JP2001040231A - Aqueous emulsion composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition excellent in both water resistance and low-temperature leaving stability, by including an aqueous emulsion having respectively specific dispersant and dispersoid and a specific waterproofing agent. SOLUTION: This composition is obtained by including (A) an aqueous emulsion wherein a vinyl alcohol-based polymer having a saponification degree of >=95 mol% and containing 1 to 20 mol% of a, <=4C α-olefin unit in the molecule and a 2nd vinyl alcohol-based polymer containing carboxyl group in the molecule are used as dispersants, and a polymer having monomeric unit(s) consisting of ethylenically unsaturated monomer and/or a diene-based monomer is used as a dispersoid and (B) a waterproofing agent which is at least one kind selected from an epoxy compound, an amino group-containing aqueous resin, an aluminum compound and a titanium compound, wherein the compounding weight ratio (solid weight ratio) of the component A to the component B is (99.9:0.1) to (50:50), preferably (99.8:0.2) to (70:30).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous emulsion composition, and more particularly, to a method in which a vinyl alcohol polymer having an .alpha.-olefin unit and a vinyl alcohol polymer having a carboxyl group are used as a dispersant, and Aqueous emulsion composition comprising a water-based emulsion containing a polymer having at least one monomer unit selected from a saturated monomer and a diene-based monomer as a dispersoid and a water-resistant agent such as an epoxy compound and an amino-containing aqueous resin. About things. More specifically, the present invention relates to an aqueous emulsion composition having excellent water resistance and shelf stability.

[0002]

2. Description of the Related Art Conventionally, polyvinyl alcohol (hereinafter sometimes abbreviated as PVA) has been used as a protective colloid for emulsion polymerization of ethylenically unsaturated monomers, particularly vinyl ester monomers represented by vinyl acetate. Widely used, vinyl ester-based aqueous emulsions obtained by emulsion polymerization using this as a protective colloid can be used for various adhesives for paper, woodworking and plastics, and various adhesives for impregnated paper and non-woven products. It is widely used in fields such as binders, admixtures, jointing materials, paints, paper processing and textile processing. Such an aqueous emulsion generally has a low viscosity by adjusting the degree of saponification of the PVA-based polymer, has a viscosity close to a Newtonian flow, and has a relatively good water resistance. Since it has a high viscosity and relatively low temperature dependence of emulsion viscosity, it has been awarded for various uses. However, some of the aqueous emulsions lack fluidity (high-speed coating properties), have poor water resistance, have a large temperature dependence of emulsion viscosity, and have a marked increase in emulsion viscosity at low temperatures. It is known that it has drawbacks and that these properties largely depend on the PVA-based polymer used in the emulsion polymerization.

That is, PV as a dispersant for emulsion polymerization
The A-based polymers generally include so-called "completely saponified PVA" having a degree of saponification of about 98 mol% and "partially saponified PVA" having a degree of saponification of about 88 mol%. Although the fluidity (high-speed coating property) is good, there is a disadvantage that the viscosity of the emulsion at the time of leaving at low temperature is remarkably increased and gelation is easily caused. On the other hand, when the latter PVA-based polymer is used, the emulsion has an improved viscosity at low temperatures and a tendency to gel at low temperatures, but has a disadvantage of poor water resistance. In order to improve such disadvantages, both PVA-based polymers are used in combination, and PVA-based polymers having an intermediate saponification degree between the two are used. Sex was not satisfied at the same time. Then, a vinyl alcohol-based polymer containing an ethylene unit was proposed, and the water resistance and the low-temperature storage stability were greatly improved. However, even if it has ethylene units, since it is a so-called fully saponified PVA, from the viewpoint of emulsion polymerization stability, a vinyl alcohol-based polymer containing a large amount of ethylene units is used in order to use partially saponified PVA. Must be used as a dispersant. In addition, since a large amount of a vinyl alcohol-based polymer is used, both water resistance and low-temperature storage stability cannot be completely satisfied at present.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide an aqueous emulsion composition which is excellent in both water resistance and low-temperature storage stability under such circumstances.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to develop an aqueous emulsion composition having the above-mentioned preferable properties.
Contains 1 to 20 mol% of an olefin unit and has a saponification degree of 95
Mol% or more of a vinyl alcohol polymer (A) and a carboxyl group-containing vinyl alcohol polymer (B) are used as a dispersant, and at least one kind selected from an ethylenically unsaturated monomer and a diene monomer. An aqueous emulsion composition comprising a polymer containing monomer units as a dispersoid and an aqueous emulsion composition comprising at least one water-resistant agent selected from an epoxy compound, an amine group-containing aqueous resin, an aluminum compound and a titanium compound. The inventors have found that they are satisfactory, and have completed the present invention.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION An aqueous emulsion used in the aqueous emulsion composition of the present invention contains 1 to 20 mol% of an α-olefin unit having 4 or less carbon atoms in a molecule and has a saponification degree of 95 mol%. The above vinyl alcohol polymer (A) can be obtained by saponifying a copolymer of a vinyl ester and an α-olefin having 4 or less carbon atoms. Here, the α-olefin unit having 4 or less carbon atoms includes ethylene, propylene, butylene, and isobutylene units, and ethylene units are preferable.

