance with other physical properties such as adhesion strength, heat creep resistance and water resistance can be obtained.

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Claims (1)

[Claims] 1. A multilayer emulsion having a core part and a shell part, wherein the core part has a glass transition temperature of 80 ° C. or higher and a solubility in water at 25 ° C. of 1%.
g of a radical polymerizable monomer mixture containing a radical polymerizable monomer (A) less than 1 g and an epoxy resin, wherein the shell portion has a glass transition temperature of 80 ° C. or higher and 25 ° C. At least one radical polymerizable monomer selected from the group consisting of a radical polymerizable monomer (B-1) having a solubility in water of 1 g or more and a polymer having a glass transition temperature of less than 80 ° C. (B-2). A curable multilayered emulsion obtained by emulsion polymerization of a mixture of monomers.