JPH0718156A - Emulsion composition - Google Patents

Abstract

PURPOSE:To obtain an emulsion composition long in pot life, high in the wet strength of a coated film, excellent in the resistances to water, hot water and heat of the coated film. CONSTITUTION:This emulsion composition comprises (B) a polyimide resin such as a polyamide epichlorohydrin and (A) an aqueous emulsion comprising the polymer of an ethylenic unsaturated monomer such as vinyl chloride as a dispersoid and a modified polyvinyl alcohol as a dispersant, the modified polyvinyl alcohol being produced by saponifying a copolymer containing (a) the vinyl ester of a >=5C fatty acid, an alkylvinyl ether having a >=4C alkyl or a >=6C alpha-olefin, (b) an ethylenic unsaturated carboxylic acid or its acid anhydride, and (c) a vinyl acetate as essential comonomers.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an emulsion composition, and more specifically, it has a long pot life and has a high wet strength of a film obtained by evaporating water after coating and has a high wet strength. The present invention relates to an emulsion composition having excellent water resistance, heat resistance and hot water resistance.

[0002]

2. Description of the Related Art Emulsions prepared by using polyvinyl alcohol as a protective colloid (dispersant) have been used for many applications such as paints, adhesives, fiber processing agents and paper processing agents since ancient times. However, polyvinyl alcohol
Since it is water-soluble, the film obtained by evaporating the water from the emulsion is easily swollen in water, and when the film is immersed in water, polyvinyl alcohol is easily eluted and the water resistance is insufficient. . Furthermore, when this film is put into water and boiled, the above-mentioned swelling and elution are promoted, and the film cannot keep its original shape. Further, usually, the emulsion often forms a film and exhibits the performance. Therefore, the glass transition temperature of the resin, which is the dispersoid, is adjusted to the extent that it can be formed into a film by heating at room temperature or for a short time. Therefore, when the glass transition temperature is exceeded, the film is softened and the heat resistance is also insufficient.

Under the circumstances described above, various means have been attempted so far in order to enhance the water resistance, hot water resistance and heat resistance of a film obtained from an emulsion containing a polyvinyl alcohol polymer as a dispersant. . As a typical example thereof, a method is known in which a polyvalent isocyanate compound is mixed with an emulsion having a polyvinyl alcohol polymer as a dispersant. In this method, isocyanate reacts with water, so that the pot life of the composition is short and there is a problem in workability. In addition, various adhesives using an aqueous emulsion containing a polyvinyl alcohol polymer as a dispersant have been proposed. For example, (1) an adhesive comprising an aqueous emulsion containing a polyvinyl alcohol having a ratio Mw / Mn of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of 2.4 or less as a dispersant and a cross-linking agent (JP-A-61-61). -108603), (2) an aqueous emulsion using polyvinyl alcohol as a dispersant, and an adhesive comprising an aliphatic aldehyde such as glyoxal (Japanese Patent Laid-Open No. 55-94937), (3) polyvinyl alcohol, an aqueous emulsion, Adhesives composed of cross-linking agents and amino compounds such as chitosan (JP-A-3-45678), (4) Adhesives composed of polyvinyl alcohol, aqueous emulsions, cross-linking agents such as aluminum chloride, and polyvalent isocyanate compounds (JP-B-57) -16150) and the like are disclosed.

However, in the adhesive of the above (1), there is no concrete example of the cross-linking agent, and if a conventional cross-linking agent is used, the pot life is short and there is a problem in workability. . Further, the adhesives (2) and (3) have a drawback that the obtained film has low wet strength. The adhesive of (4) has a short pot life and has a problem in workability.

[0005]

Under the circumstances, the present invention has a long pot life and good workability.
The purpose of the present invention is to provide an emulsion composition having a high wet strength of a film obtained by evaporating water after coating and having excellent water resistance, hot water resistance and heat resistance of the film.

