JPH07185296A - New quaternary ammonium type surfactant, emulsifier for emulsion polymerization, dispersant for suspension polymerization and resin modifier - Google Patents

Abstract

PURPOSE:To obtain an emulsifier for emulsion polymerization, a dispersant for suspension polymerization and a resin modifier excellent in water resistance, weatherability and durability by using a new surfactant represented by a specific general formula. CONSTITUTION:A new surfactant is represented by formula I [wherein R1, R2 and R4 are a 1-36C straight chain or branched chain alkyl group of which the hydrogen atom may be substituted with a fluorine atom, an alkenyl group or an aryl group and may be different or same, R3 is a group represented by formula II (wherein R' is hydrogen or methyl), A is a 2-4C alkylene group or a substituted alkylene group, X is halogen, OH, NO3 or SO4CH3 and n is 0 or a positive integer].

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel quaternary ammonium type surfactant. Further, the present invention relates to a novel emulsifier for emulsion polymerization, a novel dispersant for suspension polymerization, and a novel surfactant comprising the surfactant. Vinyl-based resin modifier.

[0002]

2. Description of the Related Art Conventionally, surfactants have been emulsified, dispersed,
It has many functions such as cleaning, wetting, and foaming. Utilizing these properties, fibers, paper, rubber, plastic, metal, paint, ink, adhesives, pigments, civil engineering, etc. It is used in all fields.

Particularly in recent years, there has been an increasing movement toward higher performance of terminal products using a surfactant, and along with this, secondary defects of the surfactant have been pointed out. For example, paints, printing inks, adhesives, etc. are indispensable for surface active agents at the time of manufacturing the product, or for stabilizing the product, and in terms of workability, etc. A surfactant is not required when used for printing, adhesion, adhesion, etc., and rather the existing surfactants have properties such as water resistance and oil resistance of the coating film, printing surface, adhesive film, etc. Often worsens.

As measures against these problems, attempts have been made to reduce the blending amount of surfactants and to make the surfactants higher in molecular weight, but until the stability of products and workability are still sufficiently solved. Has not reached.

Conventional emulsifiers for emulsion polymerization include anionic surfactants such as alkyl sulfates, alkylbenzene sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, and pluronic type interfaces. Nonionic surfactants such as activators have been used.

The emulsifier for emulsion polymerization is involved not only in the initiation reaction and the formation reaction of the polymerization but also in the mechanical stability, the chemical stability, the freezing stability and the storage stability of the produced emulsion. Emulsion physical properties such as particle size, viscosity and foamability, water resistance when formed into a film,
It is known that physical properties of the film such as weather resistance, adhesiveness, and heat resistance are greatly affected. However, in emulsions emulsion-polymerized using a normal emulsifier, the foaming of the emulsion due to the emulsifier is high, and when the emulsion is made into a film, the emulsifier remains in the film in a free state, so that the adhesiveness, Problems such as deterioration of film physical properties such as water resistance, weather resistance, and heat resistance have been pointed out.

In order to eliminate such drawbacks, in recent years, a molecule having a group having surface activity and a group having a polymerizable group,
Proposals have been made regarding reactive surfactants that not only act as emulsifiers but are gradually incorporated into the polymer during polymerization by chemical bonds. For example, there are JP-A No. 2-111427 and JP-A No. 2-164430, but none of them has sufficiently solved the above problems.

As a conventional dispersant for suspension polymerization, when a vinyl resin is industrially produced, a vinyl chloride monomer is dispersed in an aqueous medium in the presence of a dispersion stabilizer to obtain an oil-soluble catalyst. A suspension polymerization method in which the polymerization is carried out is widely practiced. Factors that govern the quality of such resins include the rate of polymerization, water / monomer ratio, polymerization temperature, type and amount of catalyst,
The type of the polymerization tank, the stirring speed, the kind and amount of the dispersion stabilizer, and the like can be mentioned, but it is known that the kind of the dispersion stabilizer has a great influence. As a conventional dispersant for suspension polymerization of a vinyl resin, a cellulose derivative such as methylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, or a water-soluble polymer such as gelatin or polyvinyl alcohol. And so on. However, there is a problem in that such a dispersant remains in the vinyl resin after polymerization in a free state, resulting in deterioration of physical properties of the resin such as water resistance, weather resistance and durability of the vinyl resin. It was

