JPH09299782A - Water dispersion type resin composition containing amphiphilic polymer as dispersion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a high-polymer surfactant with which the unequal presence of a polymer layer having high hydrophilicity in the surface phase of an emulsion is possible without liberation into a water phase by copolymerizing a reactive surfactant expressed by a specific formula having succinic acid skeleton and a hydrophilic ethylenic satd. compd. SOLUTION: The high-polymer surfactant used in the case of efficient production of water dispersant emulsion particles is prepd. by copolymerizing 0.1 to 90wt.% reactive surfactant expressed by formulas I to IV and 10 to 99.9wt.% hydrophilic ethylenic unsatd. compd. In the formulas, R1 is 6-48C straight chain or branched satd. hydrocarbon group, etc.; R2 to R4 are each hydrogen atom, etc.; M is a hydrogen atom or alkaline metal, org. base, etc.; X is NH, N(-CH2 - CH=CH2 ), etc.; (n) is an integer from 1 to 3. The water dispersion type resin compsn. is obtd. by subjecting a hydrophobic ethylenic unsatd. compd. to emulsion polymn. in the presence of such high-polymer surfactant.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel polymer surfactant and a water-dispersible synthetic resin composition having a heterophasic structure, more specifically, a synthetic resin composition whose surface is coated with an amphipathic polymer. Regarding things.

[0002]

2. Description of the Related Art There is known a technique of introducing a functional group into the surface of a polymer emulsion to control the reactivity and charge state of the emulsion surface and improve the mechanical stability of the emulsion.

[0003]

As a method for distributing a highly hydrophilic functional group in the particle surface phase, a method of synthesizing a hydrophilic monomer and a hydrophobic monomer by soap-free emulsion copolymerization is known. However, this method naturally forms particles with a heterogeneous structure in which highly hydrophilic monomer units are distributed in the surface phase, but the amount of water-soluble polymer that does not remain on the particle surface during the polymerization process and is eluted in the aqueous phase is neglected. However, there is a problem that the target particles cannot be produced efficiently.

Also known is a method of producing particles having a heterophasic structure by using a hydrophilic polymer as a seed. In this case, it is known that the distribution of the hydrophobic polymer after polymerization is greatly influenced by the degree of crosslinking of the seed particles, and generally, when the degree of crosslinking is increased, the hydrophobic polymer phase is distributed in the vicinity of the particle surface. On the other hand, when a hydrophilic polymer having a low degree of cross-linking is used for the seed, there is a problem that the amount of the hydrophilic polymer free from the particles cannot be ignored.

The present invention relates to a method for efficiently producing water-dispersible emulsion particles having a heterophasic structure whose surface is covered with a highly hydrophilic polymer, which has been insufficient in the conventional techniques.

[0006]

DISCLOSURE OF THE INVENTION The present inventors have used a copolymer of a reactive surfactant having a succinic acid skeleton and a hydrophilic ethylenically saturated compound as a dispersant to prepare an emulsion of a hydrophobic ethylenically unsaturated compound. The present invention has been found out that by carrying out polymerization, a highly hydrophilic polymer layer can be unevenly distributed in the surface phase of the emulsion without being released into the aqueous phase, and the present invention has been completed. That is, the present invention comprises 0.1 to 90% by weight of a reactive surfactant represented by the following general formulas (1) to (4) [Chemical formula 2] and 10 to 99.9% by weight of a hydrophilic ethylenically unsaturated compound. Polymeric surfactant formed by copolymerization,

[0007]