[0006]

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted earnest studies to develop an emulsion composition having the above-mentioned preferable properties, and as a result, modified polyvinyl alcohol obtained by saponifying a specific copolymer. It was found that an emulsion composition comprising an aqueous emulsion containing a polymer of an ethylenically unsaturated monomer as a dispersoid, and a polyamide resin has a desired property.
The present invention has been completed based on such findings. That is, the present invention relates to at least one monomer (a selected from a vinyl ester of a fatty acid having 5 or more carbon atoms, an alkyl vinyl ether having an alkyl group having 4 or more carbon atoms and an α-olefin having 6 or more carbon atoms (a ), An ethylenically unsaturated carboxylic acid and at least one monomer (b) selected from the acid anhydrides thereof, and a vinyl acetate (c) three component as an essential copolymerization component. To provide an emulsion composition comprising an aqueous emulsion (A) containing a polymer of an ethylenically unsaturated monomer as a dispersant and a polyamide resin (B) as a dispersant. Is. The emulsion composition of the present invention is composed of a specific aqueous emulsion (A) and a polyamide resin (B). Here, the aqueous emulsion which is the component (A) is
As mentioned above, modified polyvinyl alcohol is used as a dispersant,
A polymer of an ethylenically unsaturated monomer is used as the dispersoid. The modified polyvinyl alcohol that is this dispersant is
At least one monomer (a) selected from a vinyl ester of a fatty acid having 5 or more carbon atoms, an alkyl vinyl ether having an alkyl group having 4 or more carbon atoms, and an α-olefin having 6 or more carbon atoms, ethylenically unsaturated Obtained by saponifying a copolymer containing at least one monomer (b) selected from carboxylic acid and its acid anhydride and vinyl acetate (c) as three essential copolymerization components. It is a thing.

Examples of the vinyl ester of a fatty acid having 5 or more carbon atoms in the monomer of the component (a) used as an essential component in the above-mentioned copolymer include valeric acid vinyl ester; capric acid vinyl ester; myristic acid vinyl ester. A fatty acid vinyl ester having a linear alkyl group such as stearic acid vinyl ester or a pivalic acid vinyl ester; 1,1,3,3-tetramethylbutyric acid vinyl ester; a saturated branched fatty acid vinyl ester having an average carbon number of 10 And fatty acid vinyl esters having a branched alkyl group such as pivalic acid vinyl ester; 1,1,3,3-
Tetramethylbutyric acid vinyl ester; a fatty acid vinyl ester having a branched alkyl group such as a saturated branched fatty acid vinyl ester having an average carbon number of 10 is preferable. Also,
Examples of the alkyl vinyl ether having an alkyl group having 4 or more carbon atoms include vinyl ethers having a branched alkyl group such as butyl vinyl ether, octyl vinyl ether, lauryl vinyl ether, and isoamyl vinyl ether, and among them, isoamyl vinyl ether is particularly preferable. Vinyl ether having such a branched alkyl group is preferable because it gives a good emulsion polymer. Further, preferable examples of the α-olefin having 6 or more carbon atoms include heptene-1, octene-1, dodecene-1 and the like. These (a) component monomers may be used alone or in combination of two or more.

In the copolymer, the component (b) monomeric ethylenically unsaturated carboxylic acid or its acid anhydride used as an essential component is, for example, acrylic acid, methacrylic acid, crotonic acid, maleic acid. , Itaconic acid, citraconic acid, maleic anhydride, aconitic acid, and the like, among which citraconic acid, maleic acid, itaconic acid, and maleic anhydride are particularly preferable. These (b) component monomers may be used alone or in combination of two or more. The modified polyvinyl alcohol used in the present invention is a copolymer containing the above-mentioned three components (a) component monomer, (b) component monomer and (c) component vinyl acetate as essential copolymerization components. The copolymerization ratio of the components (a), (b) and (c) and the saponification ratio of the acetyl group of the component (c) are represented by the following formula (I). D value is 0.05 to 4
It is desirable to choose to be within the range. D = [nA + (1-Δ) C / 27.5] / kB ... (I)