Further, as a vinyl-based resin modifier, conventionally,
JP-A-1-174511 discloses a modifier for a vinyl polymer. However, when this modifier was used, a uniform copolymer could not be obtained because of poor compatibility with the monomer. As an attempt to improve the compatibility, there is JP-A-1-174512, but there is a problem that the compatibility is still insufficient and the effect of modifying the polymer is insufficient.

Therefore, an object of the present invention is to provide a good surfactant which does not have the above-mentioned drawbacks, an emulsifier for emulsion polymerization, a dispersant for suspension polymerization and a resin modifier which are composed of the surfactant.

[0011]

That is, the present invention has the general formula
(1)

[Chemical 3] (In the formula, R ₁ , R ₂ , and R ₄ are each an alkyl group or an alkenyl group in which a linear or branched hydrogen atom having 1 to 36 carbon atoms may be substituted with a fluorine atom, or an aryl group. R ₃ may be the same or different.

[Chemical 4] And R'is hydrogen or methyl.
A is an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group, and may be the same or different. X is a _{halogen, OH, NO 3, SO 4} CH 3. n is 0 or a positive number).

The present invention further provides a novel emulsifier for emulsion polymerization, a novel dispersant for suspension polymerization, and a novel vinyl-based resin modifier comprising the surfactant.

The above compound of the present invention can be obtained, for example, as follows. General formula

[Chemical 5] The secondary amine represented by the general formula

[Chemical 6] It can be obtained by reacting a glycidyl ether compound represented by the formula (3) to give a tertiary amine and then quaternizing with a quaternizing agent such as allyl halide having a group corresponding to R ₃ .

Further, instead of the above allyl halide or alkyl halide, dimethylsulfate and its derivatives, etc.,
Other quaternizing agents having groups corresponding to R ₃ can also be used.

Further, the surfactant of the present invention can be obtained by substituting the anion group of these compounds by a known method.

The method for synthesizing the surfactant of the present invention is not limited to the above.

In the compound of the present invention, the linear or branched alkyl or alkenyl group having 1 to 36 carbon atoms represented by R ₁ and R ₂ is methyl, ethyl, butyl, octyl, decyl, dodecyl, Tetradecyl, hexadecyl, octadecyl, docosyl, tetracosyl,
Triacontyl, 2-ethylhexyl, 2-octyldodecyl, 2-dodecylhexadecyl, 2-tetradecyloctadecyl, monomethyl-branched-isostearyl, octenyl, decenyl, dodecenyl, tetradecenyl, hexadecenyl, octadecenyl, docosenyl, tetracocenyl, triacontenyl, tridecenyl. Decafluorooctyl,
Heptadecafluorododecyl, heneicosafluorododecyl, pentacosafluorododecyl, nonacosafluorododecyl, tritriacontafluorooctadecyl,
2-pentafluoroethyl pentafluorohexyl, 2
-Tridecafluorohexyl tridecafluorodecyl,
2-Heneicosafluorodecyl Heneicosafluorotetradecyl, 2-pentacosafluorododecyl pentacosafluorohexadecyl, 2-nonacosafluorotetradecyl nonacosafluorooctadecyl group, etc. are listed, and the aryl group has a carbon number. A phenyl group substituted with 1 to 15 straight chain or branched chain alkyl group, for example, ethylphenyl, butylphenyl, hexylphenyl, octylphenyl, nonylphenyl group, etc., aminophenyl, cumylphenyl, O-phenylphenyl, P −
Examples thereof include phenylphenyl, styrenated phenyl, paracumylphenyl, α-naphthonyl and β-naphthonyl groups.

