JP3459102B2 - New surfactants, new emulsifiers for emulsion polymerization, new dispersants for suspension polymerization, new resin modifiers - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention has a reactivity with vinyl groups.
The present invention also relates to a novel emulsifier for emulsion polymerization, a novel dispersant for suspension polymerization, and a novel vinyl-based resin modifier comprising the surfactant.

[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, the emulsion produced by emulsion polymerization using a normal emulsifier has high foaming of the emulsion due to the emulsifier, and when the emulsion is formed into a film, the emulsifier remains in the film in a free state, and It has been pointed out that there are problems such as deterioration of film physical properties such as water resistance, weather resistance and heat resistance.

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 among them, the effect of the kind of the dispersion stabilizer is very large. 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, such a dispersant is free in the vinyl resin after polymerization.
However, there is a problem that the physical properties of the resin such as water resistance, weather resistance, and durability of the vinyl resin are deteriorated due to the residual.

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 comprise the surfactant.

[0011]

That is, the present invention is based on the general formula (1)

[Chemical 3] (In the formula, R ₁ is an alkyl group, an alkenyl group, or an aryl group in which linear or branched hydrogen having 1 to 36 carbon atoms may be substituted with a fluorine atom. R ₂
Is the general formula (2)

[Chemical 4] And R'is hydrogen or methyl.
k is 2 and m is 1 . A is an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group, n is a positive number, and X is halogen, OH, NO ₃ , SO ₄ CH ₃
Is shown. ) Is represented by
The present invention relates to a novel surfactant having reactivity with a diol group .

Further, the present invention relates to a novel emulsifier for emulsion polymerization, a novel dispersant for suspension polymerization, and a novel vinyl resin modifier, which comprises the surfactant.

The above-mentioned surfactant of the present invention can be obtained, for example, as follows.

[Chemical 5] The secondary amine represented by (R ₁ is the same as above) has 2 carbon atoms.
~ 4 alkylene oxide is added to form a tertiary amine, and then a quaternizing agent having a substituent corresponding to R ₂ such as allyl halide is acted to quaternize, or

[Chemical 6] (R 'is the same as above), the secondary amine has 2 carbon atoms
~ 4 alkylene oxide is added to give a tertiary amine, and then a quaternizing agent having a substituent corresponding to the above R ₁ such as an alkyl halide is allowed to act to effect quaternization, whereby M is halogen. A surfactant can be obtained.

Further, instead of the above allyl halide or alkyl halide, dimethylsulfate and its derivatives, etc.,
Other quaternizing agents having groups corresponding to R ₁ and R ₂ 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.

Examples of the linear or branched alkyl or alkenyl group having 1 to 36 carbon atoms represented by R ₁ in the compound of the present invention include 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, tridecafluorooctyl, heptadecafluorododecyl, heneicosafluorododecyl, pentacosafluorododecyl, nonacosafluorododecyl, trito A contour-fluoro-octadecyl, 2
-Pentafluoroethyl pentafluorohexyl, 2-
Tridecafluorohexyl tridecafluorodecyl, 2
-Heneicosafluorodecyl heneicosafluorotetradecyl, 2-pentacosafluorododecyl pentacosafluorohexadecyl, 2-nonacosafluorotetradecyl nonacosafluorooctadecyl group, etc.
As the aryl group, a phenyl group substituted by a linear or branched alkyl group having 1 to 15 carbon atoms, for example, ethylphenyl, butylphenyl, hexylphenyl,
Examples include octylphenyl, nonylphenyl groups, aminophenyl, cumylphenyl, O-phenylphenyl, P-phenylphenyl, styrenated phenyl, paracumylphenyl, α-naphthonyl, β-naphthonyl and the like.

When k is 2, R ₁ may be the same or different. Further, A in the above formula is an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group, for example, ethylene, propylene, butylene, isobutylene, etc., which may be a single or a block or random mixture thereof, preferably Is 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 preferably has 8 to 24 carbon atoms, n is 1 to 150, and more preferably n is 1 to 100.
Is good. Also, the amount used is 0.01 to 10
%, Preferably 0.1-5% by weight.

When the surfactant of the present invention is used as a wetting agent, R ₁ preferably has 8 to 24 carbon atoms, n is 1 to 150, and more preferably n is 1 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 resin modification (hydrophilicity adjustment, compatibility improvement, 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 has 8 to 24 carbon atoms, n is 1 to 150, and more preferably n. Is preferably 1 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-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 emulsifier for emulsion polymerization of the present invention to be used can be arbitrarily used within the range of the conventionally used amount of the conventionally known emulsifier for emulsion polymerization, but it is generally 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 has 1 to 24 carbon atoms, and n is more preferably 1 to 150. n is preferably 1-100.