However, A indicates the copolymerization ratio (molar basis) of the component (a), is 0.0005 or more in terms of mole fraction, and B indicates the copolymerization ratio (mol basis) of the component (b), which is The ratio is 0.001 or more, C is the copolymerization ratio (molar basis) of the component (c), and the molar fraction is 0.5 or more. n represents a number of 4 or more. When the component (a) is a vinyl ester of a fatty acid, the number of carbon atoms in the fatty acid is −1, when the component (a) is an alkyl vinyl ether, the number of carbon atoms in the alkyl group, and the component (a) is α
-In the case of olefin, it is carbon number -2 of alpha olefin. k represents the number of carboxyl groups in the component (b), Δ represents the saponification ratio (molar basis) of the component (c), and Δ = saponified (c) component / (c) component. The D value represented by the above formula (I) is 0.05 to 4
When a modified polyvinyl alcohol out of the range is used, it is difficult to obtain an emulsion composition sufficiently satisfying the performance which is the object of the present invention. The suitable range of the degree of saponification of the modified polyvinyl alcohol is represented by the above D value, but it may be water-soluble, preferably the structural unit derived from the component (a) is not saponified, and (c)
The degree of saponification of the constituent units derived from the components is 70 to 100 mol%, particularly preferably 80 to 100 mol%.

The modified polyvinyl alcohol used in the present invention is obtained by saponifying a copolymer containing the above-mentioned three components (a), (b) and (c) as essential components. Other copolymerizable components such as ethylene, isobutylene, acrylonitrile, methacrylonitrile, trimethyl- (3-acrylamido-3-dimethylpropyl) ammonium chloride, vinyl chloride, vinyl bromide, vinyl fluoride within a range not impairing the object of the invention. , Vinylidene chloride, vinylidene fluoride, tetrafluoroethylene,
Sodium vinyl sulfonate, sodium allyl sulfonate, methacrylamide, N-substituted methacrylamide,
Acrylamide, N-substituted acrylamide, N-vinylpyrrolidone, vinyl ether having an alkyl group having a carbon number of 3 or less, an olefin having a carbon number of 5 or less are added to the above three components (a), (b), and (c). Even if a modified polyvinyl alcohol obtained by saponifying a copolymer obtained by copolymerization is used, there is no problem.

The method for producing the modified polyvinyl alcohol used in the present invention is not particularly limited, and conventionally known polymerization methods and saponification methods can be applied. That is, as the polymerization method, the components (a), (b) and (c) are added to the polymerization system collectively or in a divided manner or continuously according to the respective copolymerization reactivity ratios, without solvent or in an aqueous medium. 2, in the presence of lower alcohols such as methyl alcohol and ethyl alcohol
A method of polymerizing with a radical polymerization catalyst such as 2'-azobisisobutyronitrile or benzoyl peroxide can be applied. As a method of saponifying the copolymer containing the components (a), (b) and (c) thus obtained,
For example, various known methods used for saponification of polyvinyl acetate copolymer can be applied, but usually, in an alcohol solvent or a hydrous alcohol solvent, an alkali such as sodium alcoholate, sodium hydroxide or potassium hydroxide is allowed to act. The method of saponification is suitable. As the alcohol, lower alcohols such as methyl alcohol and ethyl alcohol are particularly suitable. Moreover, these alcohol solvents are 40% by weight or less of acetone,
It may contain a solvent having a low dielectric constant such as acetic acid methyl ester, acetic acid ethyl ester, or benzene. The degree of polymerization of the modified polyvinyl alcohol in the present invention is not particularly limited, but is preferably in the range of 50 to 3000,
The range of -2000 is more preferable. Further, a terminal-modified product obtained by carrying out the above polymerization and saponifying it in the presence of a thiol compound such as thiol acetic acid and mercaptopropionic acid can also be used.