Embedded image (In the above formula, R ₁ is a linear or branched saturated hydrocarbon group having 6 to 48 carbon atoms, or an unsaturated double bond is 1
It represents a linear or branched unsaturated hydrocarbon group having 6 to 48 carbon atoms and containing 12 or less. R ₂ and R ₃ independently represent a hydrogen atom or a methyl group, and R ₄ represents a hydrogen atom, a methyl group or an ethyl group. M represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, or an organic base. X is _{NH, N (-CH 2 -CH =} CH 2), it represents one of O. n represents an integer of 1 to 3. ) Polymeric surfactant whose hydrophilic ethylenically unsaturated compound described is a nonionic water-soluble monomer, 0.1-90% by weight of the reactive surfactant described and 10-99.9% by weight of a nonionic water-soluble monomer % With 1% reactive surfactant when copolymerizing with
Polymeric surfactant produced by performing polymerization in the presence of 0.1 to 10 mol, in the presence of the polymeric surfactant according to any one of, obtained by emulsion polymerization of a hydrophobic ethylenically unsaturated compound The present invention relates to a water-dispersed resin composition.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The reactive surfactant used in the present invention has a succinic acid amide or succinic acid ester structure substituted with a hydrophobic group represented by the general formulas (1) to (4) as a skeleton. It has an allyl compound or a vinyl compound. These compounds are obtained by reacting an oligomer of an olefin produced from ethylene, propylene, isobutene, butadiene or the like with a maleic anhydride (hereinafter abbreviated as ASA) as a raw material, and using allylamine (MA) or diallylamine ( DA), methallylamine, allyl alcohol (AL), methallyl alcohol, 2-hydroxyethyl methacrylate (HEM
A), 2-hydroxyethyl acrylate (HEA),
It is produced by the reaction with 3-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 2-hydroxybutyl acrylate, etc. (with ASA) The reaction products are referred to below as ASA-MA and ASA-D.
A, ASA-AL, ASA-HEMA, ASA-HEA
Etc.).

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;
48 linear or branched paraffins or a mixture thereof obtained by a known technique such as a reaction product of internal olefins obtained by dehydrogenation with maleic anhydride. It may be a mixture of those having different double bond positions. When the number of carbon atoms of the olefin oligomer is less than 6 or more than 48, the amphiphilic property as a reactive surfactant such as ASA-MA and ASA-DA is hindered.
It does not meet the purpose of the invention and is less preferred.

The reactive surfactant used in the present invention has a carboxyl group in the molecule and becomes soluble in water when neutralized with an alkali. The pH at which water becomes soluble varies depending on the type of the hydrophobic group and the chain length. For example, in the case of an alkenyl group having 18 carbon atoms, the pH is 8 or higher, and uniform polymerization with a hydrophilic monomer using water as a solvent. Will be possible. Even under water-insoluble pH conditions, emulsion polymerization can be carried out in the presence of a surfactant, or polymerization can be carried out in a solvent that dissolves both a reactive surfactant and a hydrophilic monomer.

The polymeric surfactant of the present invention comprises 0.1 to 90% by weight of a reactive surfactant having a succinic acid structure represented by the above general formulas (1) to (4) and a hydrophilic ethylenic unsaturated. It can be obtained by copolymerizing 10 to 99.9% by weight of the compound.

Examples of hydrophilic ethylenically unsaturated compounds are one or more compounds selected from the group consisting of unsaturated carboxylic acid compounds, unsaturated carboxylic acid amide compounds, other vinyl compounds, and hydrophilic allyl compounds. is there.

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 ionic vinyl compounds and nonionic vinyl compounds. Examples of the ionic vinyl compound include sulfonic acids such as vinyl sulfonic acid, styrene sulfonic acid, 2-acrylamido-2-phenylpropane sulfonic acid and 2-acrylamido-2-methylpropane sulfonic acid, and their alkali metal salts and ammonium salts. , Organic amine salts, N, N-dimethylaminoethyl acrylate (DA), N, N-dimethylaminoethyl methacrylate (DM), N, N-
Dimethylaminopropyl acrylamide (DMAPA
A), cationic vinyl compounds such as N, N-dimethylaminopropyl methacrylamide (DMAPMA), and further, DA, DM, DMAPAA, DMAPMA, etc., with dimethylsulfate, halogenated alkyls such as methyl chloride and methyl bromide, and allyl. Examples thereof include halogenated benzyls such as chloride, benzyl chloride and benzyl bromide, epihalohydrins such as epiclohydrin and epibromohydrin, and vinyl compounds quaternized with epoxides such as propylene oxide and styrene oxide.

As the nonionic vinyl compound, N-
Vinyl-2-pyrrolidone, N-vinylformamide, N
-Vinylacetamide, N-vinyloxazolidone, N
-Vinyl-5-methyloxazolidone, N-vinylsuccinimide, 2-hydroxyethyl acrylate, 2-
Examples thereof include hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate.

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, methallyl You can give alcohol etc.

The polymeric surfactant of the present invention is a reactive surfactant represented by the above general formulas (1) to (4).
-90% by weight and nonionic water-soluble monomer 10-99.9% by weight, the polymerization should be carried out in the presence of 0.1-10 mol of the colloid agent with respect to 1 mol of the reactive surfactant. Also manufactured by.

