JPH10130455A - Emulsion composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an emulsion composition which has a long pot life, is excellent in workability and exhibits excellent resistance to water even when dried at a relatively low temperature, by using an emulsifying and dispersing agent comprising a PVA resin that can be produced by an industrially advantageous process. SOLUTION: An aqueous emulsion (A) obtained by using an emulsifying and dispersing agent comprising a polyvinyl alcohol modified with a diacetoneacrylamide copolymer containing 0.1-15mol% diacetoneacrylamide units and a dispersoid comprising a polymer of an ethylenically unsaturated monomer is blended with a water-soluble hydrazine compound (B) and a component (C) comprising a water-soluble organic amine or ammonia to give the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an emulsion composition capable of obtaining a film having excellent workability and excellent water resistance.

[0002]

2. Description of the Related Art Emulsions produced by using polyvinyl alcohol (hereinafter abbreviated as PVA) as an emulsifying / dispersing agent (protective colloid agent) have been used for a long time in many applications including adhesives and paints. However, PV
Since A itself is water-soluble, a film obtained by evaporating water from the emulsion easily swells in water, and when the film is immersed in water, PVA is eluted, so that its water resistance is insufficient. There was a problem.

[0003] For this reason, various methods have heretofore been attempted to increase the water resistance of a film obtained from an emulsion using a PVA-based polymer as an emulsifying / dispersing agent. For example, an adhesive obtained by adding an aliphatic aldehyde such as glyoxal to an aqueous emulsion using PVA as an emulsifying / dispersing agent (Japanese Patent Laid-Open No. 55-94937), and a crosslinking agent using an aqueous emulsion using PVA as an emulsifying / dispersing agent. And an adhesive containing an amino compound such as chitosan (JP-A-3-456)
No. 78), however, these adhesives do not have sufficient water resistance, and when coexisting with an emulsion and a cross-linking agent, have a problem in that they gel immediately and have poor workability. Was.

[0004]

On the other hand, as a method for solving these problems, PV having an acetoacetyl group is used.
A method for obtaining an emulsion composition having a long pot life by allowing a water-soluble organic amine to coexist when reacting a hydrazine compound with an emulsion using A (Japanese Patent Laid-Open No. 8-113).
687). This water resistance method is
The film obtained from the emulsion is excellent in water resistance and workability is good, but in order to produce the acetoacetylated PVA used here, a diketene is added to the PVA-based resin or transesterification of the acetoacetyl group is performed. A complicated manufacturing process such as reaction is required, which is an industrially disadvantageous method and has a problem in the uniformity of the product. In addition, the present inventors have proposed an industrially advantageous production method which has high homogeneity in the product and has a diacetone group in the side chain.
Proposed an emulsion composition comprising an emulsion using a VA polymer and a hydrazine compound (Japanese Patent Application No. 8-189).
No. 905), the water resistance of the film obtained from this composition was very good, but the pot life was not sufficient, and there was still a problem in workability.

The present invention solves the drawbacks of the prior art and uses an industrially advantageous PVA-based resin as an emulsifying / dispersing agent so that even if a cross-linking agent coexists in the resulting emulsion mixture, It is an object of the present invention to provide an emulsion composition having a long pot life, excellent workability, and capable of obtaining a film exhibiting excellent water resistance even when dried at a relatively low temperature.

[0006]

The present invention relates to (A) a diacetone acrylamide copolymer-modified PVA containing 0.1 to 15 mol% of diacetone acrylamide units as an emulsifying / dispersing agent, An emulsion composition characterized by comprising (B) a water-soluble hydrazine compound and (C) a water-soluble organic amine or ammonia in an aqueous emulsion containing a polymer as a dispersoid.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The diacetone acrylamide copolymer modified PVA used as an emulsifying / dispersing agent for the aqueous emulsion (A) used in the present invention is useful for saponifying a polymer obtained by copolymerizing a fatty acid vinyl ester and diacetone acrylamide. It can be manufactured by a known method.

The fatty acid vinyl ester used in the above copolymerization includes vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, and the like. Of these, vinyl acetate is industrially preferred.