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 conventional amount of a 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 has 1 to 2 carbon atoms.
4 is preferable, n is 1 to 150, and more preferably n is 1 to 100.

Suitable for applying the vinyl-based resin modifier of the present invention is a resin from a vinyl-based monomer,
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 uses such as water resistance, adhesiveness, antistatic property, antifogging property, dyeability, film forming property, weather resistance, blocking resistance, etc., or polymers 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, in order 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.

[0034]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. Production Example A 5 mol of ethylene oxide was added to 1 mol of (C ₁₂ H ₂₅ ) ₂ NH according to a conventional method, and then the obtained compound was reacted with an equimolar amount of allyl chloride according to a conventional method.

[Chemical 7] The following surfactant (A) was obtained.

Preparation Example B Instead of the (C ₁₂ H ₂₅ ) ₂ NH used in Preparation Example A, C ₁₆ H
₃₃ (C ₈ H ₁₇ ) NH was used, the same reaction as in Production Example A was carried out except that the addition number of ethylene oxide was changed to 10 mol.

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

Preparation Example C Instead of (C ₁₂ H ₂₅ ) ₂ NH used in Preparation Example A, (C ₁₈ H
₃₇ ) Use NH and adjust the number of ethylene oxide added to 20
The reaction was performed in the same manner as in Production Example A except that the molar ratio was changed to

[Chemical 9] The following surfactant (C) was obtained.

Production Example D The same reaction as in Production Example A was conducted except that the ethylene oxide used in Production Example A was replaced with a mixture of 10 moles of ethylene oxide and 10 moles of propylene oxide.

[Chemical 10] The following surfactant (D) was obtained.

[0038]

Preparation Example F Instead of the (C ₁₂ H ₂₅ ) ₂ NH used in Preparation Example A, (C ₁₄ H _25
29 ) ₂ NH was used, and in place of ethylene oxide, 30 mol of ethylene oxide, 20 mol of propylene oxide, and 5 mol of butylene oxide were added in blocks.
The same reaction as in Production Example A was carried out except that allyl bromide was used instead of allyl chloride, and the structural formula

[Chemical 12] The following surfactant (F) was obtained.

Preparation Example G Instead of the (C ₁₂ H ₂₅ ) ₂ NH used in Preparation Example A, C ₁₆ H
₃₃ (C ₁₈ H ₃₅ ) NH was used, 50 mol of ethylene oxide and 10 mol of propylene oxide were added in a block form in place of ethylene oxide, and allyl bromide was used instead of allyl chloride. The same reaction is performed and the structural formula

[Chemical 13] 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
Production Example except that ₂₁ (C ₅ H ₁₁ ) NH was used, 80 mol of ethylene oxide and 20 mol of propylene oxide were added in a block form in place of ethylene oxide, and methallyl iodide was used instead of allyl chloride. A
The reaction is performed in the same manner as above, the resulting compound is dissolved in water, silver oxide is added to liberate the base, and the solution from which the silver salt has been removed is distilled to obtain the structural formula

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

[0042]

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

Comparative Example 2 Hydroxypropyl methyl cellulose

Comparative Example 3 Ethylene oxide 30 mol adduct of nonylphenol

Example 1 The surface tensions of the aqueous solutions of the surfactants (A) to (D), (F) to (H) 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.

[0047]

[Table 1]

Example 2 With respect to the surfactants (A) to (D), (F) to (H) of the present invention and Comparative Examples (1) to (3), the dispersion performance of carbon black and the emulsification performance of toluene were evaluated. It was measured. The results are shown in Table 2. The test method is as follows. <Dispersion Test method> capacity surfactant co stoppered measuring cylinder 100 ml 1
g and 10 g of carbon black were added, dissolved and dispersed in water to adjust to 100 ml. Next, the graduated cylinder was shaken 100 times in 1 minute and then left still at 25 ° C. for 1 hour. Then, after removing 30 cc from the liquid upper surface and filtering with a 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 (%) = residual weight of glass filter (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 kerosene After adding 5 ml, the mixture was shaken 100 times for 1 minute and then left standing 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 (%) = emulsified layer (ml) / 10 (ml) x 100

[0049]

[Table 2]