Examples of the nonionic water-soluble monomer include those exemplified as the hydrophilic ethylenically unsaturated compound, and include unsaturated carboxylic acid amide compounds and N-vinyl-2.
-Pyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinyloxazolidone, N-vinyl-
5-methyloxazolidone, N-vinylsuccinimide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2
-Hydroxypropyl acrylate, 2-hydroxypropyl methacrylate allyl alcohol, methallyl alcohol and the like are exemplified.

Examples of the colloid agent include those represented by the general formula (1)
A compound having the ability to reduce the water solubility of the reactive surfactant represented by (4), and examples of the colloid agent are classified into the compound group of inorganic acid, organic acid, inorganic base, and organic base. It The colloid agent is used alone or in any combination of two or more. The colloid agent is used in an amount of 0.1-10 mol, preferably 0.2-5 mol, per 1 mol of the reactive surfactant. If the colloid agent is not used, the reaction system will be in the form of a dry gel, which is not preferable when used as a sizing agent.

Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, boric acid and the like. As the organic acid, formic acid,
Acetic acid, succinic acid, citric acid, tartaric acid, L-ascorbic acid, acrylic acid, methacrylic acid, crotonic acid, angelic acid, tiglic acid, 2-pentenoic acid, β-methylcrotonic acid, β-methyltiglic 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,
Unsaturated carboxylic acid compounds such as 2,3-dimethylmaleic acid, 2-methylglutaconic acid, 3-methylglutaconic acid, 2-methyl-α-dihydromuconic acid and 2,3-dimethyl-α-dihydromuconic acid, and Vinyl sulfonic acid,
Unsaturated sulfonic acid compounds such as styrene sulfonic acid, 2-acrylamido-2-phenylpropane sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid are exemplified.

Examples of the inorganic base include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, ammonia and the like. Examples of the organic base include hydrazine, ethylenediamine, ethanolamine, dimethylamine, diethylamine, trimethylamine, triethylamine and salts thereof, and N,
N-dimethylaminoethyl acrylate (DA), N,
N-dimethylaminoethyl methacrylate (DM),
N, N-dimethylaminoethyl acrylate, N, N-
Basic vinyl such as dimethylaminoethyl methacrylate, N, N-diethylaminoethyl acrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminopropyl acrylamide (DMAPAA), and N, N-dimethylaminopropyl methacrylamide (DMAPMA). There are compounds and salts thereof, and allylamines such as allylamine, N-methylallylamine, 2-methylallylamine, diallylamine and salts thereof. Furthermore, DA, DM, DMAPAA, DMAP
MA etc. with dimethyl sulfate, halogenated alkyls such as methyl chloride and methyl bromide, allyl chloride,
Examples include halogenated benzyls such as benzyl chloride and benzyl bromide, epihalohydrins such as epiclohydrin and epibromohydrin, vinyl compounds quaternized with epoxies such as propylene oxide and styrene oxide, and dimethyldiallylammonium chloride. it can.

A reactive surfactant having a succinic acid structure,
When copolymerizing a hydrophilic ethylenically unsaturated compound to produce a polymer surfactant, a hydrophobic ethylenically unsaturated compound as described below may be used as a copolymerization component for the purpose of strengthening the hydrophobicity. . If the amount of the hydrophobic ethylenically unsaturated compound used at this time is too large, the water dispersibility of the amphiphilic polymer will be lost, and further, the hydrophobic resin dispersed only with the reactive surfactant Since the water-dispersible resin composition aimed at by the present invention cannot be obtained due to problems such as generation of particles, it is generally 30% or less with respect to the hydrophilic ethylenically unsaturated compound. Is preferred.

The polymer surfactant of the present invention comprises a reactive surfactant having a succinic acid structure represented by the general formulas (1) to (4) and a hydrophilic ethylenic unsaturated compound in an aqueous medium. Can be produced by copolymerization by a known method. Usually, polymerization is carried out by maintaining the polymerization solution at 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 the monomer used and the type of the polymerization initiator, and in the case of a single initiator, it is generally 30 to 100.
The temperature is in the range of 0 ° C, which is lower in the case of a redox-based polymerization initiator, is approximately -5 to 50 ° C when performing the polymerization in a batch, 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 water-soluble initiator can be used as the polymerization initiator. Examples of peroxides include 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. Examples of the reducing agent include sulfite, bisulfite, iron, copper, salts of low-order ions such as cobalt,
Examples thereof include hypophosphorous acid, hypophosphite, organic amines such as N, N, N ′, N′-tetramethylethylenediamine, and reducing sugars such as aldose and ketose. Further, in the azo compound system, 2,2'-azobis-2-amidinopropane hydrochloride, 2,2'-azobis-2,4-dimethylvaleronitrile,
4,4'-Azobis-4-cyanovaleic acid and salts thereof can be used. Further, two or more of the above-mentioned polymerization initiators may be used in combination. The addition amount of the polymerization initiator is in the range of 0.0001 to 10% by weight, preferably 0.01 to 8 with respect to the monomer.
% By weight. In the case of redox system, the amount of reducing agent added to the polymerization initiator is 0.1 to 100 on a molar basis.
%, Preferably 0.2 to 80%.