The above-mentioned copolymerization method of a fatty acid vinyl ester and diacetone acrylamide can be carried out by various polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like. Is preferably industrially used as a solvent.

As a method for saponifying a polymer obtained by copolymerizing a fatty acid vinyl ester and diacetone acrylamide, conventionally known alkali saponification or acid saponification can be applied. Industrially preferred is a method in which an alkali hydroxide is added to a mixed solution of methanol, water, methyl acetate, benzene, etc. to add alcohol and decompose.

Aqueous emulsion (A) used in the present invention
The diacetone acrylamide copolymer-modified PVA used as an emulsifying / dispersing agent can be copolymerized with a fatty acid vinyl ester or diacetone acrylamide as long as the effect of the present invention is not impaired. For example, crotonic acid, acrylic acid, methacrylic acid Unsaturated monocarboxylic acids such as acids and their esters, salts, anhydrides, amides and nitriles, unsaturated dicarboxylic acids such as maleic acid, itaconic acid and fumaric acid and salts thereof, and unsaturated monocarboxylic acids such as monomethyl maleate and monomethyl itaconate Saturated dibasic acid monoalkyl esters, α-olefins having 2 to 30 carbon atoms, alkyl vinyl ethers
It may be copolymerized with ters and vinylpyrrolidones. In addition, the obtained diacetone acrylamide copolymer modified PVA was post-modified by a reaction such as acetalization, urethanization, etherification, grafting, phosphoric esterification, etc., within a range not to impair the effects of the present invention. It may be something.

The diacetone acrylamide copolymer-modified PVA used in the present invention has a diacetone acrylamide unit content in the range of 0.1 to 15 mol%, preferably 0.5 to 10 mol%. If the content of diacetone acrylamide units is less than 0.1 mol%, the purpose of water resistance cannot be achieved. Further, when the content exceeds 15 mol%, not only does the water resistance effect become saturated, but also the water solubility is reduced, causing a problem in workability.

The degree of polymerization and the degree of saponification of the diacetone acrylamide copolymer-modified PVA are not particularly limited.
The viscosity of a 4% aqueous solution at 3 ° C. is preferably 3 mPa · s or more, and the saponification degree is 85 mol% or more.

Aqueous emulsion (A) used in the present invention
Examples of the ethylenically unsaturated monomer as a raw material of the dispersoid polymer include ethylene, propylene, olefins such as isoprene, vinyl chloride, vinyl fluoride, vinylidene chloride, and halogenated olefins such as vinylidene fluoride;
Vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl versatate, and vinyl pivalate; acrylics such as acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate Methacrylates such as acid esters, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, 2-hydroxyethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate and these And acrylamide, methacrylamide, N
Acrylamide monomers such as -methylolacrylamide and N, N-dimethylacrylamide; and diene-based weight bodies such as N-vinylpyrrolidone, butadiene, isoprene and chloroprene. These may be used alone or in combination of two or more. Used as a mixture.

Aqueous emulsion (A) used in the present invention
The method of producing the emulsion polymerization is to use an aqueous solution of diacetone acrylamide copolymerized modified PVA as an emulsifying and dispersing agent, and to temporarily or continuously add the ethylenically unsaturated monomer in the presence of a polymerization initiator to carry out emulsion polymerization. And diethylacetone acrylamide copolymer modified ethylenically unsaturated monomer
There is a method in which a mixture emulsified using an aqueous solution of VA is continuously added to a polymerization reaction system to carry out emulsion polymerization, and in addition, the diacetone acrylamide copolymer-modified PVA is added by post-addition to an aqueous emulsion. It may be something.

The amount of the diacetone acrylamide copolymer modified PVA to be used is usually 1 to 30 parts by weight based on 100 parts by weight of the polymer of the ethylenically unsaturated monomer. If too much diacetone acrylamide copolymer modified PVA is used, the polymerization stability may deteriorate.

