JP2906051B1 - Method for producing emulsifier for emulsion polymerization and aqueous resin dispersion - Google Patents

Abstract

The present invention provides an emulsifier for emulsion polymerization capable of obtaining a resin aqueous dispersion having a high concentration and a low viscosity and giving a film having excellent water resistance. An emulsifier for emulsion polymerization of an ethylenically unsaturated monomer (A), having a weight average molecular weight of 5,000 to 500,000, and an SP value of the (co) polymer (A). Has an SP value of 2 or less, and an HLB of 6 to 40.
(B) having the following formula:

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an emulsifier for emulsion polymerization and a method for producing an aqueous resin dispersion. More specifically, the present invention relates to an emulsifier for emulsion polymerization capable of obtaining an aqueous resin dispersion having a high concentration and low viscosity and providing a film having excellent water resistance, and a method for producing an aqueous resin dispersion using the same.

[0002]

2. Description of the Related Art Conventionally, as a method of emulsion-polymerizing an ethylenically unsaturated monomer, a method of using a low-molecular-weight water-soluble surfactant as an emulsifier for emulsion polymerization, or a method of protecting a water-soluble polymer compound such as polyvinyl alcohol. A method of using as a colloid is known.

[0003]

However, the method using a low molecular weight water-soluble surfactant has a problem that the water resistance of a film obtained from the resulting aqueous resin dispersion is extremely low. Further, in the method using polyvinyl alcohol or the like, there is a problem that the viscosity of the resulting aqueous resin dispersion is too high, and it is difficult to increase the resin concentration.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have identified a polymer having excellent affinity with a (co) polymer obtained from an ethylenically unsaturated monomer. It has been found that by using the compound of the formula (1) as an emulsifier for emulsion polymerization, an aqueous resin dispersion which can solve the above-mentioned disadvantages can be obtained, and the present invention has been achieved.

That is, the present invention relates to an emulsifier for emulsion polymerization of an ethylenically unsaturated monomer (A),
(A) having a weight average molecular weight of 00,000
The difference from the SP value of the polymer has an SP value of 2 or less, and
An emulsifier for emulsion polymerization, comprising a compound (B) having an HLB of 6 to 40. A method for producing an aqueous resin dispersion, comprising subjecting an ethylenically unsaturated monomer (A) to emulsion polymerization in the presence of the emulsifier for emulsion polymerization;
A paint, a woodworking or paperworking adhesive, an ink, a fiber texture improving agent or a paper treating agent comprising the aqueous resin dispersion obtained by the production method.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the compound (B) has a weight average molecular weight of usually 5,000 to 500,000, preferably 10,000 to 400,000, more preferably 15,000 to 200,000. is there. If the weight average molecular weight is less than 5,000, the water resistance of the film from the obtained aqueous resin dispersion cannot be improved, and
If it exceeds 00, the obtained aqueous resin dispersion has a high viscosity, which does not meet the object of the present invention of obtaining an aqueous resin dispersion having a high concentration and a low viscosity.

The SP value of the compound (B) in the present invention is as follows:
It is necessary that the difference from the SP value of the (co) polymer of the ethylenically unsaturated monomer (A) is usually 2 or less, and preferably 1 or less. If the SP value difference exceeds 2, the resin in the film from the resulting aqueous resin dispersion and the emulsifier have poor compatibility with each other and tend to separate, resulting in insufficient water resistance of the film. The difference between the SP value of (B) and the SP value of the (co) polymer of (A) is adjusted by adjusting the type and content of the hydrophobic group and the type and content of the hydrophilic group in (B). It can be performed by adjusting the amount. The SP value can be determined, for example, by the method described in Chemical Handbook Application Edition, 3rd Edition, p. 764, edited by The Chemical Society of Japan (Maruzen, published in 1980).

The HLB of the compound (B) in the present invention is 6
~ 40. If it is less than 6 or more than 40, the power to emulsify the ethylenically unsaturated monomer becomes weak, and a stable aqueous resin dispersion cannot be obtained. The adjustment of the HLB in (B) can be performed, for example, by adjusting the type and content of the hydrophobic group in (B) and adjusting the type and content of the hydrophilic group in (B). The HLB is, for example, Teijin Times 9 22
Page (issued in 1952) and the synthesis and application of surfactants can be determined by the method described on page 501 (issued by Maki Shoten, 1957).

The SP value and HLB of the compound (B) in the present invention are preferably 8 to 1 when the (A) is an unsaturated monomer (A1) composed of vinyl esters.
6, and having an HLB of 10 to 30 (B1);
More preferably, the SP value is 9 to 12, and the HLB is 1.
2-20. When the (A) is an unsaturated monomer (A2) composed of (meth) acrylic acid esters, the (B2) preferably has an SP value of 7 to 20 and an HLB of 8 to 40, More preferably, the SP value is 9 to 15,
And HLB is 12-30. When the (A) is an unsaturated monomer (A3) comprising styrenes and dienes, the SP value is preferably 7 to 15, and the HLB is preferably 6 to 15.
25 (B3), more preferably an SP value of 9 to 13 and an HLB of 12 to 25. (A)
Is an unsaturated monomer comprising a nitrile and a diene (A
In the case of 4), preferably, the SP value is 8 to 17, and H
The LB is 8 to 30 (B4), and more preferably the SP value is 9 to 15 and the HLB is 10 to 25. When said (A) is an unsaturated monomer (A5) composed of a vinyl halide, it preferably has an SP value of 9 to 18 and an HLB of 6 to 25 (B5), more preferably SP value is 10 to 13 and HLB is 12 to 2
0.