In the polymerization of the polymer surfactant of the present invention, a pH adjusting agent, a chain transfer agent or the like may be used, if necessary, for the purpose of adjusting the molecular weight or the polymerization rate.

As the pH adjuster, hydrochloric acid, sulfuric acid, phosphoric acid,
Inorganic acids such as boric acid; organic acids such as formic acid, acetic acid, succinic acid, citric acid, tartaric acid, L-ascorbic acid; inorganic bases such as sodium hydroxide, potassium hydroxide, ammonia; ethanolamine, trimethylamine, triethylamine, etc. And organic salts thereof; and 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 and nitroso compounds 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 ethylenediaminetetraacetic acid sodium salt (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%, and the chain transfer agent and other additives are 1.0 ppm to 5.0% relative to the weight of the monomer. Is in the range.

The reactive surfactant having a succinic acid structure, a monomer, a solvent, a polymerization initiator, a chain transfer agent, etc., to be used for the polymerization may be charged into the reaction vessel at a time when the polymerization is started, but the progress of the polymerization Depending on the situation, one or more components may be added individually or as a mixture with a solvent or the like. When a colloid agent is used, the additive solution may be a mixed solution, but the reactive surfactant and the colloid agent must be added separately so that they do not become the same solution. Further, before the polymerization, the pH of the solution is adjusted to 7 or more with a pH adjuster so that the carboxyl group of the reactive surfactant becomes an alkali metal salt or an ammonium salt. The colloid agent should be added continuously or intermittently over about 10 minutes to 40 hours, and the reactive surfactant should be charged into the reaction vessel at least before the addition of the colloid agent is completed.

Next, the water-dispersible resin composition of the present invention is produced by emulsion-polymerizing a hydrophobic ethylenically unsaturated compound in the presence of the polymer surfactant of the present invention.

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

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.

The vinyl cyanide compound may, for example, be acrylonitrile or 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, dimethacrylic acid Ethylene glycol, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, dimethacrylic acid-1,3-butylene glycol, polyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate,
Examples include ethoxy polyethylene glycol (meth) acrylate, propoxy polyethylene glycol (meth) acrylate, isopropoxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, and divinyl compounds such as epoxy acrylates and urethane acrylates. .

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

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.

Further, as the hydrophobic allyl compound,
Examples thereof include diallyl isophthalate, diallyl terephthalate, diethylene glycol diallyl carbonate, triallyl cyanurate and the like.

The compositional ratio of the polymeric surfactant (A) of the present invention to the hydrophobic ethylenically unsaturated compound (B) is such that (A) is 1% by weight based on the total weight of (A) and (B). If it is less than 10% by weight, the emulsion stability of the resin composition of the present invention is lowered, which is not preferable.
9 to 1% by weight, preferably 5 to 90% by weight of (A),
(B) is in the range of 95 to 10% by weight.

The water-dispersible resin composition of the present invention uses the polymer surfactant of the present invention as an emulsifier, and if necessary, a pH adjusting agent, chain transfer agent, protective colloid agent, or known surfactant. Can be used to produce a known emulsion polymerization method. As the pH adjuster, chain transfer agent, and metal ion sealant, those already exemplified when producing the polymer surfactant are used.

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.

As the polymerization initiator, a general polymerization initiator can be used, and among them, the water-soluble ones can be used as those exemplified in the production of the polymer surfactant. Peroxides as oil-soluble initiators, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 1,1,1,
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, and as the azo compound,
Azobisisobutyronitrile, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis Isobutyronitrile, 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), dimethyl2,2'-azobis (2-methylpropionate), etc. Can be used. Furthermore, it is also possible to use two or more of the above-mentioned polymerization initiators 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. 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.