Next, the polymer of the ethylenically unsaturated monomer which is the dispersoid in the aqueous emulsion of the component (A) is
There are various kinds, but preferable examples of the ethylenically unsaturated monomer as the raw material of this polymer include olefins such as ethylene, propylene and isobutylene, vinyl chloride,
Halogenated olefins such as vinyl fluoride, vinylidene chloride, vinylidene fluoride, vinyl formate, vinyl acetate, vinyl propionate, vinyl esters such as vinyl versatate, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, acrylic acid Butyl, 2-ethylhexyl acrylate, dodecyl acrylate, 2-hydroxyethyl acrylate, etc. Acrylic esters, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, 2-methacrylate Methacrylic acid esters such as hydroxyethyl, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate and their quaternary compounds, as well as acrylamide, methacrylamide, and N-meth Acrylamide, N, N-dimethylacrylamide, acrylamide-based monomers such as acrylamido-2-methylpropanesulfonic acid and its sodium salt, styrene, alpha-methyl styrene, p
-Styrene-based monomers such as styrenesulfonic acid and its sodium and potassium salts, N-vinylpyrrolidone and the like, and diene-based monomers such as butadiene, isoprene and chloroprene, and these may be used alone or in combination. The above is mixed and used.

Among the above ethylenically unsaturated monomers, vinyl ester, (meth) acrylic acid ester, styrene and diene type monomers are preferable, and particularly vinyl ester, a combination of ethylene and vinyl ester and (meth)
Acrylate esters are preferred. The aqueous emulsion which is the component (A) is prepared by temporarily or continuously adding the above ethylenically unsaturated monomer in the presence of a polymerization initiator using the above-mentioned aqueous solution of modified polyvinyl alcohol as a dispersant. It is obtained by emulsion-polymerizing the ethylenically unsaturated monomer. Further, an emulsion polymerization method in which an ethylenically unsaturated monomer previously emulsified with a modified polyvinyl alcohol aqueous solution is continuously added to the polymerization reaction system can also be adopted. The amount of the modified polyvinyl alcohol used is 1 to 100 parts by weight of the polymer of the ethylenically unsaturated monomer.
It is in the range of 15 parts by weight, preferably 2 to 12 parts by weight.
If the amount used is less than 1 part by weight or more than 15 parts by weight, the polymerization stability is lowered, or the wet strength and water resistance of the obtained film are lowered. In the composition of the present invention, the above-mentioned modified polyvinyl alcohol is used as a dispersant in the aqueous emulsion used as the component (A), and if necessary, a conventionally known anionic, nonionic or cationic agent may be used. A surfactant, a polyvinyl alcohol polymer, hydroxyethyl cellulose and the like can also be used in combination.

In the composition of the present invention, the polyamide resin used as the component (B) is preferably one which causes a crosslinking reaction with the aqueous emulsion which is the component (A), and a modified polyvinyl alcohol which is a dispersant for the aqueous emulsion. Those having a functional group that reacts with the carboxyl group of are more preferable. As a specific example of the component (B), a reaction product of a polyamide and an epoxy group-containing compound is preferable,
A reaction product of a polyamide and a glycidyl group-containing compound is more preferable, and a reaction product of a polyamide and epichlorohydrin is particularly preferably polyamide epichlorohydrin.

The polyamide epichlorohydrin is a water-soluble resin which is quaternized by allowing epichlorohydrin to act on a polyamide resin obtained by a condensation reaction of an alkylpolyamine compound and an alkyldicarboxylic acid,
For example, a polyamide obtained from adipic acid and diethylenetriamine may be treated with epichlorohydrin. The degree of polymerization of the polyamide resin as the component (B) is not particularly limited, but the Brookfield type viscosity (B type viscosity) of a 10% by weight aqueous solution at a temperature of 25 ° C. is preferably 5 to 10,000 mPas.
s · s (millipascal second), more preferably 10 to 5,0
00 mPas · s, more preferably 10 to 1,000 m
It should be in the range of Pas · s. The functional group content of the polyamide resin is not particularly limited, but 0.01
The range is preferably from 1 to 100 mol / 100 g, more preferably from 0.03 to 0.5 mol / 100 g.

There are various methods for preparing the emulsion composition of the present invention. Generally, the polyamide resin as the component (B) is used as it is or as an aqueous solution.
Alternatively, it is prepared by dissolving it in an appropriate water-soluble solvent and then adding and mixing it with the aqueous emulsion which is the component (A). The amount of the component (B) added is 0.1 to 3 parts by weight based on 100 parts by weight of the solid content of the emulsion.
The range of 0 parts by weight is preferable, and the range of 0.2 to 15 parts by weight is more preferable. If the amount of the component (B) added is less than 0.1 part by weight, the effect of the present invention, that is, the wet strength, water resistance, hot water resistance, and heat resistance of the film, tends to be insufficient. If it exceeds the above range, the mixing stability with the emulsion may be decreased, the pot life may be shortened, and the water resistance may be decreased, which is not preferable.