In the present invention, the compound (B) comprises a nonionic group [polyoxyethylene group, hydroxyl group, etc.],
Anionic [carboxylic acid (salt) group, sulfonic acid (salt)
Group, sulfate ester (salt) group, phosphate ester (salt) group, etc.], cationic group [primary amine (salt) group, secondary amine (salt) group, tertiary amine (salt) group, Quaternary ammonium (salt) group, etc.] and zwitterionic groups [amino acid (salt) group, betaine group, etc.] or at least one hydrophilic group. When the content of the hydrophilic group is a polyoxyethylene group, the content of the oxyethylene unit is usually 20 to 99% by weight, preferably 50% by weight.
-95% by weight, more preferably 70-95% by weight. If the content of oxyethylene units is less than 20% by weight or more than 99% by weight, a stable aqueous dispersion having weak emulsifying power cannot be obtained. Further, the hydrophilic group is a hydroxyl group,
In the case of an anionic group, a cationic group or a zwitterionic group, the hydrophilic group accounts for 1 to 99% by weight, preferably 5 to 9% by weight.
0% by weight, more preferably 10 to 70% by weight. The content of the hydrophilic group is less than 1% by weight or 99% by weight
If it exceeds, a stable aqueous dispersion having a weak emulsifying power cannot be obtained.

The method for introducing these hydrophilic groups may be a conventional method, for example, a method in which ethylene oxide is added to an active hydrogen-containing compound, a method in which a hydroxyl group is sulfated with sulfuric anhydride, chlorosulfonic acid, or the like;
A method of adding sulfuric anhydride to a carbon-carbon unsaturated bond, a method of phosphorylating a hydroxyl group with phosphoric anhydride or the like, a method of (poly) hydroxy (poly) carboxylic acid or (poly)
There is a method of using hydroxy (poly) amine as a raw material for synthesizing the compound (B).

In the present invention, the compound (B) is
It is preferred that the (A) polymer has at least two, preferably at least three, hydrophobic groups having a SP value of usually 2 or less, preferably 1 or less, in the molecule. If the difference in SP value exceeds 2, the effect of improving the water resistance of the coating from the obtained aqueous resin dispersion tends to be insufficient. Examples of the hydrophobic group include, for example, those having 3 carbon atoms.
~ 100 or more (preferably 4-80) hydrocarbon groups [butyl, butylene, hexyl, hexylene, dodecyl, cetyl, oleyl, alkylphenyl, styrenated phenyl, bisphenols Such as bisphenol A, bisphenol S, and bisphenol F) excluding the hydroxyl group], a (poly) oxyalkylene (polyoxypropylene group having a polymerization degree of 100 or less) having 3 to 10 or more carbon atoms in the alkylene group; Polyoxybutylene group, polystyrene oxide group, etc.) and polyorganosiloxane (polymerization degree 2 to 10)
0) group (polydimethylsiloxane group, polydiethylsiloxane group, etc.). Further, the hydrophobic group and (B)
Examples of a bonding mode with a hydrophilic group or a hydrophilic group-containing group that is essentially contained therein include a urethane bond, a urea bond, an ester bond, an amide bond, and an ether bond. Among these, a urethane bond, a urea bond and an ester bond are preferable, and a urethane bond is particularly preferable.

Preferred examples of the compound (B) include:
The following general formula (1)

[0014]

Embedded image

[Wherein, R ¹ is a residue of an alcohol or phenol compound (D1) having ¹ to 6 hydroxyl groups, X is a residue of an organic polyisocyanate compound (E), and R ² is two hydroxyl groups. The residue of an alcohol or phenol compound (D2) having a group, at least one of the k Zs is -O- (AO) r-Q, and the remainder is -N
(R ³ ) ₂ and / or —NH—R ³ , wherein Q is a residue or a hydrogen atom of the monohydroxy compound (F) having 1 to 100 carbon atoms, and R ³ is the same or different 1 to ³ carbon atoms. 100 hydrocarbon groups and / or hydroxyl group-containing hydrocarbon groups. ｝, A has 2 to 30 carbon atoms
(However, when m, n, p or r oxyalkylene groups OA are composed of two or more oxyalkylene groups, the bonding mode may be either block or random). Represents m, n, p and r
Are each independently 0 or an integer of 1 to 500 (provided that
The sum of m, q n, q p, and all r is an integer of at least 10. ), Q is 0 or an integer of 1 to 500, and k is an integer of 1 to 6. And a water-soluble polyurethane compound (U1).

R ¹ in the general formula (1) is a residue of an alcohol or phenol compound (D1) having ¹ to 6 hydroxyl groups. Specific examples of (D1) include compounds having one hydroxyl group [methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, lauryl alcohol, cetyl alcohol, oleyl alcohol, polydimethylsiloxane monocarbinol And monohydric alcohols such as polydiethylsiloxane monocarbinol; nonylphenol, dodecylphenol, octylphenol, cumylphenol, styrenated (usually 1 to 10 mol added, preferably 2 to 5 mol added) phenol, styrenated (usually Monohydric phenols such as cumylphenol, monomethyl ether of bisphenol A, monobutyl ether of bisphenol S, etc.]; two hydroxyl groups [Ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, polypropylene glycol, polytetramethylene ether glycol, polybutadiene glycol, polycaprolactone diol, dimethylolpropionic acid (salt), polydimethylsiloxane dicarbinol, polydiethyl Dihydric alcohols such as siloxane dicarbinol; hydroquinone, catechol, bisphenol A, bisphenol S, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (3,5-dimethyl-4-) Dihydric phenols such as hydroxyphenyl) sulfone]; compounds having 3 to 6 hydroxyl groups (glycerin, trimethylolpropane, trimethylolethane, pentae Suritoru, polyhydric alcohols sorbitol; polyhydric phenols tris-4-hydroxyphenyl methane, etc); and mixtures of two or more thereof. Preferred among these are compounds having one or two hydroxyl groups. The molecular weight per hydroxyl group of (D1) is usually 30 to 2,
000 or more, preferably 30 to 1,000.

In the general formula (1), X is a residue of the organic polyisocyanate compound (E), and X generally has 4 to 18, preferably 6 to 15 carbon atoms. Examples of (E) include 4,4′-diphenylmethane diisocyanate (MDI), 2,4- or 2,6-tolylene diisocyanate (TDI), 4,4′-dibenzyl diisocyanate, 1.3- Aromatic diisocyanates such as 1,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate and xylylene diisocyanate; aliphatic diisocyanates such as ethylene diisocyanate, hexamethylene diisocyanate (HDI) and lysine diisocyanate; isophorone diisocyanate (IPDI); Cycloaliphatic diisocyanates such as 4,4'-dicyclohexylmethane diisocyanate;
And mixtures of two or more of these. Of these, preferred are MDI, TDI, HD
I and IPDI.