A vinyl alcohol polymer (B) containing a carboxyl group can be prepared by a known method (Japanese Patent Publication No.
31844) can be obtained by saponifying a copolymer of a vinyl ester and a monomer having a carboxyl group. Although the carboxyl group content of the polymer is not particularly limited, it is usually 0.1 to 20 mol%, preferably 0.2 to 15 mol%, more preferably 0.25 to 15 mol%.
10 mol% is used. Here, as the monomer having a carboxyl group, acrylic acid, methacrylic acid,
Examples thereof include (anhydride) phthalic acid, (anhydride) maleic acid, and (anhydride) itaconic acid. Of these, dicarboxylic acid and its anhydride are preferable.

Examples of the vinyl ester include vinyl formate, vinyl acetate, vinyl propionate, and vinyl pivalate. Vinyl acetate is economically preferable.

The content of the α-olefin unit having 4 or less carbon atoms must be 1 to 20 mol%,
Preferably it is 3 to 15%, more preferably 5 to 10%. When the content of α-olefin units having 4 or less carbon atoms is 1
If the amount is less than 20 mol%, an aqueous emulsion satisfying the above-mentioned water resistance and low-temperature storage stability cannot be obtained at the same time. If the amount exceeds 20 mol%, the water solubility decreases, and a stable aqueous emulsion can be obtained. No concerns arise.

The vinyl alcohol polymer (A) used for the dispersant may be a copolymer of an ethylenically unsaturated monomer copolymerizable within a range that does not impair the effects of the present invention. Such ethylenically unsaturated monomers include, for example, acrylic acid, methacrylic acid, (anhydrous) phthalic acid, (anhydride) maleic acid, (anhydride) itaconic acid, acrylonitrile, methacrylonitrile, acrylamide,
Methacrylamide, trimethyl- (3-acrylamido-3-dimethylpropyl) -ammonium chloride, acrylamido-2-methylpropanesulfonic acid and its sodium salt, ethyl vinyl ether, butyl vinyl ether, N-vinyl pyrrolidone, vinyl chloride, vinyl bromide, Examples include vinyl fluoride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, sodium vinyl sulfonate, sodium allyl sulfonate, and the like.
Further, in the presence of a thiol compound such as thiolacetic acid or mercaptopropionic acid, a vinyl ester-based monomer such as vinyl acetate is copolymerized with ethylene, and a terminal-modified product obtained by saponifying the copolymer may also be used. it can. Further, the vinyl alcohol-based polymer (B) used as the dispersant can also copolymerize a copolymerizable ethylenically unsaturated monomer within a range that does not impair the effects of the present invention. Examples of such an ethylenically unsaturated monomer include acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, trimethyl- (3-acrylamido-3-dimethylpropyl) -ammonium chloride, and acrylamido-2-methylpropanesulfonic acid. And sodium salts thereof, ethyl vinyl ether, butyl vinyl ether, N-vinyl pyrrolidone, vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, sodium vinyl sulfonate, sodium allyl sulfonate and the like. Can be Further, in the presence of a thiol compound such as thiolacetic acid or mercaptopropionic acid, a vinyl ester-based monomer such as vinyl acetate is copolymerized with an ethylenic monomer having a carboxyl group, and is obtained by saponification. End modified products can also be used.

The vinyl alcohol polymer having 1 to 20 mol% of α-olefin units in the molecule used as a dispersant for the aqueous emulsion of the present invention and having a saponification degree of 95 mol% or more has a saponification degree of 95.0 mol. %, More preferably 96.0 mol% or more, and even more preferably 97.0 mol% or more. Saponification degree 9
If it is less than 5.0 mol%, an aqueous emulsion composition having excellent water resistance cannot be obtained. Further, the saponification degree of the vinyl alcohol polymer containing a carboxyl group used as a dispersant is preferably 70 mol% or more,
More preferably, it is at least 80 mol%, and still more preferably 85
Mol% or more. The polymerization degree of both vinyl alcohol polymers is preferably in the range of 100 to 8000, and 300
-3000 is more preferable. When the polymerization degree is less than 100, the characteristics as a PVA protective colloid are not exhibited,
When it exceeds 8,000, there is a problem in industrial production of the PVA-based polymer.

In the aqueous emulsion constituting the aqueous emulsion composition of the present invention, at least one monomer unit selected from ethylenically unsaturated monomers and diene monomers constituting a dispersoid is ethylene, propylene And olefins such as isobutylene, halogenated olefins such as vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene fluoride; vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate and vinyl versatate; acrylic acid, methacrylic acid and acrylic Acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, 2-hydroxyethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methacrylate Methacrylates such as 2-ethylhexyl acrylate, dodecyl methacrylate, 2-hydroxyethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate and quaternary products thereof, furthermore, acrylamide, methacrylamide, N- Acrylamide monomers such as methylol acrylamide, N, N-dimethylacrylamide, acrylamide-2-methylpropanesulfonic acid and its sodium salt, styrene, α-methylstyrene, p
Styrene sulfonic acid and styrene monomers such as sodium and potassium salts, and other diene monomers such as N-vinylpyrrolidone, butadiene, isoprene, and chloroprene; these may be used alone or in combination of two or more. Used as Among the above ethylenically unsaturated monomers, a vinyl ester-based monomer or a combination use of ethylene and a vinyl ester-based monomer is preferred.