As the polymerization initiator used for producing the aqueous emulsion (A), a known initiator usually used for emulsion polymerization can be used. For example,
Persulfates such as hydrogen peroxide, potassium persulfate, sodium persulfate and ammonium persulfate are exemplified. As the redox initiator, (a) at least one selected from hydrogen peroxide, cumene hydroperoxide, t-butyl hydroperoxide, persulfate, t-butyl persulfate, and t-butyl perbenzoate; (B) Fe ²⁺ , Cr ²⁺ , V
Metal ions capable of undergoing electron transfer, such as ²⁺ , Co ²⁺ , Ti ³⁺ , Cu ²⁺ , and (c) among reducing substances such as Rongalit and 1-ascorbic acid, (a) and (b) Alternatively, it is used in a combination of (a), (b) and (c).

As the emulsifying / dispersing agent in the aqueous emulsion (A) of the present invention, as long as the effects of the present invention are not impaired, PVA-based polymers other than diacetone acrylamide copolymerized modified PVA, water-soluble synthetic polymers, anions A nonionic, cationic surfactant, a water-soluble natural polymer or a derivative thereof can be used in combination.

As the water-soluble hydrazine compound (B) used in the present invention, various compounds can be used, such as hydrazine, hydrazine hydrate, hydrazine monohydrate or salt, phenylhydrazine, methylhydrazine, and the like.
Aromatic or aliphatic hydrazines such as ethylhydrazine, n-propylhydrazine, n-butylhydrazine, ethylene-1,2-dihydrazine, propylene-1,3-dihydrazine, butylene-1,4-dihydrazine and salts thereof Benzoic acid hydrazide, formic acid hydrazide, acetate hydrazide, propionic acid hydrazide, n-butyric acid hydrazide, isobutyric acid hydrazide, n-valeric acid hydrazide, monocarboxylic acid hydrazide such as pivalic acid hydrazide, oxalic acid dihydrazide, and malonone. Dicarboxylic acid dihydrazide, carbonic acid dihydrazide, etc. Such as a polymer compound having a hydrazino group, such as hydrazine and N- amino polyacrylamide. These hydrazine compounds may be used alone or in combination.

Among them, N-aminopolyacrylamide having a number average degree of polymerization of 30 or more is more preferable because the polyvinyl alcohol-based resin has a particularly high water resistance effect and is a polymer, so that it has little adverse effect on the human body. This N-aminopolyacrylamide can be produced by reacting hydrazine hydrate with polyacrylamide. Even if all amide groups of polyacrylamide have reacted with hydrazine, unreacted amide groups remain. You may. That is, N-aminopolyacrylamide used in the present invention is represented by the following chemical formula.

[0021]

Embedded image

In the above chemical formula, n = 0.1
-100 mol%, and m = 0 to 99.9 mol%. That is, the content of the hydrazino group in the N-aminopolyacrylamide in this case is desirably 0.1 mol% or more, and more desirably 1 mol% or more.

The amount of the water-soluble hydrazine compound (B) used in the present invention can be variously varied, but the diacetone acrylamide copolymer-modified PVA 100 used as an emulsifying / dispersing agent for an aqueous emulsion can be used. Usually 0.1 to 50 parts by weight, preferably 0.1 to 50 parts by weight, based on parts by weight.
5 to 30 parts by weight are used. When the addition amount of the hydrazine compound is less than 0.1 part by weight, the water resistance effect is low, and when it exceeds 50 parts by weight, not only the water resistance effect becomes saturated, but also the unreacted hydrazine compound is dissolved in water. May be eluted.

In the water-soluble organic amine or ammonia (C) used in the present invention, various water-soluble organic amines can be used. Examples thereof include monoethanolamine, aminoethylethanolamine, and monoethylamine. Isopropanolamine, N- (2-hydroxypropyl) -ethylenediamine, 2-amino-1-butano-
2-amino-2-methyl-1-propanol, 3-
Amino-1-propanol, 2-amino-2-methyl-
1,3-propanediol, 2-amino-2-ethyl-
Primary alkanolamines such as 1,3-propanediol, tris (hydroxyethyl) -aminomethane, diethanolamine, methylethanolamine, butylmethanolamine, N-acetylethanolamine, diisopropylamine and the like. Tertiary alkanolamines such as secondary alkanolamine, triethanolamine, methyldiethanolamine, dimethylethanolamine, diethylethanolamine, ethyldiethanolamine, triisopropanolamine, etc., methylamine, ethylamine, n-propyl Amine, isopropylamine, allylamine, n-butylamine, isobutylamine, t-
Examples include primary alkylamines such as butylamine and cyclohexylamine, secondary alkylamines such as dimethylamine, diethylamine and diisopropylamine, and tertiary alkylamines such as trimethylamine. The effect is not changed by using ammonia. These water-soluble organic amines and ammonia (C) can be used alone or in combination of two or more.