In the general formula (1), the (poly) oxyalkylene group includes ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO),
1,2-, 1,3- or 2,3-butylene oxide, tetrahydrofuran, α-olefin (having 4 to 4 carbon atoms)
30) A group formed by ring-opening (co) addition of an alkylene oxide such as oxide, epichlorohydrin, and styrene oxide to the hydroxyl group-containing compound (D1). Preferred among these are (poly) oxyalkylene groups formed by EO alone and co-addition of EO and PO.

For the formation of the (poly) oxyalkylene group, EO alone or a combination of EO and an alkylene oxide other than EO is usually used. The content of oxyethylene units in the (poly) oxyalkylene group is usually at least 60% by weight, preferably at least 80% by weight. When the content of the oxyethylene unit is less than 60% by weight, the obtained polyurethane compound (U1) has insufficient emulsifiability, so that emulsion polymerization becomes difficult. When two or more alkylene oxides are used, the bonding mode may be either block or random, but the terminal portion of the (poly) oxyalkylene chain is a hydroxyethyl group from the viewpoint of reactivity with the organic polyisocyanate. Are preferred.

R ² in the general formula (1) is an alcohol or phenol compound having two hydroxyl groups (D
2) residue. Specific examples of (D2) include, for example, compounds having two hydroxyl groups among those exemplified as (D1). The molecular weight per hydroxyl group of (D2) is usually 30 to 2,000, preferably 30 to 1,000.

M, n, p and r in the general formula (1)
Is the number of moles of an alkylene oxide forming a (poly) oxyalkylene group, and m, n, p and r are each independently 0 or an integer of 1 to 500. m,
If n, p or r exceeds 500, the viscosity of the resulting aqueous solution of the polyurethane compound (U1) becomes high, and emulsion polymerization becomes difficult. The sum of m, q n, q p and all r is usually at least 10, preferably 30 to
1000 or more. If the sum of m, q n, q p, and all r is less than 10, the polyurethane compound (U1) has a small number of hydrophilic groups, resulting in insufficient emulsifiability and difficulty in emulsion polymerization.

Z in the general formula (1) is such that at least one of the k Zs is -O- (AO) r-Q, and the remainder is-
N (R ³ ) ₂ and / or —NH—R ³ (where R ³ is the same or different and is a hydrocarbon group having 1 to 100 carbon atoms or a hydroxyl group-containing hydrocarbon group);
Is a residue or a hydrogen atom of the monohydroxy compound (F) having 1 to 100, preferably 10 to 100 carbon atoms. Z
And when all of R ² are a hydrogen atom, a hydrocarbon group having less than 10 carbon atoms, or a hydroxyl group-containing hydrocarbon group, the resulting polyurethane compound (U1) has good emulsifying power and a stable aqueous resin dispersion. In order to obtain, the (poly) oxyalkylene group in (U1) is preferably composed of a hydrophobic oxyalkylene group having 3 or more carbon atoms and an oxyethylene group. In addition, the above R
³ is a hydrocarbon group having a carbon number of usually 1 to 100, preferably 1 to 30 or a hydroxyl group-containing hydrocarbon group,
Specific examples include an alkyl group (methyl group, ethyl group, butyl group, octyl group, decyl group, dodecyl group, cetyl group, stearyl group, etc.), an alkenyl group (dodecenyl group, oleyl group, etc.), an aralkyl group (benzyl group, etc.). ), Aryl group (phenyl group, naphthyl group, etc.), alkylaryl group (cresyl group, butylphenyl group, nonylphenyl group, etc.), hydroxyalkyl group (hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, hydroxyoctyl group) And the like, and a hydroxyaryl group (such as a hydroxyphenyl group and a 2-methyl-4-hydroxyphenyl group).

The hydrocarbon group having 1 to 100 carbon atoms constituting (F) may be linear, branched or cyclic, and may be aliphatic or aromatic. Specific examples of (F) include, for example, compounds having one hydroxy group among those exemplified as (D1). Of these, preferred are substituted phenols, and particularly preferred are styrenated (2 to 5).
Mole addition) phenol.

Q in the general formula (1) is usually 0 or an integer of 1 to 500, preferably 1 to 50. q is 5
When it exceeds 00, the viscosity of the obtained aqueous solution of the polyurethane compound (U1) becomes high, and emulsion polymerization becomes difficult.

K in the general formula (1) is usually an integer of 1 to 6, preferably 1 or 2, and represents the number of hydroxyl groups in (D1).

The method for producing (U1) is not particularly limited, and (D1), (D2), and (F) and (E) can be converted to urethane by a usual method for producing a polyurethane resin (one-shot method or multistage method). It is obtained by a chemical reaction.
Part of Z is -N (R ³ ) ₂ and / or -NH-R
For ³ is obtained by reacting in the same manner by replacing a portion of HN- (R ³⁾ ₂ and / or H ₂ N-R ³ in (F). The reaction temperature for urethanization is usually 30 to 200.
° C, preferably 50 to 180 ° C. The reaction time is generally 0.1 to 30 hours, preferably 0.1 to 8 hours.
The urethanization reaction is usually performed in a solventless system, but may be performed in an organic solvent inert to isocyanate, if necessary. As the organic solvent, acetone, tetrahydrofuran, dimethylformamide, dimethylsulfoxide,
Examples include toluene and dioxane. After forming (U1), the organic solvent is usually removed by a distillation method or the like.

In the above urethanization, (D1), (D
2) and the equivalent ratio of the total hydroxyl (OH) groups in (F) to the isocyanate (NCO) groups in (E) [OH /
NCO ratio] is usually 1: (0.8 to 1.5), preferably 1: (0.9 to 1.3). When the NCO group is less than 0.8 equivalent, the molecular weight of the obtained polyurethane compound (U1) becomes low, and the water resistance of the film from the obtained resin aqueous dispersion cannot be improved. Since the NCO group reacts with water, the water solubility of (U1) decreases, and the emulsion polymerization property decreases, which is not preferable.