The aqueous emulsion constituting the aqueous emulsion composition of the present invention comprises the above-mentioned vinyl alcohol polymer having an α-olefin unit having 4 or less carbon atoms (hereinafter sometimes abbreviated as α-olefin-modified PVA) and Using an aqueous solution of a vinyl alcohol polymer containing a carboxyl group (hereinafter sometimes abbreviated as a carboxyl group-modified PVA) as a dispersant, the above ethylenically unsaturated monomer is added in the presence of a conventionally known polymerization initiator. The monomer or diene-based monomer is added temporarily or continuously and emulsion-polymerized with the ethylenically unsaturated monomer or diene-based monomer. Further, the ethylenically unsaturated monomer,
An emulsion polymerization method in which a product previously emulsified using an aqueous solution of α-olefin-modified PVA and carboxyl group-modified PVA can be continuously added to a polymerization reaction system can also be adopted. The amount of the α-olefin-modified PVA and the carboxyl group-modified PVA is not particularly limited, but is preferably 1 to 30 parts by weight based on 100 parts by weight of the polymer of the ethylenically unsaturated monomer or the diene monomer. Parts, more preferably 2-2
The range is 0 parts by weight. If the amount is less than 1 part by weight or more than 30 parts by weight, polymerization stability may be reduced, and initial adhesive strength and water-resistant adhesive strength may be reduced. There is no particular limitation on the ratio of the α-olefin-modified PVA (A) and the carboxyl group-modified PVA (B), but (A) / (B) = 99/1 to 30 in a normal weight ratio.
/ 70, preferably 98/2 to 50/50, more preferably 97/3 to 70/30. As the aqueous emulsion used in the present invention, the aqueous emulsion obtained by the above method can be used as it is, but if necessary, various known emulsions may be added and used as long as the effects of the present invention are not impaired. Can be. In addition, as the dispersant in the aqueous emulsion used in the present invention, the above-mentioned ethylene-modified PVA-based polymer and α-
Olefin-modified PVA is used, but if necessary,
Conventionally known anionic, nonionic or cationic surfactants, PVA-based polymers, hydroxyethylcellulose and the like can be used in combination.

Among the water-proofing agents constituting the aqueous emulsion composition of the present invention, bisphenol A diglycidyl ether, bisphenol A diβ-methyl glycidyl ether, bisphenol F diglycidyl ether, tetrahydroxyphenylmethane tetraglycidyl ether are used as epoxy compounds. , Resorcinol diglycidyl ether, brominated bisphenol A diglycidyl ether,
Chlorinated bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, diglycidyl ether of bisphenol A alkylene oxide adduct, novolak glycidyl ether, polyalkylene glycol diglycidyl ether, glycerin triglycidyl ether, pentaerythritol diglycidyl ether, epoxy Glycidyl ether type such as urethane resin; glycidyl ether / ester type such as glycidyl ether / ester of P-oxybenzoate; diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahexaphthalate, diglycidyl acrylate Glycidyl ester type such as glycidyl ester and dimer acid diglycidyl ester; glycidyl aniline, Glycidylamine type such as laglycidyl diaminodiphenylmethane, triglycidyl isocyanurate and triglycidylaminophenol; linear aliphatic epoxy resin such as epoxidized polybutadiene and epoxidized soybean oil; 3,4 epoxy-6 methylcyclohexylmethyl-3,4 Epoxy-6 methylcyclohexanecarboxylate, 3,4 epoxycyclohexylmethyl (3,4-epoxycyclohexane) carboxylate, bis (3,4-epoxy-6methylcyclohexylmethyl) adipate, vinylcyclohexene diepoxide, dicyclopentadiene oxide, Screw (2,3
-Epoxycyclopentyl) ethers, alicyclic epoxy resins such as limonene dioxide, polyamide epichlorohydrin and the like.

The amino group-containing aqueous resin includes (1) a vinylamine polymer, (2) an allylamine polymer,
(3) Amino group-containing acrylic emulsion or amino group-containing aqueous acrylic resin.

(1) The vinylamine polymer is not particularly limited as long as it is obtained by polymerizing an N-vinylamide monomer and hydrolyzing it. Examples of the N-vinylamide-based monomers include N-vinylformamide, N-vinylacetamide, N-methyl-N-vinylformamide, and N-methyl-N-vinylacetamide. Further, an ethylenically unsaturated monomer other than N-vinylamide may be copolymerized in addition to the N-vinylamide monomer as long as the characteristics of the vinylamine-based polymer are not affected.

The vinylamine-based polymer is obtained by hydrolyzing an N-vinylamide polymer. In order to produce an N-vinylamide polymer, a precipitation polymerization method in which N-vinylamide is dissolved and the polymer is polymerized using a radical polymerization initiator in an organic solvent in which the polymer is not dissolved (precipitates) is particularly preferable. is there. Organic solvents that can be used at this time include ethyl acetate, butyl acetate, isopropyl acetate, benzene, toluene, xylene, ethylbenzene, acetone, methyl ethyl ketone, acetonitrile, methylpyrrolidone, and the like.
Any solvent can be used as long as it dissolves N-vinylamide and does not dissolve the N-vinylamide polymer. These organic solvents can also be used as a mixture as necessary, for example, by adjusting the molecular weight. A small amount of a solvent (for example, less than 10% by weight) that dissolves an N-vinylamide polymer such as water, methanol, or ethanol can be used. ) It is also possible to use a mixture. The N-vinylamide concentration at the time of polymerization is usually 1 to 40% by weight, preferably 5 to 20% by weight.

