JPH09157311A - Aqueous dispersion resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a film excellent in water resistance and heat resistance by emulsion polymn. of (B) an ethylenically unsatd. compd. in the presence of (A) a reactive N-allyl alkenylsuccinamide surfactant as the emulsifier. SOLUTION: (B) An ethylenically unsatd. compd. is emulsion-polymerized using as the emulsifier (A) a reactive N-allyl alkenylsuccinamide surfactant which has a structure of formula I [wherein R is a 6-48C linear or branched satd. hydrocarbon group or a 6-48C linear or branched unsatd. hydrocarbon group having 1-12 unsatd. double bonds; and M is H, an alkali (earth) metal, an ammonium group, or an org. base]. 0.1-20wt.% component (A) is blended with 80-99.9wt.% component (B). Examples of the component (B) include hydrophobic compds. such as arom. vinyl compds., vinyl cyanide compds., diene compds., and unsatd. carboxylic ester compds., and hydrophilic compds. such as unsatd. carboxylic acid compds. and unsatd. carboxylamides. The polymn. temp. is varied depending on the kinds of monomer and polymn. initiator to be used. Water is used as a main solvent in combination with an org. solvent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a water-dispersible synthetic resin composition.

[0002]

2. Description of the Related Art Emulsifiers (surfactants) form micelles that act as reaction sites for hydrophobic monomers in emulsion polymerization, and after polymerization function as dispersion stabilizers for the resulting polymers, providing mechanical and chemical stability to emulsions. Imparts sex. Emulsifiers are substances useful in producing synthetic resin emulsions, while synthetic resin emulsions using emulsifiers tend to cause foaming problems because the surface tension generally decreases, and further adhesion of polymer films There is a problem that physical properties such as properties, water resistance, weather resistance, and heat resistance are deteriorated. In order to solve these problems, a technique of using a copolymerizable reactive surfactant as an emulsifier is known.

[0003]

However, the reactive surfactants that have been used conventionally have a problem in that the water resistance and heat resistance of a polymer film prepared from an emulsion are not sufficient.

[0004]

[Means for Solving the Problems] The present inventors have carried out emulsion polymerization using a novel alkenylsuccinic acid allylamide type reactive surfactant as an emulsifier, thereby forming a polymer film having excellent heat resistance and water resistance. It was found that a synthetic resin emulsion having the following formula was produced, and the present invention was accomplished.

That is, the present invention provides (1) a reactive surfactant represented by the following general formulas (1) to (4)

[0006]

Embedded image (In the above formula, R is a linear or branched saturated hydrocarbon group having 6 to 48 carbon atoms, or a linear or branched unsaturated hydrocarbon group having 6 to 48 carbon atoms and 1 to 12 unsaturated double bonds. Represents a saturated hydrocarbon group, M represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, or an organic base. (2) 0.1 to 20% by weight of the reactive surfactant of (1) and ethylenic The present invention relates to a water-dispersible resin composition obtained by emulsion polymerization of an unsaturated compound (80 to 99.9% by weight).

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The reactive surfactant of the present invention is a compound having a succinic acid allylamide structure represented by the general formulas (1) to (4) as a skeleton, and ethylene, propylene,
Produced by reaction with allylamine (MA) or diallylamine (DA) using as a raw material a compound (hereinafter abbreviated as ASA) obtained by the reaction of an olefin oligomer produced from isobutene, butadiene, etc. and maleic anhydride. (Hereinafter ASA-MA, ASA
-Abbreviated as DA).

Examples of the reaction product (ASA) of an olefin oligomer and maleic anhydride include (1) 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1- Octadecene, 1
-An addition product of a linear or branched α-olefin having 6 to 48 carbon atoms such as dococene or the like and a mixture thereof with maleic anhydride; (2) a linear or branched α-olefin having 6 to 48 carbon atoms; A reaction product of maleic anhydride with an internal olefin obtained by isomerizing a branched α-olefin or a mixture thereof in the presence of a catalyst;
A reaction product of internal olefins and maleic anhydride obtained by dehydrogenating 48 linear or branched paraffins or a mixture thereof, (4) propylene, isobutene, butadiene oligomer having 6 to 6 carbon atoms.
Those obtained by known techniques such as the reaction product of 48 with maleic anhydride, which may be a mixture of those having different carbon numbers and double bond positions of internal olefins. Carbon number of olefin oligomer is less than 6 and 4
When it exceeds 8, the amphiphilic property of ASA-MA and ASA-DA as a reactive surfactant is hindered, which is not suitable for the purpose of the present invention and is not so preferable.