A and B in the above formula are alkylene groups having 2 to 4 carbon atoms or substituted alkylene groups such as ethylene, propylene, butylene and isobutylene.
They may be used alone or in a block or random mixture, which may be the same or different, preferably ethylene.

X is halogen, OH, NO ₃ , SO ₄ CH ₃
And preferably halogen.

When the surfactant of the present invention is used as a detergent, R ₁ and R ₂ preferably have 8 to 24 carbon atoms, n is 0 to 150, and more preferably n is 0. ~ 1
It should be 00. In addition, the amount used is 0.01-
10% by weight, preferably 0.1-5% by weight.

When the surfactant of the present invention is used as a wetting agent, R ₁ and R ₂ preferably have 8 to 24 carbon atoms, n is 0 to 150, more preferably 0 to 100.
Is good. Also, the amount used is 0.01 to 10
%, Preferably 0.1-5% by weight.

The surfactant of the present invention is an emulsifier for emulsion polymerization, a dispersant for suspension polymerization, a vinyl-based resin modifier (controlling hydrophilicity, improving compatibility, etc.) as a surfactant having reactivity with a vinyl group. Antistatic property, antifogging property, water resistance property, adhesive property property, dyeability property, film forming property property, weather resistance property, blocking resistance property, etc.).

The emulsifier for emulsion polymerization of the present invention comprises the above-mentioned surfactant of the present invention, preferably R ₁ and R ₂ have 8 to 24 carbon atoms, and n is 0 to 150. It is preferably 0 to 100.

Suitable for applying the emulsifying agent for emulsion polymerization of the present invention is emulsion polymerization of vinyl monomers, for example, vinyl compounds such as vinyl acetate, vinyl propionate, alkyl vinyl ether and alkyl vinyl ketone, and Acrylic acid, methyl acrylate, methyl methacrylate, acrylonitrile, acrylic monomers such as acrylamide, ethylene, propylene, 1-butene, 1-
C2-C30 α-olefins such as pentene, 1-hexane, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, Examples thereof include monomers such as halogen-containing monomers such as vinyl chloride and vinylidene chloride, maleic anhydride, maleic acid esters, and itaconic acid esters. The monomer used is not limited to the above.

The emulsion polymerization emulsifier of the present invention may be used in any amount within the range of the conventional emulsion polymerization emulsifiers generally used, but is generally about 0. 1 to 20% by weight, preferably 0.2 to 10% by weight is good.

The dispersant for suspension polymerization of the present invention comprises the above-mentioned surfactant of the present invention, preferably R ₁ and R ₂ have 1 to 24 carbon atoms, and n is 0 to 150. More preferably, it is 0 to 100.

Suitable for applying the dispersant for suspension polymerization of the present invention is suspension polymerization of vinyl monomers, for example, vinyl acetate, vinyl propionate, alkyl vinyl ether, alkyl vinyl ketone, and other vinyls. Compounds and acrylic monomers such as acrylic acid, methyl acrylate, methyl methacrylate, acrylonitrile, acrylamide, ethylene, propylene, 1-butene, 1-pentene, 1-hexane, 1-heptene, 1-octene,
The carbon number of 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, etc. is 2
.About.30 .alpha.-olefins, monomers such as halogen-containing monomers such as vinyl chloride and vinylidene chloride, maleic anhydride, maleic acid esters, and itaconic acid esters. The monomer used is not limited to the above.

The amount of the dispersant for suspension polymerization of the present invention can be arbitrarily used within the range of the conventionally used dispersant for suspension polymerization known in the related art. Therefore, 0.1 to 20% by weight, preferably 0.2 to 10% by weight is good.

The vinyl-based resin modifier of the present invention comprises the above-mentioned surfactant, and preferably R ₁ and R _{2 each} have 1 carbon atom.
It is preferable that n is 0 to 150, and more preferably 0 to 100.