The radical polymerization initiator may be any compound as long as it is soluble in the organic solvent. For example, azobisisobutyronitrile, 2,2'-azobis (4-methoxy-2,4- Dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylpropionitrile), 2,2'-azobis (2-methylbutyronitrile) , 1,1'-azobis (cyclohexane-1-carbonitrile), dimethyl 2,2'-azobis (2-methylpropionate), benzoyl peroxide, tertiary butyl hydroperoxide, di (2-ethylhexylperoxy) Dicarbonate). The amount of the polymerization initiator to be added is 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on N-vinylamide. Further, a chain transfer agent such as butyl mercaptan, dodecane thiol, bromotrichloromethane, isopropanol, thioglycolic acid, 2-ethylhexyl thioglycolate, etc. can be added in order to obtain the desired appropriate viscosity. The amount of the chain transfer agent to be added is 0.001 to 10% by weight, preferably 0.01 to 5% by weight, based on N-vinylamide. Cannot be obtained. The polymerization temperature is appropriately selected within a range from 30 ° C. or higher to the boiling point of the organic solvent used. If the polymerization temperature is too low, it has a long time to complete the polymerization, and it is not preferable because it may cause a decrease in the yield of the polymer, and is preferably 40 ° C. or higher, and particularly preferably around the boiling point of the organic solvent. Temperature. Further, if necessary, the polymerization can be carried out after degassing dissolved oxygen in the organic solvent,
When the polymerization is carried out near the boiling point of the organic solvent, the polymerization can be carried out without degassing.

The hydrolysis of the N-vinylamide polymer is
It can be performed using a basic catalyst or an acid catalyst. That is, using a basic catalyst such as sodium hydroxide, potassium hydroxide, sodium methylate, or an acidic catalyst such as p-toluenesulfonic acid, the alcohol or glycol such as methanol, ethanol, propanol, butanol, and ethylene glycol is used as a solvent. And a hydrolysis reaction is carried out. Further, in order to improve the solubility of the N-vinylamide polymer and the catalyst, tetrahydrofuran,
Solvents such as dioxane, dimethylsulfoxide, diethylene glycol dimethyl ether, toluene, acetone, and water are appropriately mixed and used. The conditions of the hydrolysis reaction are as follows:
Usually, catalyst concentration / N-vinylamide monomer unit concentration =
0.01 to 2.0 (molar ratio), reaction temperature 0 to 180 ° C,
The reaction time ranges from 0.1 to 20 hours.

The degree of hydrolysis of the N-vinylamide polymer is preferably at least 0.5 mol%, more preferably at least 1 mol%, even more preferably at least 3 mol%. If the degree of hydrolysis is less than 0.5 mol%, the reactivity with the polyurethane prepolymer may be poor due to the low amine content of the resulting vinylamine-based polymer. The upper limit of the degree of hydrolysis is not particularly limited, but is preferably 100% or less, more preferably 95% or less.

(2) The allylamine-based polymer includes (a) a homopolymer of a mono- or diallylamine derivative;
(B) Copolymers of two or more mono- or diallylamine derivatives.

The homopolymer of the mono- or diallylamine derivative (a) includes polyallylamine, polydiallylamine, poly (N-benzyldiallylamine),
Examples thereof include poly (N-alkylallylamine) and poly (N-alkyldiallylamine). However, the alkyl group of poly (N-alkylallylamine) or poly (N-alkyldiallylamine) is methyl, ethyl,
Hydroxyethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl,
Cyclohexyl groups are preferred.

The copolymer of two or more mono- or diallylamine derivatives of the above (b) includes a copolymer of monoallylamine and diallylamine, and a copolymer of monoallylamine and N
-A copolymer of alkylallylamine, a copolymer of monoallylamine and N-alkyldiallylamine, a copolymer of diallylamine and N-alkyldiallylamine,
A copolymer of diallylamine and N-alkylallylamine, a copolymer of N-alkylallylamine and N-alkyldiallylamine, a copolymer of two or more N-alkylallylamines, and a copolymer of two or more N-alkyldiallylamines Can be exemplified. However, the term "alkyl" in the above copolymer is to be understood in a broad sense, and includes a chain alkyl group such as methyl, ethyl, propyl, isopropyl, sec-butyl and tert-butyl, a cycloalkyl group such as cyclohexyl, It includes an aralkyl group such as benzyl and an alkyl group having a functional group such as a hydroxyl group and a cyano group.

Among (3), the amino group-containing acrylic emulsion having active hydrogen is exemplified by an amino group-containing emulsion having active hydrogen obtained by modifying a carboxyl group-containing acrylic emulsion with alkyleneimine. The acrylic emulsion containing a carboxyl group includes unsaturated monocarboxylic acids such as (meth) acrylic acid, cinnamic acid and crotonic acid; unsaturated dicarboxylic acids such as itaconic acid, maleic acid and fumaric acid; One or more monomers selected from the group of carboxyl group-containing unsaturated monomers such as esters, and monomers copolymerizable with the carboxyl group-containing unsaturated monomer, for example, (meth) ) Acrylamide, N-methylol (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (Meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) Acrylate, t- butyl (meth) acrylate, 2-Echiruechiru (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylonitrile,
One or two or more monomers selected from the group of dimethylaminoethyl (meth) acrylate, diethylethylamino (meth) acrylate, styrene and the like can be obtained by a generally known method, for example, potassium persulfate and the like. In the presence of a polymerization initiator, an emulsifier such as an anionic or nonionic surfactant is used, or a copolymer obtained by emulsion polymerization in water using a vinyl alcohol-based polymer as a protective colloid It is. The amount of carboxyl groups must be 2% by weight or more as a monomer,
Preferably, it is 2.5 to 30% by weight. In addition, in the emulsion containing the carboxyl group, the interior of the emulsion is previously crosslinked with divinylbenzene or another monomer having two or more copolymerizable unsaturated groups in one molecule during the emulsion polymerization. Or a multi-layer (core-shell type) emulsion obtained by sequentially polymerizing two or more monomers, or a polymer having a controlled degree of polymerization using a chain transfer agent such as t-dodecyl mercaptan, It may be emulsion-polymerized by a known method such as feed.