The emulsion composition of the present invention basically comprises the above-mentioned aqueous emulsion which is the component (A) and a polyamide resin which is the component (B), and, if necessary, starch, modified starch, and oxidation. Starch, sodium alginate, carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, maleic anhydride /
Water-soluble polymer compounds such as isobutene copolymer, maleic anhydride / styrene copolymer, maleic anhydride / methyl vinyl ether copolymer, urea / formalin resin, urea / melamine / formalin resin, phenol / formalin resin, etc. The thermosetting resin used as the adhesive can be used as appropriate. Further, the emulsion composition of the present invention contains fillers such as clay, kaolin, talc, calcium carbonate, and wood flour, extenders such as wheat flour, reaction accelerators such as boric acid and aluminum sulfate, pigments such as titanium oxide, and the like. In addition, various additives such as preservatives and rust preventives can be added as appropriate.

[0018]

EXAMPLES 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 weight basis unless otherwise specified. The pot life of the composition, the wet tensile strength of the film, the water resistance of the film, the hot water resistance and the heat resistance were measured as follows. (1) Pot life The gelling time (time until the composition loses fluidity) when the composition was placed in a lidded container and left at 20 ° C. was measured. (2) Wet Tensile Strength of Coating Film The composition was cast on a glass plate and dried at 50 ° C. to form a coating film having a thickness of 0.5 mm. 20 this film
After soaking in water at ℃ for 24 hours, pull the film from the water,
The maximum strength was measured as it was without drying, using an autograph (manufactured by Shimadzu Corporation) at a tensile speed of 100 mm / min. (3) Water resistance of coating film The coating film obtained as described in (2) above was immersed in water at 30 ° C for 24 hours, then the coating film was taken out of water and the surface water was wiped with filter paper to obtain the weight change. The swelling degree was calculated by the following formula. Swelling degree = (weight after immersion−weight before immersion) / weight before immersion (4) Hot water resistance of the film The film obtained as in the above (2) was immersed in hot water at 100 ° C. for 1 hour. , And examined the changes with the naked eye. (5) Heat resistance of the film Cross-section 1 is formed on the tip of the film obtained as described in (2) above.
A weight of 10 g per mm ² was attached, the outside air was raised by 5 ° C. per minute, and the temperature at which the film softened and the weight fell was measured.

Example 1 In a 1 liter glass-made polymerization vessel equipped with a reflux condenser, a dropping funnel, a thermometer and a nitrogen inlet, 400 g of water and modified polyvinyl alcohol [0.3 mol% of lauryl vinyl ether as a component (a)] were added. , (B) component crotonic acid 3.
97.8 mol% of the vinyl acetate component of the polyvinyl acetate ester-based copolymer containing 7 mol% is saponified,
Further, 24 g of a 4% aqueous solution having a viscosity of 37 centipoise at 20 ° C. of D = 0.99] was charged and completely dissolved at 95 ° C. Next, after cooling this polyvinyl alcohol aqueous solution and purging with nitrogen, 400 g of vinyl acetate was charged while stirring at 140 rpm, the temperature was raised to 60 ° C., and then polymerization was carried out in the presence of a hydrogen peroxide / Rongalit redox initiator system. . The polymerization was completed in 2 hours, and the polymerization rate was 99.8%,
A stable polyvinyl acetate emulsion having a solid content concentration of 50.4% and a viscosity of 2000 mPas · s was obtained. A composition was prepared by adding 10 parts of dibutyl phthalate as a plasticizer to 100 parts of the solid content of this emulsion, and further mixing 1 part of polyamide epichlorohydrin (WS-525, manufactured by Nippon PMC). The pot life, wet tensile strength of the coating, water resistance, hot water resistance and heat resistance of the above composition were determined. The results are shown in Table 1.