When (B) is a compound in which a polyoxyalkylene chain and a hydrophobic group are bonded via a urea group, for example, (D1) and (D1) in the above (U1)
2) and (F) exemplified by (poly) alkylene oxide adducts having an amino group introduced into the terminal thereof;
It can be obtained by reacting the polyisocyanate compound (E) in the same manner as in the case of (U1). As a method of introducing an amino group into the terminal, acrylonitrile is added dropwise to the (poly) alkylene oxide adduct at 10 to 80 ° C. in the presence of an alkali catalyst such as potassium hydroxide, and then the alkali catalyst used is added. After removal, the solvent is removed under a high pressure (eg, 30 to 100 kg / c) in a solvent such as methanol.
m ² ), and a method of hydrogenation using a catalyst such as nickel or cobalt.

When the compound (B) is a compound in which a polyoxyalkylene chain and a hydrophobic group are bonded via an ester group, the compound (U1) is replaced with a polyisocyanate compound (E) and has 4 to 4 carbon atoms. 20 polycarboxylic acids or ester-forming derivatives thereof (eg, maleic acid,
Polycarboxylic acids such as fumaric acid, adipic acid and phthalic acid; polycarboxylic anhydrides such as maleic anhydride and phthalic anhydride; and polycarboxylic acid alkyl esters such as dimethyl maleate and dimethyl terephthalate).
This and the (poly) alkylene oxide adduct of the compounds exemplified as (D1), (D2) and (F) in (U1) are dehydrated (or dehydrated) at a temperature of 20 to 250 ° C. under normal pressure or reduced pressure. Alcohol) condensation.

In the case where (B) is a compound in which a polyoxyalkylene chain and a hydrophobic group are bonded via an amide group, those exemplified in (D1), (D2) and (F) in (U1) above are exemplified. A compound in which an amino group is introduced into a terminal of a (poly) alkylene oxide adduct of a compound;
20 polycarboxylic acids or amide-forming derivatives thereof (for example, polycarboxylic acids such as maleic acid, fumaric acid, adipic acid, and phthalic acid; polycarboxylic anhydrides such as maleic anhydride and phthalic anhydride; dimethyl maleate; And a polycarboxylic acid alkyl ester such as dimethyl terephthalate) at a temperature of 20 to 250 ° C. under normal pressure or reduced pressure by dehydration (or dealcoholation) condensation.

When (B) is a compound in which a polyoxyalkylene chain and a hydrophobic group are bonded via an ether group, dichloromethane and dibromomethane are used in place of the polyisocyanate compound (E) in (U1). , Such as chlorobromomethane, dibromobenzene, etc.
0 dihalogenated hydrocarbons are used, and
The compound (D1), (D2) or (F) in (1) is admixed with the (poly) alkylene oxide adduct at a temperature of 20 to 100 ° C. in the presence of an alkali such as sodium hydroxide or potassium hydroxide. And a condensation reaction.

As the (B), a (co) polymer (B6) of an ethylenically unsaturated monomer can also be used.
In this case, as a method for obtaining the (B6), an ethylenically unsaturated monomer (a) containing a hydrophilic group such as a cationic group, an anionic group, or a nonionic group and, if necessary, another ethylenically unsaturated monomer A method of polymerizing with one or more kinds of (b), and hydrolyzing or hydrolyzing the compound (B7) obtained by polymerizing with one or more kinds of (b) And a method obtained by adding a group.

As the ethylenically unsaturated monomer (a) containing a hydrophilic group such as a cationic group, an anionic group and a polyoxyethylene group, the ethylenically unsaturated monomer having a cationic group [N, N-dialkyl] Aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, etc. and their salts (organic acid salts, inorganic acid salts, etc.) and quaternized compounds with dimethyl sulfate, methyl chloride, etc.]; Having an ethylenically unsaturated monomer [(meth) acrylic acid, (anhydride) maleic acid, fumaric acid, itaconic acid, vinylsulfonic acid, (meth) acrylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid and the like; Salts thereof (alkali metal salts, alkaline earth metal salts, ammonium salts, amine salts, etc.), etc.],
Ethylenically unsaturated monomer having an amine imide group [1,
1,1-trimethylamine methacrylimide, 1,1-
Dimethyl-1-ethylamine methacrylimide, 1,1
-Dimethyl-1- (2-hydroxypropyl) amine methacrylimide, 1,1-dimethyl-1- (2′-phenyl-2′-hydroxyethyl) amine methacrylimide, 1,1-dimethyl-1- (2 ′ -Hydroxy-3 '
-Phenoxypropyl) amine methacrylimide, 1,
Japanese Unexamined Patent Publication (Kokai) No. 5 such as 1,1-trimethylamine acrylimide
No. 25354], and an ethylenically unsaturated monomer having a nonionic hydrophilic group [monoalkyl ether mono (meth) acrylate or di (meth) acrylate of polyalkylene glycol containing oxyethylene unit essentially] Acrylate, (meth) acrylamide, N,
Α, β-unsaturated carboxylic acid amides such as N-dimethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, etc.] and a mixture of two or more thereof. Of these, preferred are ammonium or amine salts of (meth) acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid,
1,1-trimethylamine methacrylimide and 1,
1-dimethyl-1- (2-hydroxypropyl) amine methacrylimide, monoalkyl ether (meth) acrylate and di (meth) acrylate of polyethylene glycol.

The other ethylenically unsaturated monomer (b) optionally used is not particularly restricted but includes, for example, α, β-unsaturated carboxylic acid (cyclo) alkyl esters [the above α, β
-Unsaturated carboxylic acids and alcohols having 1 to 25 carbon atoms (methyl alcohol, ethyl alcohol, butyl alcohol, stearyl alcohol, ethylene glycol,
Esters with 1,4-butanediol, cyclohexanol, etc.); unsaturated monomers containing cyano groups [such as (meth) acrylonitrile]; vinyl esters (such as vinyl acetate, vinyl propionate, divinyl phthalate);
Styrenes (styrene, α-methylstyrene, vinyltoluene, divinylbenzene, etc.); halogen-containing unsaturated monomers (vinyl chloride, vinylidene chloride, chloroprene, etc.); hydroxyl-containing unsaturated monomers [hydroxyalkyl (C2 To 4) (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc.]; aliphatic hydrocarbon-based unsaturated monomers (ethylene, propylene, butadiene, isoprene, etc.); and mixtures of two or more of these. .