By reacting the above ASA with MA and DA,
ASA-MA or ASA-DA is manufactured. AS
A-MA or ASA-DA becomes soluble or dispersible in water when the carboxyl group in the molecule is neutralized with an alkali, and the emulsion stability to a hydrophobic monomer or a mixture containing a hydrophobic monomer is improved. The pH at which water becomes soluble depends on the chain length of the hydrocarbon group of ASA, temperature conditions, the presence or absence of ionic monomers and additives, and the amount present. For example, when the alkenyl group has 16 carbon atoms, it is at room temperature. Then, the condition is usually pH 8 or higher. In addition, without neutralizing the carboxyl group, ASA-MA or ASA-DA
It is also possible to dissolve the above in a hydrophobic monomer or a mixture containing the hydrophobic monomer and carry out emulsion polymerization under weakly acidic to neutral conditions, but the polymerization system becomes unstable and aggregates are easily formed. To prevent this, it is effective to add an alkali to the polymerization system to carry out the polymerization while neutralizing it, or to use a known surfactant together. When no alkali is added, it is preferable to neutralize the carboxyl group by adding an alkali after emulsion polymerization from the viewpoint of stabilizing the emulsion, but it may be used without neutralization to improve heat resistance. .

The water-dispersible resin composition of the present invention refers to an emulsion obtained by polymerization, which is dispersed by forming micelles in water. The water-dispersible resin composition of the present invention is a compound having the succinic acid allylamide structure represented by the general formulas (1) to (4) (the ASA-MA, A
SA-DA) and an ethylenically unsaturated compound can be produced by emulsion polymerization. Examples of the ethylenically unsaturated compound to be emulsion polymerized include (I) a hydrophobic ethylenically unsaturated compound and (II) a hydrophilic ethylenically unsaturated compound.

Examples of (I) hydrophobic ethylenically unsaturated compounds are aromatic vinyl compounds, vinyl cyanide compounds, diene compounds, unsaturated carboxylic acid ester compounds,
It is one or more compounds selected from the group consisting of alkyl vinyl ether compounds, other vinyl compounds, and hydrophobic allyl compounds.

As the aromatic vinyl compound, styrene,
α-methylstyrene, α-chlorostyrene, p-ter
Examples thereof include t-butylstyrene, p-methylstyrene, p-chlorostyrene, o-chlorostyrene, 2,5-dichlorostyrene, 3,4-dichlorostyrene, divinylbenzene and the like. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. Examples of the diene compound include diolefin compounds such as allene, butadiene and isoprene, and chloroprene.

Examples of unsaturated carboxylic acid ester compounds include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate and lauryl. Methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, glycidyl acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3
-Hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate,

Ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol acrylate, Ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, dimethacrylic acid-1,3-butylene glycol, polyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, ethoxy polyethylene glycol ( Meta)
Examples thereof include acrylates, propoxy polyethylene glycol (meth) acrylates, isopropoxy polyethylene glycol (meth) acrylates, phenoxy polyethylene glycol (meth) acrylates, and divinyl compounds such as epoxy acrylates and urethane acrylates.

As the alkyl vinyl ether compound,
Vinyl methyl ether, vinyl ethyl ether, vinyl isopropyl ether, vinyl n-propyl ether,
Examples thereof include vinyl isobutyl ether, vinyl-2-ethylhexyl ether, vinyl-n-octadecyl ether and the like.

Other vinyl compounds include vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride, ethylene, propylene, butene, isoprene and α-.
Examples thereof include olefins, divinyl adipate, divinyl sebacate, and other divinyl esters, maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and the like. Furthermore, as the hydrophobic allyl compound,
Examples thereof include diallyl isophthalate, diallyl terephthalate, diethylene glycol diallyl carbonate, triallyl cyanurate and the like.