Comparative Example 1 Example 1 was repeated except that no polyamide resin was added to the polyvinyl acetate emulsion prepared in Example 1.
A composition was prepared and evaluated in the same manner as in. The results are shown in Table 1.

Comparative Examples 2 to 4 In Example 1, except that aluminum chloride (Comparative Example 2), diphenylmethane diisocyanate (Comparative Example 3) and glyoxal (Comparative Example 4) were used instead of polyamide epichlorohydrin, respectively. A composition was prepared and evaluated in the same manner as in 1. The results are shown in Table 1.

Comparative Example 5 The procedure of Example 1 was repeated except that unmodified polyvinyl alcohol (polymerization degree: 1750, saponification degree: 87.5 mol%) was used in place of the modified polyvinyl alcohol. Emulsion polymerization was performed. As a result, the polymerization rate was 99.8%, the solid content concentration was 50.4%, and the viscosity was 2800 mP.
A stable polyvinyl acetate emulsion of as.s was obtained. To 100 parts of the solid content of this emulsion, 10 parts of dibutyl phthalate and 6 parts of the modified polyvinyl alcohol of Example 1 were post-added, and further 1 part of polyamide epichlorohydrin (WS-525, manufactured by Nippon PMC Co., Ltd.) was added to the composition. The product was prepared and evaluated. The results are shown in Table 1.

Comparative Example 6 In Comparative Example 5, polyamide epichlorohydrin (WS-52) was used instead of 1 part of polyamide epichlorohydrin.
5, a composition was prepared and evaluated in the same manner as in Comparative Example 5 except that 1 part of Nippon PMC Co., Ltd. and 2.5 parts of chitosan (OTS, Dainichiseika Co., Ltd.) were used. The results are shown in Table 1.

Comparative Example 7 A composition was prepared and evaluated in the same manner as in Comparative Example 5, except that the modified polyvinyl alcohol was not added later. The results are shown in Table 1.

Comparative Example 8 A composition was prepared and evaluated in the same manner as in Comparative Example 5 except that 1 part of diphenylmethane diisocyanate was used in place of 1 part of polyamide epichlorohydrin in Comparative Example 5. The results are shown in Table 1.

Comparative Example 9 A composition was prepared and evaluated in the same manner as in Comparative Example 5, except that 1 part of diphenylmethane diisocyanate and 0.3 part of aluminum chloride were used in place of 1 part of polyamide epichlorohydrin in Comparative Example 5. . The results are shown in Table 1.

[0027]

[Table 1]

Note 1) It is parts by weight based on 100 parts by weight of the monomer. 2) Parts by weight based on 100 parts by weight of solid content. 3) HL-PVA: 0.3 mol% of lauryl vinyl ether as the component (a) and 3. 3% of crotonic acid as the component (b).
97.8 mol% of the vinyl acetate component of the polyvinyl acetate ester-based copolymer containing 7 mol% is saponified,
And modified polyvinyl alcohol having a 4% aqueous solution viscosity at 20 ° C. of 37 centipoise and D = 0.99 4) Unmodified PVA: degree of polymerization 1750, degree of saponification 87.5 mol%

[0029]

[Table 2]

Example 2 A 1 liter glass-made polymerization vessel equipped with a reflux condenser, a dropping funnel, a thermometer and a nitrogen blowing port was charged with 400 g of water and a modified polyvinyl alcohol having a thiol group at the end [average carbon as component (a)]. 0.5 mol% of branched fatty acid vinyl ester having a number of 10 (VeoVa-10 manufactured by Shell Co.),
As component (b), 96.5 mol% of the vinyl acetate component of the polyvinyl acetate ester-based copolymer containing 3.0 mol% of itaconic acid and having a thioacetic acid ester group at the terminal is saponified, and 20 4% aqueous solution viscosity at ℃ 1
0 centipoise, [SH] concentration is 5.0 × 10 ^-5 mol / g
-Polyvinyl alcohol having D = 0.60] 28
g was charged and completely dissolved at 95 ° C. Next, after cooling this polynyl alcohol aqueous solution, the pH was adjusted to 4.0 with dilute sulfuric acid, nitrogen substitution was carried out, and while stirring at 140 rpm, 80 g of methyl methacrylate and 80 g of n-butyl acrylate were charged, and 70 After the temperature was raised to 0 ° C., 5 g of a 5% ammonium persulfate aqueous solution was added to initiate polymerization. Then, 120 g of methyl methacrylate and 120 g of n-butyl acrylate were sequentially added over 2 hours. The polymerization was completed in 4 hours, and a stable poly (methyl methacrylate / butyl acrylate) copolymer emulsion having a polymerization rate of 99.9%, a solid content concentration of 51.5% and a viscosity of 1100 mPas · s was obtained.