Suitable for applying the vinyl resin modifiers of the present invention are resins from vinyl monomers,
For example, vinyl compounds such as vinyl acetate, vinyl propionate, alkyl vinyl ether, and alkyl vinyl ketone, acrylic monomers such as acrylic acid, methyl acrylate, methyl methacrylate, acrylonitrile, and acrylamide, ethylene, propylene, 1-butene, 1
-Pentene, 1-hexane, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, and the like α-olefin having 2 to 30 carbon atoms. , Monomers such as halogen-containing monomers such as vinyl chloride and vinylidene chloride, maleic anhydride, maleic acid esters, and itaconic acid esters. The monomer used is not limited to the above.

The vinyl-based resin modifier of the present invention is capable of simultaneously improving the compatibility with the monomer and the modifying effect. Further, by using the modifier of the present invention,
It is possible to impart permanent antistatic property and antifogging property to the resin used.

The amount of the modifier of the resin of the present invention to be used can be variously changed depending on the kind of the monomer, the purpose of the modification, the required performance and the like. 1 to
95% by weight can be used, and particularly, when a water-soluble resin having insufficient hydrophilicity is to be converted into a highly hydrophilic polymer, it is preferable to use 10 to 80% by weight based on the monomer. .

Polymers for other applications such as water resistance, adhesiveness, antistatic property, antifogging property, dyeing property, film forming property, weather resistance and blocking resistance, or for polymer alloys. When it is intended to impart compatibilization property to the monomer, it is preferably used in an amount of 0.1 to 20% by weight based on the monomer.

When the vinyl resin modifier of the present invention is used, divinylbenzene is added to improve the physical properties of the polymer.
A cross-linkable divinyl compound such as ethylene glycol dimethacrylate or methylene bisacrylamide can be arbitrarily used within the range of the usual amount used.

[0035]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. Production Example A (C ₁₂ H ₂₅ ) ₂ NH

[Chemical 7] The compound represented by the formula:

[Chemical 8] The following surfactant (A) was obtained.

Preparation Example B CH was used instead of (C ₁₂ H ₂₅ ) ₂ NH used in Preparation Example A.
₃ (C ₁₂ H ₂₅ ) NH is used

[Chemical 9] Instead of

[Chemical 10] Was used, except that allyl iodide was used instead of allyl chloride, the same reaction as in Production Example A was performed, the obtained compound was dissolved in water, silver oxide was added to liberate the base, and the silver salt was formed. The removed liquid is distilled and structural formula

[Chemical 11] The following surfactant (B) was obtained.

Preparation Example C Instead of the (C ₁₂ H ₂₅ ) ₂ NH used in Preparation Example A, (C ₁₈ H
₃₇ ) ₂ NH is used,

[Chemical 12] Instead of

[Chemical 13] Except that the same reaction as in Production Example A was performed except that

[Chemical 14] The following surfactant (C) was obtained.

Production Example D Instead of (C ₁₂ H ₂₅ ) ₂ NH in Production Example A, C ₃ H ₇ (C ₉ H ₁₉
Ph) NH is used

[Chemical 15] Instead of

[Chemical 16] And using the same reaction as in Preparation Example A except that allyl bromide was used instead of allyl chloride.

[Chemical 17] The following surfactant (D) was obtained.

Preparation Example E Instead of the (C ₁₂ H ₂₅ ) ₂ NH used in Preparation Example A, (C ₁₄ H _25
29 ) ₂ NH, except that the same reaction as in Production Example A was performed

[Chemical 18] The following surfactant (E) was obtained.

Preparation Example F Instead of the (C ₁₂ H ₂₅ ) ₂ NH used in Preparation Example A, (C ₁₈ H
₃₅ ) ₂ NH is used,

[Chemical 19] Instead of

[Chemical 20] And using methallyl bromide instead of allyl chloride to carry out the reaction in the same manner as in Production Example A,
Structural formula

[Chemical 21] The following surfactant (F) was obtained.