The proportion of (a) in (B6) is
Usually at least 2 based on the total weight of (a) and (b)
0% by weight, preferably 25 to 80% by weight. (A)
As a method for (B) obtaining (B6) by (co) polymerizing (b) if necessary, a usual solution polymerization method can be used.
Examples of the method for adding the monomer include, but are not limited to, the following methods. Batch charging method [aqueous medium (water or a mixed solvent of water and a water-miscible solvent such as an alcohol such as methanol or isopropanol or a ketone solvent such as acetone) and a polymerization initiator, an ethylenically unsaturated monomer [(a) And, if necessary, (b)], etc., in a batch in a reaction vessel to carry out polymerization] Monomer addition method [Part or all of the polymerization initiator and, if necessary, one monomer in an aqueous medium] Parts into a reaction vessel, and monomer (with the remaining polymerization initiator if necessary)
Method for Performing Polymerization by Sequentially Adding as the Polymerization Proceeds] The monomer concentration in the above solution polymerization reaction is usually 5 to 70% by weight, preferably 30 to 50% by weight. Further, the temperature in the system in the solution polymerization reaction is usually −5 to 100 ° C., preferably 30 to 80 ° C., the reaction time is usually 0.1 to 50 hours, preferably 2 to 10 hours. The polymerization is carried out until the total amount of the monomers used is usually 5% by weight or less, preferably 1% by weight or less. If necessary, the monomer remaining in the system and the organic solvent used in combination can be removed by, for example, distillation under reduced pressure.

Examples of the polymerization initiator include organic polymerization initiators [peroxides (benzoyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, t-amyl hydroperoxide, t-butyl peroxide). Benzoate, t-butyl peroxyacetate, etc.), azo compounds [azobisisobutyronitrile, azobisisovaleronitrile, 2,2 ′
-Azobis (2-amidinopropane) hydrochloride, 2,2 '
-Azobis [2- (2-imidazolin-2-yl) propane] hydrochloride, 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] hydrochloride,
4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-methylpropionamide), etc.]; inorganic polymerization initiator [persulfate (sodium persulfate, ammonium persulfate, persulfate) Potassium), percarbonate (such as sodium percarbonate), hydrogen peroxide and the like]. These are used alone or in combination of two or more. The amount of the polymerization initiator to be used is usually 0.01 to 5% by weight based on the ethylenically unsaturated monomer (A).

For the polymerization, known additives (reducing agents such as sodium pyrobisulfite, chelating agents such as glycine, pH buffering agents such as sodium tripolyphosphate) may be used, if necessary.
Alternatively, a chain transfer agent (α-methylstyrene dimer, alkyl mercaptan having 8 to 18 carbon atoms, etc.) may be used.

As a method for obtaining the compound (B6) by hydrolyzing or adding a hydrophilic group to the compound (B7), for example, a compound containing a vinyl ester or the like as a structural unit (B6)
7) is heated and hydrolyzed in a non-aqueous medium (acetone, methanol, etc.) or an aqueous medium (water and methanol, isopropanol, etc.) in the presence of an alkali such as sodium hydroxide or sodium methoxide to obtain (B6). A method for obtaining (B6) by adding sulfuric anhydride in a non-aqueous medium such as a halogenated hydrocarbon to obtain (B6) containing (B7) containing styrenes as a constituent unit; (B7) having active hydrogen (hydroxyl group, etc.) Polyethylene oxide is added using an alkali catalyst (B6)
(B7) having a hydroxyl group is sulfated with sulfuric anhydride or the like, or (B7) is phosphorylated with phosphoric anhydride or the like to obtain (B6).

Further, (B) may contain an unsaturated group copolymerizable with the ethylenically unsaturated monomer (A). As a method for introducing this unsaturated group into (B), for example, a method using hydroxyalkyl (meth) acrylate or the like as a part of (D1); the urethanation reaction, ureation reaction, esterification reaction, amidation A method in which (meth) acrylic acid chloride is subjected to a condensation reaction at a temperature of 20 to 100 ° C. in the presence of an alkali such as sodium hydroxide or potassium hydroxide on the hydroxyl group-containing compound obtained by the reaction, etherification reaction or the like. No.

The ethylenically unsaturated monomer (A) used in the emulsion polymerization in the present invention is not particularly limited.
Examples thereof include those exemplified in the above (a) and (b) and mixtures of two or more of them.

Examples of industrial use of the ethylenically unsaturated monomer (A) include, for example, (A1) unsaturated monomers composed of vinyl esters [vinyl esters (vinyl acetate, vinyl propionate, (A2) (meth) acrylic acid; vinyl butyrate, divinyl phthalate, etc.) and a combination of at least one of these with one or more aliphatic hydrocarbon monomers (ethylene, propylene, 1-butene, etc.) Unsaturated monomers composed of esters [(meth) acrylates ((cyclo) alkyl (C1-25) (meth)
Acrylates, such as methyl (meth) acrylate,
Ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, etc .; hydroxyalkyl (2-4 carbon atoms) (meta A) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4
-Hydroxybutyl (meth) acrylate and the like; aromatic ring-containing (meth) acrylate such as benzyl (meth)
Acrylates and the like; alkylene (C2-8) glycol di (meth) acrylate, for example, ethylene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, 1,6-hexylene glycol di (meth) acrylate Acrylates and the like; mono- or di (meth) acrylates of polypropylene glycol (degree of polymerization of 2 to 50 or more) and the like;
(A3) Styrene, etc. in combination with at least one or more selected from (meth) acrylic acid (salt), styrenes (styrene, α-methylstyrene, vinyltoluene, divinylbenzene, etc.) and the vinyl esters Monomers consisting of styrenes and dienes [combination of one or more of the above-mentioned styrenes with one or more of dienes (butadiene, isoprene, chloroprene, etc.)]; (A4) consisting of nitriles and dienes (A5) unsaturated monomer composed of vinyl halide (A5) unsaturated monomer [combination of at least one of cyano group-containing unsaturated monomer [(meth) acrylonitrile and the like] with at least one of the dienes]; [Vinyl halides (vinyl chloride, vinyl fluoride, vinylidene chloride, vinylidene fluoride, etc.), and one or more thereof and the vinyl esters and (meth) Combination etc.] or the like with one or more selected from acrylic acid esters.