Examples of (II) hydrophilic ethylenically unsaturated compounds include one or more selected from the group consisting of unsaturated carboxylic acid compounds, unsaturated carboxylic acid amide compounds, other vinyl compounds, and hydrophilic allyl compounds. Is a compound of.

As the unsaturated carboxylic acid compound, acrylic acid, methacrylic acid, crotonic acid, angelic acid, tiglic acid, 2-pentenoic acid, β-methylcrotonic acid, β-
Methyl tiglic acid, α-methyl-2-pentenoic acid, β-
Methyl-2-pentenoic acid, maleic acid, fumaric acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid,
Glutaconic acid, α-dihydromuconic acid, 2,3-dimethylmaleic acid, 2-methylglutaconic acid, 3-methylglutaconic acid, 2-methyl-α-dihydromuconic acid, 2,
Examples thereof include acids such as 3-dimethyl-α-dihydromuconic acid and their alkali metal salts, ammonium salts, organic amine salts and the like.

As the unsaturated carboxylic acid amide compound,
Acrylamide, methacrylamide, diacetone acrylamide, N-methyl acrylamide, N-methyl methacrylamide, N, N-dimethyl acrylamide, N,
N-dimethylmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, N, N-diethylacrylamide, N, N-diethylmethacrylamide,
N-propylacrylamide, N-acryloylpyrrolidine, N-acryloylpiperidine, N-acryloylmorpholine, N, N-di-n-propylacrylamide, Nn-butylacrylamide, Nn-hexylacrylamide, Nn-hexyl Methacrylamide,
N-n-octyl acrylamide, N-n-octyl methacrylamide, N-tert-octyl acrylamide,
N-dodecyl acrylamide, Nn-dodecyl methacrylamide, N, N-diglycidyl acrylamide,
N, N-diglycidylmethacrylamide, N- (4-glycidoxybutyl) acrylamide, N- (4-glycidoxybutyl) methacrylamide, N- (5-glycidoxypentyl) acrylamide, N- (6 -Glycidoxyhexyl) acrylamide, methylenebisacrylamide, N, N'-ethylenebisacrylamide, N,
Examples thereof include N'-hexamethylene bisacrylamide and N-methylol acrylamide.

Other vinyl compounds include vinyl sulfonic acid, styrene sulfonic acid, 2-acrylamide-
Sulfonic acids such as 2-phenylpropanesulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid, and their alkali metal salts, ammonium salts, organic amine salts, N-vinyl-2-pyrrolidone, N-vinylformamide, N- Vinylacetamide, and N, N-dimethylaminoethyl acrylate (DA), N, N-dimethylaminoethyl methacrylate (DM), N, N-dimethylaminopropyl acrylamide (DMAPAA),
N, N-dimethylaminopropyl methacrylamide (D
Cationic vinyl compounds such as MAPMA),
DA, DM, DMAPAA, DMAPMA and the like are dimethylsulfate, halogenated alkyls such as methyl chloride and methyl bromide, halogenated benzyls such as allyl chloride, benzyl chloride and benzyl bromide, epihalohydrins such as epiclohydrin and epibromohydrin, Examples thereof include vinyl compounds quaternized with epoxies such as propylene oxide and styrene oxide.

Further, as the hydrophilic allyl compound,
Allylamines such as allylamine, N-methylallylamine, 2-methylallylamine, diallylamine, dimethyldiallylammonium chloride and salts thereof, allylsulfonic acids such as allylsulfonic acid and methallylsulfonic acid and salts thereof, allyl alcohol and the like. be able to.

The ethylenically unsaturated compound (B) emulsion-polymerized with the reactive surfactants ASA-MA or ASA-DA (A) represented by the general formulas (1) to (4) is (I) hydrophobic. The ethylenically unsaturated compound or a combination system of (I) and (II) hydrophilic ethylenically unsaturated compound is used.
When (II) is used, the amount of (II) used relative to (I) is usually in the range of 0.1 to 20% by weight.