Preparation Example G Instead of the (C ₁₂ H ₂₅ ) ₂ NH used in Preparation Example A, C ₈ H _{17 was used.}
(C ₁₆ H ₃₃ ) NH is used,

[Chemical formula 22] Instead of

[Chemical formula 23] Except that the same reaction as in Production Example A was performed,

[Chemical formula 24] The following surfactant (G) was obtained.

Preparation Example H Instead of the (C ₁₂ H ₂₅ ) ₂ NH used in Preparation Example A, C ₁₀ H
₂₁ (C ₁₂ H ₂₅ ) NH is used,

[Chemical 25] Instead of

[Chemical formula 26] And using methallyl bromide instead of allyl chloride to carry out the same reaction as in Production Example A,

[Chemical 27] The following surfactant (H) was obtained.

Preparation Example I Instead of the (C ₁₂ H ₂₅ ) ₂ NH used in Preparation Example A, C ₉ H _{19 was used.}
The same reaction as in Production Example A was performed except that (C ₁₆ H ₃₃ ) NH was used,

[Chemical 28] The following surfactant (I) was obtained.

The following surfactants were used as comparative surfactants. Comparative Example 1 3-Allyloxy-2-hydroxypropyl dimethyldecyl ammonium chloride

Comparative Example 2 Hydroxypropyl methylcellulose

Comparative Example 3 Addition product of nonylphenol with 30 mol of ethylene oxide

Example 1 The surface tension of the aqueous solutions of the surfactants (A) to (I) of the present invention and Comparative Examples (1) to (3) were measured. (Note that the surface tension was measured by the Wilhelmi method). The results are shown in Table 1.

[0048]

[Table 1]

Example 2 With respect to the surfactants (A) to (I) of the present invention and Comparative Examples (1) to (3), the dispersion performance of carbon black and the emulsification performance of toluene were measured. The results are shown in Table 2. The test method is as follows. <Dispersion performance test method> 1 g of the surfactant and 10 g of carbon black were placed in a graduated cylinder with a stopper of 100 ml, and dissolved and dispersed in water to adjust to 100 ml. next,
After shaking the graduated cylinder 100 times for 1 minute,
It was allowed to stand at 25 ° C for a time. After that, 30 cc from the liquid surface
After filtering with a sampling glass filter, it was dried at 105 ° C., and the dispersibility was measured from the weight of the residue on the glass filter by the following formula. Dispersion performance (%) = glass filter residue weight (g) / 3
(g) × 100 <Emulsification performance test method> In a test tube with a graduated stopper having a capacity of 20 ml, 5 ml of 0.5% aqueous surfactant solution and 5 m of kerosene
1 and then shaken 100 times in 1 minute, then at 25 ° C for 1 hour
Then, the volume (ml) of the emulsified layer was measured, and the emulsifying property was measured by the following formula. Emulsification performance (%) = Emulsion layer (ml) / 10 (ml) x 100

[0050]

[Table 2]

Example 3 Using the surfactants (A) to (I) of the present invention and the surfactant of Comparative Example (1), emulsion polymerization was carried out using ethyl acrylate as a monomer. Regarding the obtained polymer emulsion,
The mechanical stability, foamability and water resistance of the polymer film obtained from the polymer emulsion were measured. The results are shown in Table 3. <Polymerization method> 120 g of water was charged into a reaction vessel equipped with a reflux condenser, a stirrer, a dropping funnel and a thermometer, and the inside of the system was replaced with nitrogen gas. Separately, in 80 g of ethyl acrylate, 4 g of the surfactant compositions (A) to (I) of the present invention and the surfactant of Comparative Example (1) were dissolved. 08 g and 0.04 g of sodium hydrogen sulfite were added to the reaction vessel, and polymerization was started at 50 ° C. Then, the remaining monomer / surfactant mixture was continuously dropped into the reactor over 2 hours, and after the dropping was completed, the mixture was aged for 2 hours to obtain an emulsion. <Evaluation / Measurement method> Mechanical stability 50g of emulsion is 10k with Marron method stability tester
g, 1000 rpm, rotating for 5 minutes, the produced agglomerate is filtered through a 100-mesh wire net, the filter residue is washed with water and dried at 105 ° C. for 2 hours. It is represented by. Effervescent emulsion is diluted 2 times with water and 20 ml of this diluted emulsion is put into a 100 ml graduated test tube.
Measure the bubble height when shaken up and down for 0 seconds and display in ml. Water resistance of the film Depending on the time required for whitening the 0.2 mm polymer film by the water immersion method, ◎: 1 day or more, ◯: 1 hour or more,
X: Evaluation is made on the basis of less than 1 hour.