Example 3 Using the surfactants (A) to (D) and (F) to (H) of the present invention and the surfactant of Comparative Example (1), emulsion polymerization was carried out using ethyl acrylate as a monomer. went. Next to the obtained polymer emulsion, its mechanical stability, foamability and water resistance were measured on the polymer film obtained from the polymer emulsion. 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 system was replaced with nitrogen gas. Separately, in 80 g of ethyl acrylate, 4 g of the surfactants (A) to (D) and (F) to (H) of the present invention and the surfactant of Comparative Example (1) were dissolved. potassium sulfate 0.08 g, sodium hydrogensulfite 0.04g was added to the reaction vessel, and polymerization was initiated 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> 50g of mechanical stability emulsion is 10k with Marron method stability tester
g, 1000 rpm, rotating for 5 minutes, the produced coagulum was filtered through a 100-mesh wire net, the filter residue was washed with water and dried at 105 ° C. for 2 hours. Represent Dilute the effervescent emulsion twice with water and add 20 ml of this diluted emulsion to a 100 ml graduated test tube.
Measure the bubble height when shaken up and down for 0 seconds and display in ml. Depending on the time required to whiten a polymer film having a water resistance of 0.2 mm by a water immersion method, ⊚: 1 day or more, ∘: 1 hour or more,
X: Evaluation is made on the basis of less than 1 hour.

[0051]

[Table 3]

Example 4 150 liters of glass-lined autoclave, 150 parts by weight of deionized water, surfactants (A) to (D),
(F) to (H) and 1 part by weight of the surfactants of Comparative Example (2) as dispersants and 0.2 part by weight of di-2-ethylhexyl peroxycarbonate were charged until the inside of the autograve became 50 mmHg. After degassing to remove oxygen, 100 parts by weight of vinyl chloride monomer was charged, 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 polymerization, the pressure inside the autograve is 8.0 kg.
/ CmG, but after 7 hours from the start of polymerization, 4.0 kg /
Since it became cmG, the polymerization was stopped at this point, unreacted vinyl chloride monomer was purged, 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 the surfactants (A) and ( H) and the surfactant of Comparative Example (2) were dispersed respectively. Polymerization was performed in the same manner as in Example 4 except that 1 part by weight was used as the agent.

[0054] Instead of the vinyl chloride monomers used in Example 5 Example 4, 100 parts by weight were charged vinyl acetate monomer, surfactant (A), the surfactant (F) 及 beauty Comparative Example (2) Polymerization was carried out in the same manner as in Example 4 except that 1 part by weight of each dispersant was used.

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 surfactants (C), (D), (G) and Comparative Example (2) were prepared. The same polymerization as in Example 4 was carried out except that 1 part by weight of a surfactant was used as a dispersant.

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) were added. )
Polymerization was carried out in the same manner as in Example 4 except that 1 part by weight of each of the surfactants of Comparative Example (2) was used as a dispersant.

The following tests were conducted on the resins obtained in Examples 4 to 8 above. The results are shown in Table 4. <Evaluation method> (1) Particle size distribution: The dry resin analysis using a wire mesh based on Tyler-mesh was used to measure the weight percentage of particles of the 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).

[0058]

[Table 4]

Example 9 Compatibility with Monomers 10 g each of styrene, methacrylic acid, vinyl acetate and acrylonitrile and the surfactants (A) to (D) of the present invention ,
The surfactants of (F) to (H) and Comparative Examples (1) and (2) were used as modifiers, and 2 g of each was mixed to evaluate the compatibility of the various modifiers with the above monomers. The results are shown in Table 5.

[0060]

[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 surfactants (A) to (D), (F) to (H) of the present invention and Comparative Example (2),
7.5 g of each of the surfactants of (3) as a modifier,
A mixed solution of 2 g of benzoyl peroxide and 1 g of di-tert-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 10 g, benzoyl peroxide 0.5
g, and a mixed solution of 0.5 g of di-tert-butyl peroxide was added dropwise and reacted for 2 hours. Then cool down,
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,
The antistatic property was evaluated. The results are shown in Table 6.

Measurement / Evaluation Method 1 g of the water-resistant polymer film of the 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 surfactant (A) of the present invention,
(C), (G) 7.5 g surfactant as each modifier 及 beauty Comparative Example (3), benzoyl peroxide 2g, di-
A mixed solution of 0.5 g of tert-butyl peroxide was prepared, and the mixed solution was continuously added dropwise into the reaction vessel at a reaction temperature of 130 ° C. over 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 2
Reacted for 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 the 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.

[0064]

[Table 6]

[0065]

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.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References European patent application publication 548826 (EP, A 1) (58) Fields investigated (Int.Cl. ⁷ , DB name) B01F 17/18 B01F 17/46 C08F 2 / 18 C08F 2/24

Claims (4)

(57) [Claims] 1. A compound represented by the general formula (1): (In the formula, R ₁ is an alkyl group, an alkenyl group, or an aryl group in which linear or branched hydrogen having 1 to 36 carbon atoms may be substituted with a fluorine atom. R ₂
Is the general formula (2) And R'is hydrogen or methyl.
k is 2 and m is 1 . A is an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group, n is a positive number, and X is halogen, OH, NO ₃ , SO ₄ CH ₃
Is shown. ) Is represented by
A new surfactant that is reactive with a phenyl group . 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.