Among (3), the amino group-containing aqueous acrylic resin having active hydrogen is an amino group-containing aqueous acrylic resin having active hydrogen obtained by modifying a carboxyl group-containing aqueous acrylic resin with alkyleneimine. is there. An aqueous acrylic resin containing a carboxyl group is one or more of the carboxyl group-containing unsaturated monomers described for the emulsion containing a carboxyl group, and is copolymerizable with the carboxyl group-containing unsaturated monomer. An aqueous resin obtained by solution polymerization of one or more monomers selected from the group of monomers described in the preceding paragraph, wherein the aqueous resin is water-soluble or water-dispersible obtained by solution polymerization. It is obtained by neutralizing a copolymer or a copolymer thereof with a basic substance, for example, an amine compound such as ammonia, trimethylamine, triethylamine or monoethanolamine, or a basic substance such as sodium hydroxide or potassium hydroxide. It is a water-soluble or water-dispersible resin.

The amino group-containing acrylic emulsion and aqueous acrylic resin having active hydrogen modified with alkylene imine can be synthesized by modifying the carboxyl group-containing acrylic emulsion or aqueous acrylic resin with alkylene imine. And as the alkylene imine, for example, ethylene imine, propylene imine, butylene imine and the like can be used. N- (2-aminoethyl) aziridine, N
N- (2) such as-(2-aminoethyl) propyleneimine;
-Aminoalkyl) substituted alkylene imines can likewise be used. The amount of modification with the alkylene imine is preferably 0.2 to 0.2 to the carboxyl group of the carboxyl group-containing acrylic emulsion or aqueous acrylic resin.
It may be in the range of 5 molar equivalents, preferably 0.5 to 4
It is a molar equivalent. These carboxyl group-containing acrylic emulsions or aqueous acrylic resins are modified with alkylene imines, and the active hydrogen-containing amino group-containing acrylic emulsions or aqueous acrylic resins are used alone or as a mixture of two or more. You.

Among the water-proofing agents used in the present invention, the aluminum compound is not particularly limited, but aluminum chloride, aluminum nitrate and its hydrate, aluminum sulfate (sulfate band) and the like are preferably used.

Among the water-proofing agents used in the present invention, the titanium compound is not particularly limited, but isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, bis (dioctyl pyrophosphate) (Phosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, diisopropylbis (dioctylpyrophosphate) titanate, tetraisopropylbis (dioctylphosphite) titanate, tetraoctylbis (ditridecylphosphite) titanate, tetra (2.2)
-Diallyloxymethyl-1-butyl) bis (ditridecylphosphite) titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropyltris (dioctylpyrophosphate) titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) Ethylene titanate, diisopropyl bis (dioctyl pyrophosphate) titanate, tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, tetramethyl titanate, titanium acetylacetonate, titanium tetraacetylacetonate, polytitanium Acetylacetonate, titanium octylene glycolate, titanium lactate Nitrate, titanium lactate, titanium triethanol aminate, polyhydroxytitanium stearate, etc., and commercially available products include Plenact series (manufactured by Ajinomoto Co.), Titacoat series (manufactured by Nippon Soda Co., Ltd.), and Olga Chicks. Series (manufactured by Matsumoto Pharmaceutical Co., Ltd.).

In the aqueous emulsion composition of the present invention, the weight ratio (solid content weight ratio) of the aqueous emulsion / waterproofing agent is from 99.9 / 0.1 to 50/50, preferably 99.8 / 0. 0.2 to 70/30. When the compounding ratio exceeds 99.9 / 0.1, the water-resistant effect is low, and when it is less than 50/50, the viscosity stability of the aqueous emulsion composition may decrease.

The aqueous emulsion composition of the present invention may contain various organic solvents such as toluene, perchrene, dichlorobenzene and trichlorobenzene in order to adjust the drying property, setting property, viscosity, film forming property and the like, if necessary. , Starch, modified starch, oxidized starch, sodium alginate,
Water-soluble polymers such as carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, maleic anhydride / isobutene copolymer, maleic anhydride / styrene copolymer, maleic anhydride / methyl vinyl ether copolymer, polyvinyl alcohol, and urea / formalin resin; Thermosetting resins such as urea / melamine / folimarin resins, phenol / folimarin resins, and fillers such as clay, kaolin, talc, calcium carbonate, and wood flour;
It may contain an extender such as flour, a pigment such as titanium oxide or other additives such as an antifoaming agent, a dispersant, an antifreezing agent, a preservative, and a rust inhibitor. The aqueous emulsion composition of the present invention is used in various applications such as woodworking adhesives, paperworking adhesives, paints, and fiber treatment agents, taking advantage of its high water resistance.