In the method for producing an aqueous resin dispersion of the present invention, the amount of the emulsifier for emulsion polymerization comprising the compound (B) is usually 0.1 to 10% based on the weight of the ethylenically unsaturated monomer (A). It is 50% by weight, preferably 0.5 to 30% by weight, more preferably 1 to 5% by weight. When the amount is less than 0.1% by weight, a resin aqueous dispersion having good emulsion stability cannot be obtained, and when the amount exceeds 50% by weight, the viscosity of the obtained aqueous resin dispersion becomes high, and the dryness obtained from the dispersion becomes high. The water resistance of the coating also decreases.

If necessary, other known emulsifiers for emulsion polymerization (such as nonionic emulsifiers, anionic emulsifiers, cationic emulsifiers and various reactive emulsifiers) may be used together with (B) as long as the effects of the present invention are not impaired. Can be used together. When used in combination, the amount of the other emulsifier for emulsion polymerization used is usually at most 30% by weight, preferably at most 10% by weight, based on the total amount of the emulsifier.

As a method for producing an aqueous resin dispersion by the method of the present invention, a usual emulsion polymerization method can be used. Examples of the method for adding the monomer (A) in the emulsion polymerization include, but are not limited to, the following methods. Batch charging method [compound (B), aqueous medium (water or a mixed solvent of water and a water-miscible solvent such as an alcohol such as methanol or isopropanol or a ketone solvent such as acetone),
A method in which a polymerization initiator, an ethylenically unsaturated monomer (A), etc. are charged into a reaction vessel at a time to carry out polymerization]; a monomer addition method [in an aqueous medium containing (B), one polymerization initiator is added. Part or all and, if necessary, a part of (A) in a reaction vessel, and adding (A) (along with the remaining polymerization initiator, if necessary), sequentially and sequentially as the polymerization proceeds, to carry out polymerization]; Body dispersion liquid addition method [Part of (B), aqueous medium, part or all of the polymerization initiator and, if necessary, part of (A) are charged into a reaction vessel, and the remaining (B) is used as (A) Is dispersed in water, and the dispersion (along with the remaining polymerization initiator, if necessary) is added successively with the progress of the polymerization as the polymerization proceeds to carry out the polymerization]. The monomer concentration in the emulsion polymerization reaction is usually 20 to 75.
% By weight, preferably 40 to 60% by weight. Further, the temperature in the system in the emulsion polymerization reaction is usually -5 to 100C, preferably 30 to 80C, and the reaction time is usually 0.1 to 50 hours, preferably 2 to 10 hours. The polymerization is carried out until the total amount of the monomers used is usually 5% by weight or less, preferably 1% by weight or less. If necessary, the monomer remaining in the system and the organic solvent used in combination can be removed by, for example, distillation under reduced pressure.

Examples of the polymerization initiator include organic polymerization initiators such as peroxides (cumene hydroperoxide, t
-Butyl hydroperoxide, t-amyl hydroperoxide, t-butyl perbenzoate, t-butyl peroxyacetate, etc.), azo compounds [2, 2'-
Azobis (2-amidinopropane) hydrochloride, 2,2'-
Azobis [2- (2-imidazolin-2-yl) propane] hydrochloride, 2,2′-azobis [2- (5-methyl-
2-imidazolin-2-yl) propane] hydrochloride, 4,
4'-azobis (4-cyanovaleric acid),
2,2'-azobis (2-methylpropionamide)
And the like; inorganic polymerization initiators [persulfates (sodium persulfate, ammonium persulfate, potassium persulfate, etc.), percarbonates (sodium percarbonate, etc.), hydrogen peroxide, etc.]. These are used alone or in combination of two or more. The amount of the polymerization initiator to be used is usually 0.01 to 5% by weight based on the ethylenically unsaturated monomer (A).

In the emulsion polymerization, known additives may be used if necessary. Examples of the additive include reducing agents [sodium pyrobisulfite, sodium sulfite, sodium hydrogen sulfate, ferrous sulfate, glucose, sodium formaldehyde sulfoxylate, L-ascorbic acid (salt)], chelating agents (glycine, alanine, And a pH buffer (sodium tripolyphosphate, potassium tetrapolyphosphate, etc.).

In the emulsion polymerization, a known chain transfer agent can be used if necessary for the purpose of adjusting the molecular weight of the resin. As the chain transfer agent, α-methylstyrene dimer (2,4-diphenyl-4-methyl-1-methyl)
Pentene), terpinolene, terpinene, dipentene, alkyl mercaptan having 8 to 18 carbon atoms, and 8 carbon atoms
To 18 alkylene dithiols, alkyl thioglycolates, dialkyl xanthogen disulfides, tetraalkyl thiuram disulfides, carbon tetrachloride and the like. These can be used alone or in combination of two or more. The amount of the chain transfer agent used is usually 15% by weight or less, preferably 10% by weight, based on the ethylenically unsaturated monomer (A).
% By weight or less.

The resin content in the aqueous resin dispersion obtained by the method of the present invention is usually 20 to 75% by weight, preferably 4% by weight.
0 to 60% by weight, and the viscosity of the dispersion at 25 ° C is usually 10 to 100,000 mPa · s, preferably 5 to 100,000 mPa · s.
0 to 5,000 mPa · s. The polymer particle diameter in the aqueous dispersion is usually from 10 to 10,000 nm, preferably from 100 to 5,000 nm.

The aqueous resin dispersion obtained by the method of the present invention has a high concentration and a low viscosity and gives a film having excellent water resistance. For example, paints for architectural use and automobiles; pressure-sensitive adhesives; Adhesives (woodworking or paperworking adhesives, etc.); inks for surface printing; binders for non-woven fabrics;
Fiber treatment agents such as binders for pigment printing and texture modifiers;
It can be suitably used for a wide range of uses such as paper processing agents such as a binder for coated paper.

The aqueous dispersion obtained by the method of the present invention includes:
If necessary, known additives (for example, pigments, fillers, thickeners, crosslinking agents, heat or weather resistance stabilizers, leveling agents, defoaming agents, preservatives, etc.) may be optionally added according to the intended use. Can be.