The amount of polymerization of the emulsion-polymerizable ethylenically unsaturated compound (B) with ASA-MA or ASA-DA (A) is usually 0.1 to 0.1 based on the total weight of all monomers.
20% by weight, 80 to 99.9% by weight of (B), preferably (A)
Is in the range of 0.5 to 10% by weight and (B) is in the range of 90 to 99.5% by weight. If the content of (A) is less than 0.1% by weight, the emulsion stability of the resin composition of the present invention will decrease, and if it exceeds 20% by weight, the water resistance of the dry coating film of the resin composition will decrease, such being undesirable.

The water-dispersible resin composition of the present invention comprises ASA-
Using MA or ASA-DA (A) as emulsifier,
If necessary, it can be produced by a known emulsion polymerization method in the presence of a pH adjusting agent, a chain transfer agent, a protective colloid agent and the like.

As the pH adjuster, hydrochloric acid, sulfuric acid, phosphoric acid,
Inorganic acids such as boric acid, formic acid, acetic acid, succinic acid, citric acid, tartaric acid, organic acids such as L-ascorbic acid, sodium hydroxide, potassium hydroxide, inorganic bases such as ammonia, ethanolamine, trimethylamine, triethylamine, etc. And organic salts of sodium hydrogen carbonate, sodium carbonate, sodium acetate, sodium dihydrogen phosphate and the like.

As the chain transfer agent, one or a mixture of two or more of hexyl mercaptan, octyl mercaptan, dodecyl mercaptan, tetradecyl mercaptan, cetyl mercaptan, stearyl mercaptan, xanthogen disulfide, sulfur, nitroso compounds and the like can be used. It can be used as appropriate.

Further, for the purpose of sealing metal ions or adjusting the polymerization rate, a compound such as sodium ethylenediamine tetraacetate (EDTA-Na), urea or thiourea may be used in combination. The amount of pH adjuster, chain transfer agent, etc. used varies depending on the purpose of use, but the pH adjuster is generally 100 ppm to 10% relative to the monomer weight, and the chain transfer agent and other additives are 1.0 ppm to 5.0%. Is in the range.

As the protective colloid agent, partially saponified polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polyacrylamide and the like can be used. The amount of protective colloid used is generally in the range of 0.1 to 20%, preferably 0.1 to 10%, based on the total amount of the monomers.

There are no particular restrictions on the emulsion polymerization method of the ethylenically unsaturated compound, and the polymerization can be carried out by a known method. Usually, polymerization is carried out by maintaining a predetermined temperature in the presence of a radical polymerization initiator. It is not necessary to maintain the same temperature during the polymerization, and the temperature may be changed appropriately as the polymerization progresses. The heating is performed or the heat is removed as necessary. The polymerization temperature varies depending on the type of monomer used, the type of polymerization initiator, etc., and is generally in the range of 30 to 200 ° C. in the case of a single initiator, lower in the case of a redox type polymerization initiator, and collectively. The temperature is generally -5 to 50 ° C when polymerization is performed, and is generally 30 to 90 ° C when sequentially added. The atmosphere in the polymerization vessel is not particularly limited, but it is preferable to replace with an inert gas such as nitrogen gas in order to carry out the polymerization rapidly. The polymerization time is not particularly limited, but is generally 1 to 40 hours.

Although water is used as the polymerization solvent, an organic solvent such as methanol, ethanol, isopropanol, acetone, ethylene glycol or propylene glycol may be used in combination.

A general polymerization initiator can be used as the polymerization initiator. Peroxides as oil-soluble initiators include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 1,1,3,3, -tetramethylbutyl peroxide. , 2,5-dimethylhexane-2,5-dihydroperoxide, cumene hydroperoxide, tert-butyl perbenzoate, tert-butyl peracetate, tert
-Butyl perphenyl acetate, tert-butyl peroxylaurate, cumyl perbivalate Further, as the azo compound, azobisisobutyronitrile, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) ), 2,
2'-Azobis (2,4-dimethylvaleronitrile), 2,2'-
Azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 2,2'-azobis (2,4,4 -Trimethylpentane), 2,2'-azobis (2-methylpropane), dimethyl 2,2'-azobis (2-methylpropionate) and the like can be used. Furthermore, it is also possible to use two or more of the above-mentioned polymerization initiators in combination.