[0031]

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

Production Example 1 (Production example of vinylamine-based polymer) N-vinylacetamide (100 parts) was treated with ethyl acetate 900
Of azobisisobutyronitrile as a radical polymerization initiator, and the mixture was kept in a boiling state. As the polymerization proceeds, the produced N-vinylamide polymer precipitates in ethyl acetate, and is kept for 3 hours. After allowing to cool, the polymer was suction-filtered, dried under vacuum at 50 ° C. for 24 hours, and crushed to obtain 98 parts of a fine powdery N-vinylacetamide polymer.

10 parts of this N-vinylacetamide polymer was dissolved in 50 parts of methanol, and the temperature was raised to 60 ° C. To this solution, 20 parts of a 10% sodium hydroxide methanol solution was added, and the mixture was stirred for 2 hours to carry out hydrolysis. The degree of hydrolysis of the obtained vinylamine-based polymer (polyamine-1) was measured by conductivity titration and found to be 83 mol%.

Production Example 2 (Production Example of Amino Group-Containing Acrylic Emulsion) 780 parts of ion-exchanged water and anion were placed in a 2-liter separable flask equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel. After charging 75 parts of a surfactant (25% aqueous solution), 68
The temperature was raised to ° C. 90 parts of acrylic acid, 100 parts of methyl methacrylate and 200 parts of butyl acrylate, 35 parts of styrene
80 parts of a polymerizable monomer mixture consisting of 0 parts was added to a flask and stirred for 30 minutes, and then 8 parts of a 2% by weight aqueous hydrogen peroxide solution and 8 parts of a 2% by weight L-ascorbic acid aqueous solution were added. The polymerization was started. From 15 minutes after the start of the polymerization, the remaining polymerizable monomer mixture was dropped uniformly over 90 minutes. During this time, 80 parts of a 2% by weight aqueous hydrogen peroxide solution and 70 parts of a 2% by weight aqueous L-ascorbic acid solution were divided and dropped into the flask every 10 minutes until the dropping of the polymerizable monomer mixture was completed. After completion of the dropwise addition, the mixture was aged for 1 hour, cooled, and had a nonvolatile content of 45% by weight.
Emulsion was obtained. Next, 32 parts of a 17% by weight aqueous solution of ethyleneimine was added to 150 parts by weight of the emulsion with stirring, and the reaction was carried out at 50 ° C. for 2 hours.
8 mol / 100 g emulsion solid content, non-volatile content 4
1% by weight of an amino group-containing acrylic emulsion (polyamine-2) was obtained.

Production Example 1 of Aqueous Emulsion A 1-liter glass polymerization vessel equipped with a reflux condenser, a dropping funnel, a thermometer and a nitrogen inlet was charged with 260 parts of ion-exchanged water.
g, PVA-1 (polymerization degree 1000, saponification degree 99.0)
%, Ethylene-modified amount 7.0 mol%) 30 g and PVA-
7 g (2, polymerization degree: 1700, saponification degree: 89.0%, maleic anhydride copolymerized modification amount: 1.0 mol%) was completely dissolved at 95 ° C. Next, this PVA aqueous solution was cooled, replaced with nitrogen, and then stirred at 200 rpm with 37 g of vinyl acetate.
After the temperature was raised to 60 ° C., polymerization was started in the presence of a hydrogen peroxide / tartaric acid redox initiator system. From 15 minutes after the start of the polymerization, 333 g of vinyl acetate was continuously added over 3 hours to complete the polymerization. Solids concentration 48.
A 3% polyvinyl acetate emulsion was obtained. 5 parts of dibutyl phthalate was added to and mixed with 100 parts by weight of this emulsion (Em-1).

Production Example 2 of Aqueous Emulsion A 1-liter glass polymerization vessel equipped with a reflux condenser, a dropping funnel, a thermometer and a nitrogen inlet was charged with 260 parts of ion-exchanged water.
g, PVA-3 (degree of polymerization 1700, degree of saponification 98.0)
%, Ethylene modification amount 4.0 mol%) 30 g and PVA-
4 g (polymerization degree 1700, saponification degree 97.0%, maleic anhydride copolymerization modified amount 1.0 mol%) was charged and completely dissolved at 95 ° C. Next, after cooling this PVA aqueous solution and purging with nitrogen, 37 g of vinyl acetate was charged while stirring at 200 rpm, the temperature was raised to 60 ° C., and polymerization was started in the presence of a hydrogen peroxide / tartaric acid redox initiator system. . From 15 minutes after the start of the polymerization, 333 g of vinyl acetate was continuously added over 3 hours to complete the polymerization. Solids concentration 48.4
% Polyvinyl acetate emulsion was obtained. 5 parts of dibutyl phthalate was added to and mixed with 100 parts by weight of this emulsion (Em-2).

Production Example 3 of Aqueous Emulsion PVA-1 used in Production Example 1 of Aqueous Emulsion,
Instead of using PVA-2, PVA-5 (Kuraray PV
A-217: Aqueous emulsion (Em-3) was obtained in the same manner as in Aqueous emulsion production example 1 except that the degree of polymerization was 1700 and the degree of saponification was 88.0 mol%.

Aqueous emulsion production example 4 PVA-1 used in aqueous emulsion production example 1
An aqueous emulsion (Em-4) was obtained in the same manner as in the aqueous emulsion production example 1 except that only PVA-1 was used instead of using PVA-2.