The amount of the water-soluble organic amine or ammonia (C) used in the present invention can be varied and can be selected depending on the purpose of use. Equimolar or more is desirable. When the amount is less than equimolar to the hydrazine compound, the pot life is improved as compared with the case where no water-soluble organic amine or ammonia is added, but the effect is small.

The emulsion composition of the present invention may contain, if necessary, PVA other than the present invention, starch, methylcellulose,
Cellulose derivatives such as carboxymethyl cellulose, polyacrylic acid derivatives, other natural polymers such as gelatin, synthetic polymers, inorganic fillers such as clay, kaolin, talc, silica, calcium carbonate, glycerin, sorbitol A plasticizer such as phenol, a surfactant, an antifoaming agent, a chelating agent and the like can be blended within a range that does not impair the effects of the present invention.

In the emulsion composition of the present invention,
The reaction of the diacetone acrylamide unit of the diacetone acrylamide copolymer modified PVA used as the emulsifying and dispersing agent of the aqueous emulsion (A) with the hydrazine compound (B) is carried out in the absence of the water-soluble organic amine or ammonia (C). Since it occurs rapidly and it is difficult to exert the effects of the present invention, it is desirable to add and mix the hydrazine compound (B) after mixing the aqueous emulsion with the water-soluble organic amine or ammonia (C).

In the emulsion composition of the present invention, in the state of the emulsion mixture, the reaction between the diacetone acrylamide unit in the PVA-based resin and the hydrazine compound is suppressed. An acetone acrylamide unit reacts with a hydrazine compound. At that time, the purpose of making the emulsion film water-resistant can be achieved by drying at room temperature or by heating.

In the present invention, the mechanism by which the pot life of the emulsion composition is improved in the presence of the water-soluble organic amine or ammonia has not been sufficiently elucidated, but the water-soluble organic amine or ammonia has some form of action. It is considered that this inhibits the reaction between the diacetone acrylamide unit and the hydrazine compound. It is considered that these emulsion mixtures are concentrated in the course of drying and at the same time react with the diacetone acrylamide unit and the hydrazine compound, so that the composition finally achieves water resistance.

[0030]

The present invention will be specifically described below with reference to examples. In addition, the performance of the emulsion composition was evaluated as follows.

[0031] Viscosity Stability (Pot Life) Test of Emulsion Composition The emulsion composition was left at 30 ° C. and the time until gelation was measured.

[0032] Water resistance (water drop test)
Drying at 65 ° C and 65% RH for 4 days to produce a 200μ thick emulsion film, dropping a drop of pure water on it, and the time until the hiragana of the 8-point type printed on the newspaper below became unreadable due to whitening Was measured.

[0033] Adhesive strength The adhesive strength of the emulsion composition was evaluated according to the following method according to a normal test of compressive shear adhesive strength and a water resistance test (JIS-K6852). The emulsion composition was applied to a 25 mm × 35 mm × 10 mm rod material on a 25 mm × 20 mm adhesive surface.
It was applied with a 00g / m ^2, bonded 5kgf / cm ²
And dried at 20 ° C. and 65 RH% for 48 hours. In the normal state test, the compressive shear strength was measured as it was, and in the water resistance test, each was immersed in water at 30 ° C. for 3 hours, and then, while still wet, the compressive shear strength was measured.

[0034] Comprehensive evaluation ：: The above-mentioned stability, water resistance and adhesive strength of the emulsion composition are all excellent. ：: The above-mentioned stability, water resistance and adhesive strength of the emulsion composition have all reached practical levels. X: Any of the above-mentioned stability, water resistance, and adhesive strength of the emulsion composition has not reached a practical level.