Examples of the water-soluble initiator include peroxides such as ammonium persulfate, potassium persulfate, hydrogen peroxide, and tert-butyl peroxide.
In this case, although it can be used alone, it can also be used as a redox polymerizing agent in combination with a reducing agent. As the reducing agent, for example, sulfite, bisulfite, iron, copper, salts of lower ions such as cobalt, hypophosphorous acid, hypophosphite, N,
Examples thereof include organic amines such as N, N ′, N′-tetramethylethylenediamine, and reducing sugars such as aldose and ketose. Further, as the azo compound, 2,2'-azobis-2-amidinopropane hydrochloride, 2,2'-azobis-2,4-
Dimethylvaleronitrile, 4,4'-azobis-4-cyanovaleic acid and salts thereof, etc. can be used. Further, two or more of the above-mentioned polymerization initiators may be used in combination. The amount of the polymerization initiator added is in the range of 0.0001 to 10% by weight, preferably 0.01 to 8% by weight, based on the monomers. Further, in the case of a redox system, the amount of the reducing agent added to the polymerization initiator is 0.1 to 100%, preferably 0.2 to 80% on a molar basis.

ASA-MA or ASA used for polymerization
-DA, monomers, a polymerization initiator, a solvent, a chain transfer agent, etc. may be charged into the reaction vessel at a time at the time of starting the polymerization, but one or more components may be used alone or in accordance with the progress of the polymerization. One mixed with a solvent or the like, for example, an emulsion solution of a monomer or the like may be sequentially added.

From the thus obtained water-dispersible resin composition which is the emulsion of the present invention, a film can be obtained by removing the solvent by drying after casting or coating, as in a general emulsion. In this case, ASA-MA or ASA-DA in the emulsion is usually a carboxylic acid salt and contributes to the stabilization of the emulsion. The polymer film produced from this emulsion has improved water resistance as compared with the case where a non-polymerizable surfactant is used. Further, when the film is acid-treated and then heat-treated, the water resistance is further improved and the heat resistance is also improved. As the acid used at this time, one or both of inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid and organic acids such as formic acid, acetic acid and citric acid are used. The heat treatment temperature and time can be appropriately changed depending on the film thickness, polymer composition, etc.
It is carried out at 150 ° C for a few seconds to a few tens of minutes. The heat treatment is performed in air or an inert gas such as nitrogen or argon.

The water-dispersible resin composition of the present invention may further contain an antiseptic agent, an antifoaming agent, a cross-linking agent, a viscosity modifier, a film-forming aid, a plasticizer, an antistatic agent, an adhesive agent, and a freezing agent, if necessary. Additives such as stabilizers, pigments, fillers and dyes may be added. The water-dispersible resin composition of the present invention is used in fields such as plasticizers, heat resistant resins, antistatic agents, lubricants, paints, adhesives, cement admixtures, and papermaking additives.

[0036]

The present invention will be described in detail below with reference to Examples.
The present invention is not limited to these examples. In the following,% is based on weight and viscosity is B at 25 ° C.
It is a value measured by a viscometer. Example 1 ASA-MA (Pavelus NP (Mitsubishi Petroleum): reaction product of ASA having C18 alkenyl group and allylamine) 5.
220.0 g, 40% caustic soda aqueous solution 1.28 g, and distilled water 53.5 g were uniformly dissolved in an aqueous solution with vigorous stirring with a magnetic stirrer, and 100.0 g of styrene was added dropwise over 30 minutes to prepare a milky white monomer emulsion. 300m equipped with stirrer, reflux condenser, nitrogen introduction pipe and dropping funnel
Add 98.3 g of distilled water to a 4-neck flask of l and replace with nitrogen.
After the temperature was raised to 0 ° C., 5.0 g of a 10% potassium persulfate aqueous solution was added, and then a monomer emulsion prepared in advance was continuously added dropwise from a dropping funnel for 2 hours. After the completion of dropping, the mixture was aged for 2 hours to obtain a milky white stable emulsion without aggregation. The pH of this emulsion is 8.20, and the solid concentration is 40.5%.
And the viscosity was 8.5 cp.