Aqueous emulsion production example 5 PVA-1 used in aqueous emulsion production example 1
An aqueous emulsion (Em-5) was obtained in the same manner as in the aqueous emulsion production example 1 except that only PVA-2 was used instead of PVA-2.

Example 1 Em-1 100 obtained in Production Example 1 of aqueous emulsion
An aqueous emulsion composition was prepared by mixing 5 parts by weight of the polyamine-1 obtained in Production Example 1 with respect to parts by weight.
The coating water resistance, water resistance and adhesive stability of the obtained aqueous emulsion composition were evaluated in the following manner. Table 1 shows the results.

(Evaluation of Emulsion) (1) Water Resistance of Film The obtained aqueous emulsion was prepared at 20 ° C. and 65% RH under P
It was cast on ET and dried for 7 days to obtain a dry film of 500 μm. This film was punched out to a diameter of 2.5 cm, and the sample was immersed in water at 20 ° C. for 24 hours to determine the water absorption and elution rate of the film. (2) Water resistant adhesive strength 150 g of the obtained aqueous emulsion was applied to hemlock material (straight grain).
/ M ² applied and bonded together with a load of 7 kg / m ² for 16
Time clamped. Then, after decompressing and curing for 5 days at 20 ° C. and 65% RH, it was immersed in warm water of 60 ° C. for 3 hours, and the compressive shear strength was measured in a wet state. (3) Viscosity stability 30 minutes when the emulsion was left at 5 ° C. and 50 ° C.
The change in viscosity after one day was observed.

Example 2 A test was conducted in the same manner as in Example 1 except that 5 parts by weight of the polyamine-2 obtained in Production Example 2 was used instead of using the polyamine-1 used in Example 1. The results are shown in Table 1.

Example 3 Instead of using polyamine-1 used in Example 1, polyallylamine (manufactured by Nitto Boseki Co., Ltd., molecular weight 10
000) was used in the same manner as in Example 1 except that 5 parts by weight was used. The results are shown in Table 1.

Example 4 A test was conducted in the same manner as in Example 1 except that 0.5 part of polyamine-1 was used. The results are shown in Table 1.

Example 5 A test was conducted in the same manner as in Example 1 except that 30 parts of polyamine-1 was used. The results are shown in Table 1.

Comparative Example 1 A test was conducted in the same manner as in Example 1 except that the polyamine-1 used in Example 1 was not used. The results are shown in Table 1.

Example 6 The same as Example 1 except that Em-2 obtained in Aqueous Emulsion Production Example 2 was used instead of Em-1 obtained in Aqueous Emulsion Production Example 1 used in Example 1. The test was performed. The results are shown in Table 1.

Comparative Example 2 A test was conducted in the same manner as in Example 6 except that the polyamine-1 used in Example 6 was not used. The results are shown in Table 1.

Comparative Example 3 The same as Example 1 except that Em-3 obtained in Aqueous Emulsion Production Example 3 was used instead of Em-1 obtained in Aqueous Emulsion Production Example 1 used in Example 1. The test was performed. The results are shown in Table 1.

Example 7 A test was conducted in the same manner as in Example 1 except that 5 parts by weight of ethylene glycol diglycidyl ether was used instead of the polyamine-1 used in Example 1. The results are shown in Table 1.

Example 8 Instead of using the polyamine-1 used in Example 1, polyamide epichlorohydrin (manufactured by Nippon PMC; WS
-525) was tested in the same manner as in Example 1 except that 5 parts by weight was used. The results are shown in Table 1.

Example 9 A test was conducted in the same manner as in Example 1 except that 5 parts by weight of aluminum chloride was used instead of the polyamine-1 used in Example 1. The results are shown in Table 1.

Example 10 A test was conducted in the same manner as in Example 1 except that 5 parts by weight of aluminum nitrate heptahydrate was used instead of using polyamine-1 used in Example 1. The results are shown in Table 1.

Example 11 A test was conducted in the same manner as in Example 1 except that 5 parts by weight of a sulfuric acid band was used instead of using the polyamine-1 used in Example 1. The results are shown in Table 1.

Example 12 Instead of using polyamine-1 used in Example 1, titanium lactate ("Orgatics TA-1" manufactured by Matsumoto Pharmaceutical Co., Ltd.) was used.
0 ") was conducted in the same manner as in Example 1 except that 5 parts by weight was used. The results are shown in Table 1.

Comparative Example 4 100 ml of ion-exchanged water was placed in a 1-liter glass polymerization vessel equipped with a reflux condenser, a dropping funnel, a thermometer, and a nitrogen inlet.
Part, acetoacetyl group-modified PVA (polymerization degree 1030, saponification degree 98.5%, acetoacetyl group modification amount 5.0 mol%)
Of vinyl alcohol polymer was completely dissolved at 95 ° C. Next, the PVA aqueous solution was cooled, replaced with nitrogen, charged with 10 parts of vinyl acetate while stirring at 140 rpm, heated to 60 ° C., and then started to polymerize in the presence of a hydrogen peroxide / tartaric acid redox initiator system. did. Initiation of polymerization 1
After 5 minutes, 90 parts of vinyl acetate was continuously added over 3 hours to complete the polymerization. A polyvinyl acetate emulsion having a solid content of 55% was obtained. 5 parts of dibutyl phthalate was added to and mixed with 100 parts by weight of this emulsion (Em-6). The obtained “Em-6” 100
An aqueous emulsion composition was prepared by mixing 5 parts by weight of a 40% aqueous glyoxal solution with respect to parts by weight. The film water resistance, water resistance adhesive strength, and viscosity stability of the obtained aqueous emulsion composition were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 5 The same as Example 1 except that Em-4 obtained in Aqueous Emulsion Production Example 4 was used instead of Em-1 obtained in Aqueous Emulsion Production Example 1 used in Example 1. The test was performed. The results are shown in Table 1.