Diacetone acrylamide copolymer modified PV
Synthesis Example A Synthesis Example 1 In a flask equipped with a stirrer, a thermometer, and a dropping funnel reflux condenser, 672 parts by weight of vinyl acetate, 10 parts by weight of diacetone acrylamide, and 178 parts of methanol were added.
After charging parts by weight and purging with nitrogen in the system, the internal temperature was reduced to 6%.
The temperature was raised to 0 ° C. A solution prepared by dissolving 1 part by weight of 2,2-azobisisobutylylonitrile in 50 parts by weight of methanol was added to the system, and polymerization was started. A solution of 55 parts by weight of diacetone acrylamide dissolved in 35 parts by weight of methanol was dropped at a constant rate over 5 hours after the initiation of the polymerization.
After a lapse of time, m-dinitrobenzene was added as a polymerization inhibitor to terminate the polymerization. The polymerization yield was 78%. The remaining vinyl acetate was distilled out while adding methanol vapor to the obtained reaction mixture to obtain a 50% aqueous methanol solution of a vinyl acetate polymer containing a diacetone acrylamide copolymer component. 500 parts by weight of this mixture was added to methanol 5
0 parts by weight and a 4% methanol solution of sodium hydroxide 10
Parts by weight and mixed well, and a saponification reaction was carried out at 40 ° C. The obtained gel was pulverized, thoroughly washed with methanol, and dried to obtain a diacetone acrylamide copolymer-modified PVA. In addition, elemental analysis revealed that the content of diacetone acrylamide units in this resin was 5.0 mol%. The viscosity of a 4% aqueous solution of this resin at 20 ° C. is 26.8 mPa · s, and the saponification degree is 98.
It was 4 mol%. This viscosity was measured using a B-type viscometer.
The measurement was performed at a rotation speed of rpm.

Synthesis Examples 2 and 3 Diacetone acrylamide copolymer modified PV as shown in Table 1 was prepared in the same manner as in Synthesis Example 1 by changing the charge composition.
A was obtained.

[0037]

[Table 1]

Example 1 A glass polymerization vessel equipped with a reflux condenser, a dropping funnel, a thermometer, and a nitrogen inlet was charged with 500 parts by weight of ion-exchanged water, and copolymerized with the diacetone acrylamide obtained in Synthesis Example 1. P
VA resin (4% aqueous solution viscosity at 20 ° C. 26.8 m
(Pa.s, 98.4 mol% saponification degree, 5.0 mol% modification degree) 39 parts by weight were charged and completely dissolved at 95 ° C. This was cooled to 70 ° C., 0.5 parts by weight of ammonium persulfate was added, and 460 parts by weight of vinyl acetate was continuously added over 2 hours while stirring under a nitrogen atmosphere.
The temperature was raised to ° C., and a thermoforming reaction was further performed for 2 hours to complete the emulsion polymerization, thereby obtaining a vinyl acetate resin emulsion.

To 100 parts by weight of this emulsion was added 2 parts by weight of a 10% aqueous solution of monoethanolamine, mixed well, and then mixed with N-aminopolyacrylamide (manufactured by Otsuka Chemical Co., Ltd.).
2 parts by weight of a 10% aqueous solution of a polyacrylic hydrazide L type, a degree of polymerization of 100, and a degree of hydrazino group modification of 10.0 mol%) were added and mixed again to prepare an emulsion composition.

This emulsion composition did not gel at 30 ° C. even if left for one month or more. Further, when a water drop test was performed on the film obtained from this emulsion composition, the film was dried again before the film completely whitened, and the water resistance was very excellent. The compression shear adhesion strength of the emulsion, the normal test was 84.5kgf / cm ^2, the water resistance test was 73.5kgf / cm ^2. Table 2 shows the results
It was shown to.

Example 2 An emulsion composition was prepared in the same manner as in Example 1 except that 4 parts by weight of a 10% aqueous solution of adipic dihydrazide was added instead of 2 parts by weight of a 10% aqueous solution of N-aminopolyacrylamide. , Stability test, water drop test and compression shear strength measurement test. The results are shown in Table 2. The stability, water resistance and adhesion strength of the emulsion composition were good.