The polymer surfactant, monomers, polymerization initiator, solvent, chain transfer agent and the like to be used for the polymerization may be charged into the reaction vessel at one time at the time of starting the polymerization, but depending on the progress of the polymerization, 1 One or more components alone or mixed with a solvent or the like, for example, monomers prepared as an emulsion solution in the presence of a polymer surfactant, may be added successively.

The water-dispersible resin composition produced by the present invention is basically spherical particles, the inside of which is composed of a hydrophobic polymer and the outside of which is composed of a hydrophilic polymer, and the particles are separated from the particles. The characteristic is that there are almost no hydrophilic polymers. The polymer surfactant of the present invention forms particles in a dilute aqueous solution, and its size can be measured by a dynamic light scattering method. The particle size of the emulsion in which the hydrophobic monomer is polymerized does not change until the amount of the hydrophobic monomer becomes a certain amount with respect to the polymer surfactant, but with this amount as the boundary, the emulsion increases with the amount of the hydrophobic monomer. This is supported by the fact that the diameter of the particles increases and the particles having the grain system observed in the case of only the polymer surfactant do not exist.

The water-dispersible resin composition of the present invention may further contain a preservative, an antifoaming agent, a cross-linking agent, a viscosity modifier, a film-forming aid, a plasticizer, an antistatic agent, a pressure-sensitive adhesive, 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.

[0049]

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 the value measured by a viscometer, and since the emulsion aqueous solution exhibits thixotropy, it is the value measured with the rotation speed fixed at 30 rpm.

(Example 1) ASA-MA (Coropearl Z-100 [manufactured by Seikou Kagaku]): C16 alkenyl group was placed in a 300 ml four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen introducing tube and a feed tube. Reaction product of ASA with allylamine) with 20% neutralized with an equimolar amount of caustic soda
An aqueous solution in which 15.0 g of (Na salt) aqueous solution, 134.6 g of distilled water, and 0.075 g of sodium hypophosphite monohydrate were uniformly dissolved was added, and the temperature was raised to 80 ° C. after purging with nitrogen while stirring. A 50% acrylamide aqueous solution (48.4 g), DM (2.8 g), distilled water (66.9 g) and ammonium persulfate (APS) (0.15 g) were uniformly mixed with this solution, and the pH was adjusted to 6.0 with 35% hydrochloric acid (1.8 g). Over 2 hours. 1 hour after the addition is complete
Stirring was continued at 80 ° C. to obtain a slightly cloudy aqueous solution. Subsequently, a mixed solution of 30.0 g of styrene as a hydrophobic ethylenically unsaturated compound (hydrophobic monomer) and 0.3 g of benzoyl peroxide (BPO) was added dropwise to this aqueous solution through a feed tube in 20 minutes, and the mixture was further heated at 80 ° C for 3 minutes. Stirring was continued to obtain a milky white emulsion solution. The solid content concentration of the emulsion aqueous solution is 20.3
%, PH 6.22, and viscosity 96.0 cp.

(Examples 2 to 3) Polymerization was carried out in the same manner as in Example 1 except for the monomer composition shown in Table 1. However, the dropping time of styrene was 30 minutes in Example 2 and in Example 3.
The operation was performed for 40 minutes to obtain a milky white emulsion.
The results are summarized in Table 1.

Examples 4 to 6 Polymerization was carried out in the same manner as in Examples 1 to 3 except that the hydrophobic monomer was changed from styrene to methyl methacrylate (MMA) to obtain milky white emulsions.

(Example 7) ASA-MA (Coropearl Z-100 [manufactured by Seikou Kagaku]): C16 alkenyl group was placed in a 300 ml four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen introducing tube and a feed tube. Reaction product of ASA with allylamine) with 20% neutralized with an equimolar amount of caustic soda
An aqueous solution in which 50.0 g of (Na salt) aqueous solution, 469.8 g of distilled water, and 0.25 g of sodium hypophosphite monohydrate were uniformly dissolved was added, and the temperature was raised to 80 ° C. after purging with nitrogen while stirring. To this solution, 161.2 g of 50% acrylamide aqueous solution, DM9.4 g, distilled water 303.0 g and ammonium persulfate (APS) 0.50 g were uniformly mixed, and then the pH was adjusted to 4.5 with 5.9 g of 35% hydrochloric acid. Over 2 hours. 1 hour after the addition was completed, 10 ml of 2.5% APS aqueous solution and 2.5% sodium sulfite (SB
S) 10 ml of aqueous solution was added, and stirring was continued for further 2 hours at 80 ° C. to obtain a slightly cloudy aqueous solution. The solid concentration of this solution is 10.5%,
The pH was 6.86 and the viscosity was 24.5 cp. This polymer surfactant aqueous solution is designated as PD-1.