This emulsion was used in the same manner as in Example 1 except that dibutyl phthalate as a plasticizer was not added. The following Examples 3 and 4 and Comparative Examples 10 to 1 were used.
The same applies to 4. ), And emulsion solid content 10
Polyamide epichlorohydrin (WS-
525, manufactured by Japan PMC Co., Ltd.) was added and mixed to prepare a composition, and the composition was evaluated. The results are shown in Table 2.

Comparative Example 10 A composition was prepared and evaluated in the same manner as in Example 2 except that polyamide epichlorohydrin was not added. The results are shown in Table 2.

Comparative Example 11 In Example 2, polyvinyl alcohol modified with a terminal thiol group (polymerization degree: 500, saponification degree: 88.2 mol%, [S
H] Concentration: 5.0 × 10 ⁻⁵ mol / g-polyvinyl alcohol) The emulsion polymerization of methyl methacrylate and n-butyl acrylate was carried out in the same manner as in Example 2. The obtained emulsion was a stable poly (methyl methacrylate / n-butyl acrylate) copolymer emulsion having a polymerization rate of 99.9%, a solid content concentration of 51.4% and a viscosity of 850 mPas · s. 1 part of polyamide epichlorohydrin was added and mixed in the same manner as in Example 2 except that this emulsion was used to prepare and evaluate a composition. The results are shown in Table 2.

Comparative Example 12 In the same manner as in Example 2 except that 16 g of a nonionic emulsifier (Nonipol 200, manufactured by Sanyo Kasei Co., Ltd.) was used in place of the modified polyvinyl alcohol having a terminal thiol group. A poly (methyl methacrylate / n-butyl acrylate) copolymer emulsion was obtained. This emulsion was stable with a polymerization rate of 99.9%, a solid content concentration of 51.4% and a viscosity of 25 mPas · s. To 100 parts of the solid content of this emulsion, 7 parts of the modified polyvinyl alcohol of Example 2 was added, and 1 part of the same polyamide epichlorohydrin as in Example 2 was added and mixed to prepare and evaluate a composition. The results are shown in Table 2.

Example 3 12 g of modified polyvinyl alcohol having a thiol group at the end as in Example 2 was dissolved by heating in 290 g of ion-exchanged water, and the solution was placed in a pressure-resistant autoclave equipped with a nitrogen blowing port and a thermometer. . After adjusting the pH to 4.0 with dilute sulfuric acid, 165 g of styrene was charged, then 135 g of butadiene was charged from a pressure resistance meter, and the temperature was raised to 70 ° C. and then 2%.
Polymerization was initiated by pressing in 10 g of an aqueous potassium persulfate solution. The internal pressure decreased from 4.8 kg / cm ² G as the polymerization proceeded, and decreased to 0.4 kg / cm ² G after 15 hours. The polymerization rate was measured and found to be 99.2%. The obtained emulsion was adjusted to pH 6.0 with aqueous ammonia, and the solid content concentration was 49.0%.
A stable poly (styrene-butadiene) copolymer emulsion having a viscosity of 1800 mPas · s was obtained. Polyamide epichlorohydrin (WS-525) was added to 100 parts of the solid content of this emulsion in the same manner as in Example 1.
1 part (manufactured by Japan PMC) was added to prepare a composition and evaluated. The results are shown in Table 2.

Comparative Example 13 A composition was prepared and evaluated in the same manner as in Example 3, except that polyamide epichlorohydrin was not added. The results are shown in Table 2.