[0051]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. In the following, "parts" indicates parts by weight and "%" indicates% by weight.

Example 1 Polyoxyethyleneoxypropylene glycol [polypropylene glycol (number average molecular weight: 3,500)
O-added; number average molecular weight 15,000] 100
And 1.2 parts of HDI were reacted at 170 ° C. for 5 hours,
An emulsifier [1] for emulsion polymerization of the present invention was obtained. S of this thing
The P value was 9.2, the HLB was 15.6, the SP value of the hydrophobic group (polyoxypropylene group) was 8.7, and the weight average molecular weight by gel permeation chromatography (the same applies hereinafter) was 230,000.

Example 2 Polyethylene glycol (number average molecular weight 20,000)
90 parts, polyoxyethylene oxypropylene glycol [polypropylene glycol (number average molecular weight 3,50)
0) with EO added; number average molecular weight 15,000
0], 10 parts of polytetramethylene ether glycol (number average molecular weight 1,000) and 1.4 parts of TDI were reacted at 160 ° C for 5 hours to obtain an emulsifier [2] for emulsion polymerization of the present invention. The SP value of this is 9.4,
HLB is 17.9, hydrophobic group (polyoxypropylene group)
Had an SP value of 8.7 and a weight average molecular weight of 89,000.

Example 3 200 parts of polyoxyalkylene polyol [hexene glycol to which EO and PO are added at random; number average molecular weight 15,000, EO content 75%] and TDI
2.2 parts were reacted at 150 ° C. for 8 hours to obtain an emulsifier [3] for emulsion polymerization of the present invention. The SP value of this is 9.2,
HLB is 15.3, hydrophobic group (polyoxyhexylene group)
Had an SP value of 8.9 and a weight average molecular weight of 75,000.

Example 4 Polyoxyalkylene monol [nonylphenol with EO added; number average molecular weight 2,000] 50
Parts, polyethylene glycol (number average molecular weight 8,000
0) 100 parts and HDI 6.6 parts were reacted at 100 ° C. for 6 hours to obtain an emulsifier [4] for emulsion polymerization of the present invention. The SP value was 9.5, the HLB was 18.3, the SP value of the hydrophobic group (nonylphenyl group) was 8.5, and the weight average molecular weight was 15,000.

Example 5 Polyoxyalkylene monool [styrene (2 mol)
EO added to activated phenol; number average molecular weight 1,
500] 15 parts, 100 parts of polyethylene glycol (number average molecular weight 20,000) and 2.6 parts of TDI
The reaction was carried out at 0 ° C. for 3 hours to obtain an emulsifier [5] for emulsion polymerization of the present invention. Its SP value is 9.5 and HLB is 1
8.0, SP value of hydrophobic group (styrenated phenol) is 1
0.3, the weight average molecular weight was 25,000.

Example 6 Polyoxyalkylene monool [styrene (2 mol)
EO added to activated phenol; number average molecular weight 1,
500] 15 parts, 100 parts of polyethylene glycol (number average molecular weight 20,000) and 1.5 parts of adipic acid were reacted at 150 ° C. for 1 hour under a nitrogen atmosphere, and then heated to 230 ° C. over 5 hours. By dehydration condensation, an emulsifier [6] for emulsion polymerization of the present invention was obtained. The SP value of this is 9.
4, HLB is 18.0, weight average molecular weight is 20,000
Met.

Example 7 A reaction vessel equipped with a stirrer, a dropping funnel, a nitrogen gas inlet tube, a thermometer and a reflux condenser was charged with 250 parts of ion-exchanged water and 250 parts of isopropyl alcohol, and the system was stirred with nitrogen gas. This was replaced and the temperature was raised to 85 ° C. At the same temperature, 40 parts of 2-hydroxyethyl acrylate and 60 parts of acrylic acid
Of butyl methacrylate, 5.6 parts of dodecyl mercaptan, 4.2 parts of azobisisovaleronitrile and 16 parts of methyl ethyl ketone were added dropwise over 3 hours, and the mixture was further reacted at the same temperature for 1 hour. 30 aqueous solutions
° C, add 51 parts of 28% aqueous ammonia and add pH
After adjusting to 8.5, it was further diluted with 595 parts of ion-exchanged water to obtain an aqueous solution (solid content: 19.8%) of the emulsifier [7] for emulsion polymerization of the present invention. The SP value of [7] is 11.
6, HLB is 25.2, weight average molecular weight is 12,000
Met.

Examples 8 to 17, Comparative Examples 1 to 4 Emulsifiers for emulsion polymerization [1] to obtained in Examples 1 to 7
[7], low molecular weight emulsifiers (EO adduct of nonylphenol, number average molecular weight 1,000,
SP value 9.3), and PVA as Comparative Examples 2 and 4.
(Partially saponified polyvinyl alcohol, polymerization degree 1,70
0, a saponification degree of 88%, and an SP value of 17.2) under the following conditions.
0.6) or emulsion polymerization of methyl methacrylate (SP value of polymer 9.9). In a reaction vessel equipped with a stirrer, a dropping funnel, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, emulsifiers for emulsion polymerization [1] to [7], one of a low molecular weight emulsifier and PVA, ion-exchanged water, Potassium sulfate, sodium bicarbonate and dodecyl mercaptan were charged, and the system was purged with nitrogen gas while stirring and the temperature was raised to 60 ° C. At the same temperature, vinyl acetate (Examples 8 to 13, Comparative Examples 1 and 2) or methyl methacrylate (Example 14)
To 17 and Comparative Examples 3 and 4) were added dropwise over 5 hours, and further reacted at the same temperature for 1 hour to complete the polymerization, thereby obtaining an aqueous resin dispersion. The amount of each raw material used is as follows. (1) 100 parts of vinyl acetate or methyl methacrylate (2) 150 parts of ion-exchanged water (3) 0.3 parts of potassium persulfate (4) 0.1 parts of sodium bicarbonate (5) 0.18 parts of dodecyl mercaptan (6) 4) Emulsifier for emulsion polymerization 4 parts (as solid content)

An evaluation test was performed on each of the obtained aqueous resin dispersions by the following test method. The results are shown in Tables 1 and 2. (Test method) Evaporation residue: The obtained resin aqueous dispersion was dried at 130 ° C for 90 minutes using a circulating drier. Viscosity: Adjust the temperature of the obtained aqueous resin dispersion to 25 ° C.
It measured using the L-type viscometer. Water absorption and elution rate: The obtained aqueous resin dispersion was poured into a polypropylene tray and dried at 100 ° C. for 2.5 hours to prepare a film having a thickness of about 0.5 mm. The obtained film was immersed in water at normal temperature for 1 hour, and the weight increase rate was measured to determine the water absorption. The film after immersion in water was dried, and the weight loss was measured and compared with the weight of the film before immersion to determine the dissolution rate.