[0052]

[Table 3]

Example 4 In 150 liters of glass lined autoglove, 150 parts by weight of deionized water was added with each of the surfactants (A) to (I) and the surfactant of Comparative Example (2) as a dispersant. Parts by weight and di-2-ethylhexylperoxycarbone.
After charging 2 parts by weight and degassing the inside of the auto grove to 50 mmHg to remove oxygen, vinyl chloride monomer
Was charged in an amount of 100 parts by weight, and the temperature was raised to 57 ° C. with stirring at a rotation speed of 500 rpm to carry out polymerization. At the start of the polymerization, the pressure in the auto grove was 8.0 kg / cmG. However, after 7 hours from the start of the polymerization, it became 4.0 kg / cmG. Vinyl monomer
Then, the contents were taken out and dehydrated and dried.

Example 5 In place of the vinyl chloride monomer used in Example 4, 100 parts by weight of ethylene monomer was charged and a surfactant was used.
Polymerization was carried out in the same manner as in Example 4 except that 1 part by weight of each of the surfactants (A), (E), (H) and Comparative Example (2) was used as a dispersant.

Example 6 In place of the vinyl chloride monomer used in Example 4, 100 parts by weight of vinyl acetate monomer was added and a surfactant was added.
Polymerization was carried out in the same manner as in Example 4 except that 1 part by weight of each of the surfactants (B), (F), (I) and Comparative Example (2) was used as a dispersant.

Example 7 In place of the vinyl chloride monomer used in Example 4, 100 parts by weight of ethyl vinyl ether monomer was charged, and the surfactants (C), (D), (G) and Comparative Example (2) were prepared. Example 4 except that 1 part by weight of each surfactant was used as a dispersant.
Polymerization similar to the above was carried out.

Example 8 In place of the vinyl chloride monomer used in Example 4, 100 parts by weight of a mixture of vinyl chloride monomer / ethyl acrylate (weight ratio 2/1) was charged, and the surfactants (A), (C )
And the surfactant of Comparative Example (2) as a dispersant, respectively.
Polymerization was carried out in the same manner as in Example 4 except that parts by weight were used.

The following tests were conducted on the resins obtained in Examples 4 to 8 above. The results are shown in Table 4. (1) Particle size distribution: The dry resin analysis using a wire mesh based on Tyler-mesh was used to measure the weight ratio of particles of the obtained resin particles that did not pass through 250 mesh. (2) Water resistance: The sol was adjusted with the following composition, and the sol was adjusted to 0.5.
The sheet having a thickness of 190 mm and heated at 190 ° C. for 10 minutes was immersed in water at 23 ° C. for 24 hours, and the light transmittance was measured. (3) Thermal stability: The same sol used for water resistance was poured into an aluminum mold and heated at 190 ° C. in a hot air atmosphere for 30 days.
The change in color tone after minute is shown in five stages from A (small change) to E (large change).

[0059]

[Table 4]

Example 9 Compatibility with Monomer 10 g each of styrene, methacrylic acid, vinyl acetate and acrylonitrile, and the surfactants (A) to (I) of the present invention and the surfactant of Comparative Example (3), respectively. As a modifier, 2 g was mixed and the compatibility between the various modifiers and the above monomer was evaluated. The results are shown in Table 5.