Example 4 12 g of the modified polyvinyl alcohol of Example 1 was dissolved in 290 g of deionized water by heating, and the solution was placed in a pressure resistant autoclave equipped with a nitrogen inlet and a thermometer. After adjusting the pH to 4.0 with dilute sulfuric acid, 300 g of vinyl acetate was charged, and then the pressure of ethylene was increased to 45 kg / cm ² G (the amount of ethylene charged corresponds to 60 g). After the temperature was raised to 60 ° C., polymerization was initiated with a hydrogen peroxide-Rongalit redox initiator. After 2 hours, the residual vinyl acetate concentration is 0.7
The polymerization was terminated when the percentage reached. Solid content concentration 52.5
%, A stable poly (vinyl acetate-ethylene) copolymer emulsion having a viscosity of 3200 mPas · s was obtained. Polyamide epichlorohydrin (WS-525) was added to 100 parts of the solid content of this emulsion in the same manner as in Example 1.
1 part (manufactured by Japan PMC) was added to prepare a composition and evaluated. The results are shown in Table 2.

Comparative Example 14 A composition was prepared and evaluated in the same manner as in Example 4 except that polyamide epichlorohydrin was not added. The results are shown in Table 2.

[0039]

[Table 3]

Note 1) It is parts by weight based on 100 parts by weight of the monomer. However, in Example 4 and Comparative Example 14, the values are based on 100 parts by weight of vinyl acetate. 2) Parts by weight based on 100 parts by weight of solid content. 3) HL-SH-PVA: a branched fatty acid vinyl ester having an average carbon number of 10 as the component (a) (V manufactured by Shell Co., V
vinyl acetate component of polyvinyl acetate ester-based copolymer containing 0.5 mol% eoVa-10), 3.0 mol% itaconic acid as component (b), and thioacetic acid ester group at the end Of which 96.5 mol% was saponified and 2
The viscosity of a 4% aqueous solution at 0 ° C is 10 centipoise, [S
H] 5.0 × 10 ⁻⁵ mol / g-PVA, modified polyvinyl alcohol with D = 0.60 4) SH-PVA: polyvinyl alcohol modified with terminal thiol group, polymerization degree 500, saponification degree 88.2 mol%, [ S
H] 5.0 × 10 ⁻⁵ mol / g-PVA 5) HL-PVA: 0.3 mol% of lauryl vinyl ether as the component (a), and crotonic acid as the component (b) of 3.
97.8 mol% of the vinyl acetate component of the polyvinyl acetate ester-based copolymer containing 7 mol% is saponified,
And 4% aqueous solution viscosity at 20 ° C. is 37 centipoise, modified polyvinyl alcohol having D = 0.99 Meaning of symbol of monomer MMA: methyl methacrylate n-BA: n-butyl acrylate St: styrene Bu: butadiene Et: ethylene VAc : Vinyl acetate

[0041]

[Table 4]

[0042]

The emulsion composition of the present invention has a long pot life, a high wet strength of a film obtained by evaporation of water after coating, and water resistance, hot water resistance and heat resistance of the film. It is a thing. Therefore, the emulsion composition of the present invention can be widely and effectively utilized in, for example, paints, adhesives, fiber processing agents, paper processing agents and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C09D 129/04 PFN 129/10 PFP 131/04 PFU 133/02 PFW 177/00 PLS // C08F 2 / 22 MBL

Claims (1)

[Claims] 1. At least one monomer (a) selected from a vinyl ester of a fatty acid having 5 or more carbon atoms, an alkyl vinyl ether having an alkyl group having 4 or more carbon atoms, and an α-olefin having 6 or more carbon atoms. Saponification of a copolymer containing at least one monomer (b) selected from ethylenically unsaturated carboxylic acids and acid anhydrides thereof and vinyl acetate (c) as an essential copolymerization component An emulsion composition comprising an aqueous emulsion (A) and a polyamide resin (B), wherein the modified polyvinyl alcohol thus obtained is used as a dispersant and a polymer of an ethylenically unsaturated monomer is used as a dispersoid.