[0061]

[Table 1]

[0062]

[Table 2]

[0063]

The method for producing an aqueous resin dispersion using the emulsifier for emulsion polymerization of the present invention has the following effects. (1) A high-concentration, low-viscosity resin aqueous dispersion can be obtained as compared with a conventional method using an emulsifier (eg, polyvinyl alcohol). (2) The film obtained from the dispersion has excellent water resistance. The resin aqueous dispersion obtained by the method of the present invention from the above effects, paints, adhesives, inks, fiber treatment agents,
It is extremely useful for various industrial uses such as paper processing agents.

──────────────────────────────────────────────────続 き Continued on front page Examiner Soichi Yuka (58) Field surveyed (Int.Cl. ⁶ , DB name) C08F 2/00-2/30 B01F 17/52

Claims (14)

(57) [Claims] 1. An emulsifier for emulsion polymerization of an ethylenically unsaturated monomer (A), having a weight average molecular weight of 5,000 to 500,000, and comprising an SP of a (co) polymer (A). Has an SP value less than or equal to 2 and an HLB of 6 to 40
An emulsifier for emulsion polymerization, comprising a compound (B) having the following formula: 2. An emulsifier for emulsion polymerization of an unsaturated monomer (A1) comprising a vinyl ester, comprising an SP of 8 to 16.
The emulsifier for emulsion polymerization according to claim 1, comprising a compound (B1) having a value and an HLB of 10 to 30. 3. An emulsifier for emulsion polymerization of an unsaturated monomer (A2) comprising (meth) acrylic esters, comprising:
The emulsifier for emulsion polymerization according to claim 1, comprising a compound (B2) having an SP value of -20 and an HLB of 8-40. 4. An emulsifier for emulsion polymerization of an unsaturated monomer (A3) comprising styrenes and dienes, wherein the emulsifier comprises 7-1.
The emulsifier for emulsion polymerization according to claim 1, comprising a compound (B3) having an SP value of 5 and an HLB of 6 to 25. 5. An emulsifier for emulsion polymerization of an unsaturated monomer (A4) comprising a nitrile and a diene, comprising 8 to 1
The emulsifier for emulsion polymerization according to claim 1, comprising a compound (B4) having an SP value of 7 and an HLB of 8 to 30. 6. An emulsifier for emulsion polymerization of an unsaturated monomer (A5) comprising a halogenated vinyl, wherein the emulsifier comprises 9 to 18 S
The emulsifier for emulsion polymerization according to claim 1, comprising a compound (B5) having a P value and an HLB of 6 to 25. 7. (B) is an SP of the (co) polymer of (A).
The emulsifier for emulsion polymerization according to any one of claims 1 to 6, wherein the compound has at least two hydrophobic groups in a molecule having a SP value of 2 or less. 8. The method according to claim 1, wherein the hydrophobic group is a hydrocarbon group having 3 to 100 carbon atoms, and a hydrophobic (poly) oxyalkylene (3 to 1 carbon atoms).
The emulsifier for emulsion polymerization according to claim 7, wherein the emulsifier is at least one member selected from the group consisting of 0) and a polyalkylsiloxane group. 9. The method according to claim 9, wherein (B) is an oxyalkylene unit having 20
The emulsifier for emulsion polymerization according to any one of claims 1 to 8, wherein the emulsifier is a compound containing at least one weight%. 10. The compound (B) wherein a polyoxyethylene chain and the hydrophobic group are bonded via at least one group selected from a urethane group, a urea group, an ester group, an amide group and an ether group. The emulsifier for emulsion polymerization according to claim 9. (B) is represented by the following general formula (1): [Wherein, R ¹ is a residue of an alcohol or phenol compound (D1) having ¹ to 6 hydroxyl groups, X is a residue of an organic polyisocyanate compound (E), and R ² has two hydroxyl groups. The residue of the alcohol or phenol compound (D2), at least one of the k Zs is-
In O- (AO) r-Q, the remaining -N (R ³⁾ ₂ and / or may be -NH-R ³ {wherein, Q is a carbon number 1 to 1
The residue or hydrogen atom of the monohydroxy compound (F) of No. 00, and R ³ are the same or different hydrocarbon groups having 1 to 100 carbon atoms and / or hydroxyl group-containing hydrocarbon groups. ｝, A is an alkylene group having 2 to 30 carbon atoms (provided that m
When n, p, or r oxyalkylene groups OA are composed of two or more oxyalkylene groups, the bonding mode may be either block or random. )
Wherein m, n, p and r are each independently 0 or an integer of 1 to 500 (provided that the sum of m, q n, q p and all r is an integer of at least 10) ,
q is 0 or an integer of 1 to 500, and k is an integer of 1 to 6. The emulsifier for emulsion polymerization according to any one of claims 1 to 10, which is a water-soluble polyurethane compound (U1) represented by the formula: 12. The polyoxyalkylene group represented by the formula (1), wherein the (poly) oxyalkylene group comprises an oxyethylene group alone or an oxyethylene group and an oxypropylene group, and has an oxyethylene unit content of at least 60% by weight. The emulsifier for emulsion polymerization according to claim 11, which is a group. 13. A method for producing an aqueous resin dispersion, comprising subjecting an ethylenically unsaturated monomer (A) to emulsion polymerization in the presence of the emulsifier for emulsion polymerization according to any one of claims 1 to 12. 14. The method according to claim 14, wherein (B) is 0.1% based on the weight of (A).
The method for producing a resin aqueous dispersion according to claim 13, which is used at a ratio of 5 to 30% by weight.