Example 3 1 part of a 10% aqueous solution of monoethanolamine was replaced by 2 parts by weight.
An emulsion composition was prepared in the same manner as in Example 1 except that 3% by weight of a 0% aminoethylethanolamine aqueous solution was added, and a stability test, a water drop test, and a measurement test of compression shear adhesive strength were performed. The results are shown in Table 2. The stability, water resistance and adhesion strength of the emulsion composition were good.

Example 4 1 part of a 10% monoethanolamine aqueous solution was replaced by 2 parts by weight.
An emulsion composition was prepared in the same manner as in Example 1 except that 3 parts by weight of an aqueous 0% 3-amino-1 propanol solution was added, and a stability test, a water drop test, and a measurement test of compression shear adhesive strength were performed. Was. The results are shown in Table 2. The stability, water resistance and adhesion strength of the emulsion composition were good.

Example 5 1 part of a 10% aqueous solution of monoethanolamine was replaced by 2 parts by weight.
An emulsion composition was prepared in the same manner as in Example 1 except that 2% by weight of a 0% aqueous ammonia solution was added, and a stability test, a water drop test, and a measurement test of compression shear adhesive strength were performed.
The results are shown in Table 2. The stability, water resistance and adhesion strength of the emulsion composition were good.

Example 6 In place of the diacetone acrylamide copolymer-modified PVA resin obtained in Synthesis Example 1, the diacetone acrylamide copolymer-modified PVA resin obtained in Synthesis Example 2 (4% aqueous solution viscosity at 20 ° C.) 25.6 mPa · s, saponification degree 98.
A vinyl acetate resin emulsion was prepared in the same manner as in Example 1 except that 39 parts by weight (2 mol%, degree of modification 1.0 mol%) was used to prepare an emulsion composition. In the same manner as in Example 1, the emulsion composition was subjected to a stability test, a water drop test, and a compression shear adhesive strength measurement test. The results are shown in Table 2. The stability, water resistance and adhesion strength of the emulsion composition were good.

Example 7 An emulsion composition was prepared in the same manner as in Example 1 except that the amount of the 10% aqueous solution of N-aminopolyacrylamide was changed from 2 parts by weight to 10 parts by weight. A compression shear adhesion strength measurement test was performed. The results are shown in Table 2. The emulsion composition did not gel until after 9 days, and had good water resistance and adhesive strength.

Example 8 An emulsion composition was prepared in the same manner as in Example 1 except that the amount of the 10% aqueous monoethanolamine solution was changed from 2 parts by weight to 0.5 parts by weight, and a stability test and a water drop test were performed. , A compression shear adhesion strength measurement test was performed. Table 2 shows the results
It was shown to. The emulsion composition did not gel until after 12 days, and had good water resistance and adhesive strength.

Example 9 The addition amount of a 10% aqueous ammonia solution was changed from 2 parts by weight to 0.5%.
An emulsion composition was prepared in the same manner as in Example 5, except that the amount was changed to parts by weight, and a stability test, a water drop test, and a measurement test of compression shear adhesive strength were performed. The results are shown in Table 2.
The emulsion composition did not gel until after 6 days, and had good water resistance and adhesive strength.

Example 10 In a glass polymerization vessel equipped with a reflux condenser, a dropping funnel, a thermometer, and a nitrogen inlet, 500 parts by weight of ion-exchanged water, copolymerized with diacetone acrylamide obtained in Synthesis Example 1 were modified. P
VA resin (4% aqueous solution viscosity at 20 ° C. 26.8 m
Pa.s, saponification degree 98.4 mol%, modification degree 5.0 mol%), 39 parts by weight were charged and completely dissolved at 95 ° C. This was cooled to 70 ° C., and an anionic surfactant (Nippon Emulsifier) was added. 1 part by weight, New Coul 707SF) and 0.5 part by weight of ammonium persulfate are added, and while stirring under a nitrogen atmosphere, 225 parts by weight of 2-ethylhexyl acrylate, 225 parts by weight of methyl methacrylate, acrylic Acid 10
After continuously adding 2 parts by weight of the mixed monomer system over 2 hours, the temperature was raised to 80 ° C., and a thermoforming reaction was further performed for 2 hours.
The emulsion polymerization was completed to obtain an acrylic copolymer resin emulsion.