Examples 2 to 4 Polymerization was carried out in the same manner as in Example 1 except for the monomer composition shown in Table 1, and good emulsions of milky white were obtained in all cases. The results are summarized in Table 1.

Example 5 ASA-DA (Pavelus NP (Mitsubishi Petroleum): reaction product of ASA having C18 alkenyl group and diallylamine)
5.24 g, 40% caustic soda aqueous solution 1.17 g, and distilled water 53.6 g were uniformly dissolved in an aqueous solution, and 100.0 g of styrene was dripped in 30 minutes while vigorously stirring with a magnetic stirrer.
A milky white monomer emulsion was prepared. 30 equipped with stirrer, reflux condenser, nitrogen inlet tube and dropping funnel
Add 98.3 g of distilled water to a 0 ml four-necked flask, replace with nitrogen and raise the temperature to 80 ° C., then add 5.0 g of 10% potassium persulfate aqueous solution.
After adding, the previously prepared monomer emulsion was continuously added dropwise from the dropping funnel for 2 hours. After the completion of dropping, the mixture was aged for 2 hours to obtain a milky white stable emulsion without aggregation. The pH of this emulsion is 8.35 and the solid content is 41.3%.
And the viscosity was 10.6 cp.

Comparative Example 1 Polymerization was carried out in the same manner as in Example 1 except that sodium alkylbenzene sulfonate was used in place of ASA-MA, and the same amount of distilled water was used in place of 40% caustic soda. An emulsion of was obtained.

[0040]

[Table 1]

[Evaluation of Film] The emulsion solution obtained in Example 1 was dried at room temperature by a casting method to obtain 0.25.
mm film was made. The dried film was dipped in a 1.0% hydrochloric acid aqueous solution for 30 minutes, lightly wiped off water drops remaining on the film surface with a filter paper, and then heat-treated in a thermostatic dryer at 100 ° C. for 1 hour. The water resistance test was conducted by immersing the film in distilled water at room temperature and measuring the amount of absorbed water. The results are shown in Table 2. The water absorption rate (%) is represented by the weight fraction (%) of the water absorption amount per polymer film. The same test was performed for Comparative Example 1, and the results are shown in Table 2.

[0042]

[Table 2]

Heat resistance is DSC according to JIS K-7121-1987
(Tg (glass transition temperature) was measured and evaluated by a transition temperature measuring method using (Shimadzu Corporation: DSC-50). Standard polystyrene samples (Scientific Polymer Products,
INC. Standard pellets) has a Tg of 104 ° C. and the emulsion film of Example 1 before acid treatment has a Tg of 102.
℃, Tg of the film sample that was heat treated after acid treatment is 10
The Tg of the film of 6 ° C. and the film of Comparative Example 1 was 100 ° C.

[0044]

Industrial Applicability The water-dispersible resin composition of the present invention is a stable emulsion, and the polymer film obtained from the emulsion can be obtained by using a conventional surfactant as an emulsifier, as is clear from the examples. Compared with water resistance and heat resistance. Although its action is not always clear, it is considered that the alkenyl succinic acid allylamide type reactive surfactant has a high copolymerizability and therefore has almost no free monomer after polymerization. Further, regarding those having a succinic acid monoallylamide structure, it is considered that when a polymer film is subjected to an acid and a heat treatment, the succinic acid amide is dehydrated and cyclized to form an imide structure, and further various performances are improved.

Claims (2)

[Claims] 1. A reactive surfactant represented by the following general formulas (1) to (4) [Chemical formula 1]. Embedded image (In the above formula, R is a linear or branched saturated hydrocarbon group having 6 to 48 carbon atoms, or a linear or branched unsaturated hydrocarbon group having 6 to 48 carbon atoms and 1 to 12 unsaturated double bonds. Represents a saturated hydrocarbon group, M represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, or an organic base.) 2. The reactive surfactant according to claim 1, which is 0.1 to
A water-dispersible resin composition obtained by emulsion polymerization of 20% by weight and 80 to 99.9% by weight of an ethylenically unsaturated compound.