Comparative Example 6 The same as Example 1 except that Em-5 obtained in Aqueous Emulsion Production Example 5 was used instead of Em-1 obtained in Aqueous Emulsion Production Example 1 used in Example 1. The test was performed. The results are shown in Table 1.

[0059]

[Table 1]

Em-1: vinyl acetate emulsion PVA-1 (polymerization degree 1000, saponification degree 99.0 mol%, ethylene modification amount 7.0 mol%) and PVA-2 (polymerization degree 1700, saponification degree 89.0 mol%, anhydrous maleic anhydride) Use: acid copolymerization modified amount 1.0 mol%), solid content concentration 48.3%. Em-2: phenylpolyester emulsion PVA-3 (polymerization degree 1700, saponification degree 98.0 mol%, ethylene modification amount 4.0 mol%) and PVA- 4 (degree of polymerization 1700, degree of saponification 97.0 mol%, maleic anhydride copolymerization modification amount 1.0 m
ol%), solid content concentration 48.4%｝ Em-3: Phenyl acetate emulsion ｛PVA-5 (Kuraray PVA-217;
Use of polymerization degree 1700, saponification degree 88.0 mol%), solid content concentration 48.5%｝ Em-4: phenyl poly emulsion PVA-1 (polymerization degree 1000, saponification degree 99.0 mol%, ethylene modification amount 7.0 mol%), Solid content concentration
48.2%｝ Em-5: Phenyl acetate emulsion ｛PVA-2 (polymerization degree 1700, saponification degree 89.0mol%, maleic anhydride copolymerization amount 1.0mol%), solid content concentration 48.4%｝ Em-6: modification Polyvinyl acetate emulsion acetoacetyl group-modified PV
A; degree of polymerization 1030, degree of saponification 98.5 mol%, acetoacetyl group modification amount 5.0mo
l%) used, solid content concentration 55%｝ Waterproofing agent; (1) polyamine-1, (2) polyamine-2,
(3) polyallylamine, ethylene glycol cyclic acid ether, (5) polyamidochloromethoritol (manufactured by Nippon PMC; WS-525) (6) aluminum chloride, (7) aluminum nitrate heptahydrate, (8) sulfate sulfate, (9 ) Titanium lactate ("Orca Chicks TA-10"; manufactured by Matsumoto Pharmaceutical Co., Ltd.), (10) 40% glyoxal aqueous solution

[0061]

Industrial Applicability The aqueous emulsion composition of the present invention has excellent standing viscosity stability as well as excellent water resistance and water resistant adhesive strength, and is used for woodworking adhesives, plywood adhesives, paper processing agents, paints,
It is widely and suitably used for fiber processing agents and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 63/00 C08L 63/00 A 101/02 101/02 101/14 101/14 // C09D 157/00 C09D 157/00 C09J 157/00 C09J 157/00 D06M 15/333 D06M 15/333 F term (reference) 4J002 AA073 AC051 AC061 AC091 BB021 BB111 BB161 BC031 BC091 BC121 BD041 BD101 BD131 BD141 BE012 BG011BG031 BG011BG013 BJ003 CD012 CD022 CD042 CD052 CD062 CD072 CD082 CD092 CD102 CD122 CD133 CD143 CD163 CD183 DD076 DF036 DG046 EC076 EE046 EG046 EZ006 FD203 FD206 FD312 GH01 GJ01 GK02 GK04 4J038 CA021 CA081 CG031 CB031 CC091 CB031 CB091 CH261 DB022 DB092 DB132 DB152 DB202 DB242 DB262 GA02 GA06 GA08 GA09 GA10 GA12 GA13 GA16 HA126 HA156 HA336 HA376 JA23 JA32 JA47 JC13 JC22 JC24 KA07 MA08 MA10 NA04 NA12 NA26 4J040 CA031 CA161 DA031 DA091 DA141 DB041 DB081 DB091 DC011 DC091 DD012 DD032 DE011 DF011 DF041 DF051 EC03 EC03 EC092 EC091 DG012 EC031 GA13 GA17 GA22 GA25 HA096 HA126 HA226 HA256 HB07 HB22 HC01 HD13 HD23 HD24 JA03 LA05 LA07 MA08 MA09 MB10 MB12 4L033 AC03 AC11 CA19 CA28 CA57

Claims (2)

[Claims] 1. A vinyl alcohol-based polymer (A) having 1 to 20 mol% of an α-olefin unit having 4 or less carbon atoms in a molecule, a saponification degree of 95 mol% or more, and a carboxyl group in a molecule. Vinyl alcohol polymer (B)
As a dispersant, an aqueous emulsion and an epoxy compound having a polymer containing at least one monomer unit selected from an ethylenically unsaturated monomer and a diene monomer as a dispersoid, an amino group-containing aqueous resin, An aqueous emulsion composition comprising at least one water-resistant agent selected from an aluminum compound and a titanium compound. 2. The aqueous emulsion composition according to claim 1, wherein the α-olefin unit having 4 or less carbon atoms is an ethylene unit.