Using this emulsion, an emulsion composition was prepared in the same manner as in Example 1, and a stability test, a water drop test and a measurement test of compression shear adhesive strength were performed. The results are shown in Table 2. The stability, water resistance and adhesion strength of the emulsion composition were good.

Comparative Example 1 An emulsion composition was prepared in the same manner as in Example 1 except that monoethanolamine and N-aminopolyacrylamide were not added, and a stability test, a water drop test, and a measurement test of compression shear adhesive strength were performed. went. The results are shown in Table 2. Although the stability of the emulsion composition was good, the film was whitened in 150 seconds in the water drop test, the compression shear adhesive strength was 29.8 kgf / cm ^{2 in the} normal test, and 5.5 k in the water resistance test.
gf / cm ² , poor water resistance and low adhesive strength.

Comparative Example 2 An emulsion composition was prepared in the same manner as in Example 1 except that monoethanolamine was not added, and a stability test was carried out. Gelation occurred in about 10 minutes, a water drop test, and compression shearing. The measurement test of the adhesive strength could not be performed.
The results are shown in Table 2.

Comparative Example 3 An emulsion composition was prepared in the same manner as in Example 1 except that N-aminopolyacrylamide was not added, and a stability test, a water drop test and a measurement test of compression shear adhesive strength were performed. The results are shown in Table 2. The stability of the emulsion composition was good, but the water resistance was poor, and the normal state and the water-resistant adhesive strength were also low.

Comparative Example 4 In place of the diacetone acrylamide copolymer-modified PVA resin obtained in Synthesis Example 1, the diacetone acrylamide copolymer-modified PVA resin obtained in Synthesis Example 3 (4% aqueous viscosity at 20 ° C.) Is 25.3 mPa · s, saponification degree 9
A vinyl acetate resin emulsion was prepared in the same manner as in Example 1 except that 39 parts by weight (8.5 mol%, degree of modification 0.05 mol%) was used to prepare an emulsion composition. In the same manner as in Example 1, the emulsion composition was subjected to a stability test, a water drop test, and a compression shear adhesive strength measurement test. The results are shown in Table 2. The stability of the emulsion composition was good, but the water resistance was poor, and the normal state and the water-resistant adhesive strength were also low.

Comparative Example 5 An emulsion composition was prepared in the same manner as in Example 10 except that no monoethanolamine was added, and a stability test was performed. As a result, gelation occurred in about 20 minutes.
The test for measuring the compressive shear bond strength could not be performed. The results are shown in Table 2.

Comparative Example 6 An emulsion composition was prepared in the same manner as in Example 10 except that N-aminopolyacrylamide was not added, and a stability test, a water drop test, and a measurement test of compression shear adhesive strength were performed. The results are shown in Table 2. Although the stability of the emulsion composition was good, the water resistance was poor, and the normal state and the water-resistant adhesive strength were low in comparison with Example 10.

[0057]

[Table 2]

[0058]

As is apparent from the above description, the emulsion composition of the present invention has a long pot life and excellent workability in the state of an emulsion mixture, and can be dried at a relatively low temperature. It was possible to obtain a film exhibiting sufficient water resistance.

The emulsion composition of the present invention is useful for a wide range of applications such as adhesives, paints, paper processing agents, various binders and mortar admixtures that require water resistance, and is particularly useful as an adhesive. , But is not limited to this.

Claims (1)

[Claims] 1. An emulsifying / dispersing agent comprising (A) diacetone acrylamide copolymerized modified polyvinyl alcohol containing 0.1 to 15 mol% of diacetone acrylamide units,
An emulsion composition comprising an aqueous emulsion containing a polymer of an ethylenically unsaturated monomer as a dispersoid, and (B) a water-soluble hydrazine compound and (C) a water-soluble organic amine or ammonia.