PD-in a 300 ml four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen introduction tube and a feed tube.
12.5% aqueous solution, distilled water 7.35g, potassium persulfate (K
(PS) 0.15 g of an evenly dissolved aqueous solution was added, the mixture was replaced with nitrogen with stirring, the temperature was raised to 60 ° C., and a mixed solution of 27.0 g of MMA and 3.0 g of 2-ethylhexyl acrylate (2EHA) was added dropwise from the feed tube in 60 minutes. Then, the mixture was further stirred at 60 ° C. for 7 hours to obtain a milky white emulsion solution. The emulsion solution had a solid content concentration of 24.3%, a pH of 5.71 and a viscosity of 640 cp.

(Examples 8 to 12) Polymerization was carried out in the same manner as in Example 7 except that the composition ratio of the hydrophobic monomer was shown in Table 1. The results are summarized in Table 1.

(Comparative Examples 1 to 6) A in Examples 1 to 6
When the same polymerization reaction was carried out without using SA-MA, the solution aggregated during the polymerization of the hydrophobic monomer,
It was not possible to obtain an emulsion.

(Particle size measurement examples 1 to 12) The particle systems of the emulsions obtained in Examples 1 to 12 in an aqueous solution were analyzed using a Coulter N4 type submicron particle analyzer manufactured by Coulter Co., Ltd. at 90 ° scattered light. The results measured in Table 1 are summarized in Table 1. Further, the particle size of only the polymer surfactant (PD-1) before adding the hydrophobic monomer is also shown.

[0058]

[Table 1]

[0059]

EFFECT OF THE INVENTION In the presence of a polymer in which ASA-MA is not copolymerized, aggregates are formed during emulsion polymerization of a hydrophobic monomer (hydrophobic ethylenically unsaturated compound), so that an emulsion can be prepared. An emulsifier is essential. However, even if an emulsifier is used, the interaction between the emulsion particles and the water-soluble polymer is weak in principle, and therefore it is presumed that most of the polymer cannot stay on the particle surface. According to the present invention, an emulsion having good stability can be prepared in the presence of the polymer surfactant of the present invention. In addition, the polymeric surfactant itself has the ability to form colloidal particles, and when the amount of copolymerization of the hydrophobic monomer becomes a certain amount (about 10%) or more, the total amount of the particles increases, so that the particles are liberated from the particles. It is considered that there is almost no hydrophilic polymer.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical location C08F 220/54 MNC C08F 220/54 MNC 222/02 MLQ 222/02 MLQ 226/02 MNL 226/02 MNL C11D 1 / 28 C11D 1/28 // C07C 69/34 C07C 69/34 69/54 69/54 A 233/05 9547-4H 233/05

Claims (4)

[Claims] 1. A compound containing 0.1 to 90% by weight of a reactive surfactant represented by the following general formulas (1) to (4) [Chemical formula 1] and 10 to 99.9% by weight of a hydrophilic ethylenically unsaturated compound. A polymeric surfactant formed by polymerization. Embedded image (In the above formula, R ₁ is a linear or branched saturated hydrocarbon group having 6 to 48 carbon atoms, or an unsaturated double bond is 1
It represents a linear or branched unsaturated hydrocarbon group having 6 to 48 carbon atoms and containing 12 or less. R ₂ and R ₃ independently represent a hydrogen atom or a methyl group, and R ₄ represents a hydrogen atom, a methyl group or an ethyl group. M represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, or an organic base. X is _{NH, N (-CH 2 -CH =} CH 2), it represents one of O. n represents an integer of 1 to 3. ) 2. A polymer surfactant in which the hydrophilic ethylenically unsaturated compound according to claim 1 is a nonionic water-soluble monomer. 3. The reactive surfactant according to claim 1, which is 0.1 to
90% by weight and nonionic water-soluble monomer 10-99.9% by weight
A polymer surfactant produced by copolymerizing a colloidal agent with 0.1 to 10 mol of the reactive surfactant relative to 1 mol of the reactive surfactant. 4. A water-dispersible resin composition obtained by emulsion-polymerizing a hydrophobic ethylenically unsaturated compound in the presence of the polymer surfactant according to claim 1.