[0061]

[Table 5]

Example 10 100 g of xylene was charged into a reaction vessel equipped with a reflux condenser, a stirrer, a dropping funnel and a thermometer, and the system was replaced with nitrogen gas. Separately, 150 g of styrene, the surfactant of the present invention
A mixed solution of 7.5 g of each of (A) to (I) and the surfactant of Comparative Example (3) as a modifier, 2 g of benzoyl peroxide, and 1 g of di-tert-butyl-peroxide was prepared,
The above mixed solution was continuously added dropwise into the reactor at a reaction temperature of 130 ° C. for 2 hours. Further, a mixed solution of 10 g of xylene, 0.5 g of benzoyl peroxide and 0.5 g of di-tert-butyl-peroxide was added dropwise and reacted for 2 hours. Then, the mixture was cooled and 90 g of xylene was added to obtain a polymer solution. A polymer film having a thickness of 0.2 mm was prepared from each of the obtained polymer solutions by a conventional method, and water resistance, antifogging property and antistatic property were evaluated by the following methods. The results are shown in Table 6.
Shown in.

Measurement / Evaluation Method Water Resistance of Film 1 g of the polymer film was placed in boiling water and boiled for 24 hours,
Then, it was dried at 105 ° C. for 2 hours and the change of the film was observed. ⊚: No change, ◯: Part of the film surface was clouded Δ: Part of the film was deformed ×: Entire film was deformed Anti-fog property of the film The contact angle of water with respect to the polymer film was measured. Antistatic Property of Film The polymer film was allowed to stand in an atmosphere having a temperature of 20 ° C. and a humidity of 45% for 24 hours, and the surface resistivity was measured.

Example 11 100 g of xylene was charged into a reaction vessel equipped with a reflux condenser, a stirrer, a dropping funnel and a thermometer, and the system was replaced with nitrogen gas. Separately, 75 g of 2-ethylhexyl acrylate,
75 g of methacrylic acid, the surfactants (A), (C) of the present invention,
7.5 g of the surfactants of (E), (G), (I) and Comparative Example (3) as modifiers, 2 g of benzoyl peroxide, di.
A mixed solution of 0.5 g of tertiary butyl peroxide was prepared, and the mixed solution was continuously added dropwise into the reactor at a reaction temperature of 130 ° C. for 2 hours. Furthermore, xylene 1
A mixed solution of 0 g, 0.5 g of benzoyl peroxide and 0.5 g of di-tert-butyl-peroxide was added dropwise and reacted for 2 hours. Then, the mixture was cooled and 90 g of xylene was added to obtain a polymer solution. 0.2 for each polymer solution obtained
A mm-thick polymer film was prepared by a conventional method, and water resistance, antifogging property and antistatic property were evaluated in the same manner as in Example 10, respectively. The results are shown in Table 6.

[0065]

[Table 6]

[0066]

The effect of the present invention is to provide a good surfactant without the above-mentioned drawbacks. Another effect of the present invention is to provide a good emulsifier for emulsion polymerization without the above-mentioned drawbacks. Another effect of the present invention is to provide a good dispersant for suspension polymerization without the above-mentioned drawbacks. Another effect of the present invention is to provide a good vinyl resin modifier which does not have the above-mentioned drawbacks.

Claims (4)

[Claims] 1. A compound represented by the general formula (1): (In the formula, R ₁ , R ₂ , and R ₄ are each an alkyl group or an alkenyl group in which a linear or branched hydrogen atom having 1 to 36 carbon atoms may be substituted with a fluorine atom, or an aryl group. R ₃ may be the same or different, and R ₃ is represented by the general formula (2): And R'is hydrogen or methyl.
A is an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group, and may be the same or different. X is a _{halogen, OH, NO 3, SO 4} CH 3. n is 0 or a positive number). 2. A novel emulsifying agent for emulsion polymerization, which comprises the surfactant according to claim 1. 3. A novel dispersant for suspension polymerization, which comprises the surfactant according to claim 1. 4. A novel vinyl-based resin modifier comprising the surfactant according to claim 1.