JP2003261605A - Reactive surfactant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a reactive surfactant which gives a polymer emulsion having good stability of a polymer emulsion during polymerization or good physical properties of a polymer coating film, a method for producing a polymer emulsion using the same and a method for producing the same. To provide a polymer emulsion and a polymer coating. SOLUTION: A reactive surfactant comprising at least one compound represented by the formula (I) or the formula (II), a method for producing a polymer emulsion in which emulsion polymerization is carried out using the same, and excellent water resistance produced by the method. Polymer emulsions and polymer coatings prepared using the same. Embedded image [In the formula, A ₁ is an alkylene group having 5 to 18 carbon atoms or an alkoxymethylethylene group (4 to 18 carbon atoms of the alkoxy group), A
₂ represents an alkylene group having 2 to 4 carbon atoms, n represents a number of 0 to 200, and M represents a cation. ]

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a reactive surfactant, a method for producing a polymer emulsion using the same, a polymer emulsion produced by this production method, and a polymer coating film prepared using this polymer emulsion.

[0002]

BACKGROUND OF THE INVENTION Polymer emulsions obtained by emulsion polymerization of vinyl monomers such as vinyl acetate and acrylic acid ester are directly used in the fields of paints, adhesives, paper processing, fiber processing, etc. Alternatively, the polymer is separated and widely used industrially as plastic and rubber. For emulsion polymerization, as an emulsifier,
Anionic surfactants such as alkyl sulfate ester salts, alkylbenzene sulfonates, polyoxyethylene alkyl ether salts, polyoxyethylene alkylphenyl ether salts, and polyoxyethylene alkyl ethers,
Nonionic surfactants such as polyoxyethylene alkyl phenyl ether have been used.

The emulsifier in the emulsion polymerization not only affects the initiation reaction and the growth reaction of the polymerization, but also the stability of the polymer emulsion during the polymerization, and the mechanical stability, chemical stability and freezing of the produced polymer emulsion. Stability, storage stability, further particle size of polymer emulsion, viscosity, emulsion physical properties such as foaming property, and further when formed into a film, its water resistance, moisture resistance, heat resistance,
It has a great influence on the physical properties of the film such as adhesiveness and tackiness. In applications such as paints and adhesives, the polymer coating film is formed by drying the polymer emulsion, but the emulsifier remaining in the polymer coating film causes a decrease in water resistance, adhesiveness, weather resistance, heat resistance, etc. It is known. For example, a polymer emulsion obtained by emulsion-polymerizing a (meth) acrylic acid ester is used for a water-based paint, but when the water resistance of this polymer coating is poor, it is necessary to use water resistance for building exterior walls, bathroom walls, etc. Can not be used for. Also,
In the production of synthetic rubber and the like, when a polymer is taken out from a polymer emulsion by means such as salting out, the emulsifier is contained in the waste water, which causes a problem of increasing the burden of waste water treatment.

In order to solve such a drawback, a method using a so-called reactive surfactant having an ethylenically unsaturated bond as a polymerizable group in the molecule has been proposed.
For example, JP-A-61-223011 discloses a method using an ether sulfate ester salt of polyoxyalkylene having an allyl or methallyl group as a polymerizable group. Also, Macromolecules, 32, p. 5967 (1999), sodium oxyalkanesulfonate having a 3-methyl-3-butenyl group as a polymerizable group, 10- (3-methyl-3-butenyloxy) decane-1. -The results of emulsion polymerization using sodium sulfonate are described.

However, when these reactive surfactants are used alone as an emulsifying agent for emulsion polymerization, the stability during polymerization is often insufficient, and in that case, a conventional emulsifying agent must be used in combination. There is a problem. Further, in the case of sodium 10- (3-methyl-3-butenyloxy) decane-1-sulfonate, there is a problem that the production of itself is not easy in terms of reaction temperature, yield and the like and is inferior in economic efficiency. is there.

The object of the present invention is to provide a reactive surfactant which gives a polymer emulsion having good stability of the polymer emulsion during polymerization or good physical properties of the polymer coating film, a method for producing a polymer emulsion using the same, and a method for producing the same. Another object of the present invention is to provide a polymer emulsion having good water resistance, and further a polymer coating film exhibiting excellent water resistance in the fields of coating materials, adhesive products and the like.

[0007]

The present invention provides a reactive surfactant comprising at least one compound represented by the formula (I) or the formula (II), and emulsion polymerization using the reactive surfactant. A method for producing a polymer emulsion for carrying out the method, a polymer emulsion having good water resistance produced by using the reactive surfactant, and a polymer coating film prepared by using the polymer emulsion.

[0008]

[Chemical 5]

[In the formula, A ₁ is a linear or branched alkylene group having 5 to 18 carbon atoms, or a compound represented by the formula (III)

[0010]

[Chemical 6]

(Wherein R represents a straight-chain or branched-chain alkyl group having 4 to 18 carbon atoms) and A ₂ is a straight-chain or branched-chain alkylene group having 2 to 4 carbon atoms. A group, n is a number from 0 to 200, and M is a cation. The present invention also provides the formula (IV) or the formula (V)

[0012]

[Chemical 7]

[In the formula, R, A ₂ and n have the above-mentioned meanings. A compound represented by the formula (I-1) or a compound represented by the formula (II-1), which is obtained by reacting a compound represented by the following formula with amidosulfuric acid in the presence of an amide compound (excluding a sulfonic acid amide compound) or an amine compound. Provide a manufacturing method.

[0014]

[Chemical 8]

[In the formula, R, A ₂ , n and M have the above-mentioned meanings. ]

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION In the above formula (I) or formula (II), the linear or branched alkylene group having 5 to 18 carbon atoms represented by A ₁ is butylethylene, octylethylene, decylethylene, Dodecyl ethylene, tetradecyl ethylene, hexadecyl ethylene and the like can be mentioned. formula
Examples of the linear or branched alkyl group having 4 to 18 carbon atoms represented by R in (III) include a butyl group, a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, and an undecyl group, Examples thereof include dodecyl group, tetradecyl group, hexadecyl group, octadecyl group and the like.

Among these A ₁ and R, when A ₁ is an alkylene group, the total number of carbon atoms is, and when A ₁ is an alkoxymethylethylene group represented by the formula (III), the carbon number of R is It is particularly preferable that the number satisfies the formula (VI).

8 ≦ (number of carbon atoms) ≦ 18 (VI) In the above formula (I) or formula (II), the linear or branched alkylene group having 2 to 4 carbon atoms represented by A ₂ is
Examples thereof include ethylene, propylene, ethylethylene and dimethylethylene. Further, n number of A ₂ may be two or more kinds of mixed groups, of which the proportion of ethylene groups is preferably 70 mol% or more, more preferably 90 mol% or more, and more preferably 100 mol%. Are particularly preferred.

N represents the average number of moles of the oxyalkylene group represented by A ₂ O, and is 0 to 200, preferably 1 to
The range is 50, particularly preferably 1 to 30. Examples of the cation represented by M include alkali metal ions such as sodium and potassium, alkaline earth metal ions such as calcium and magnesium, ammonium ion, and C1 to C4.
And an ammonium ion substituted with an alkyl group.

As the reactive surfactant of the present invention, the compound represented by the formula (I) is preferable because the coating film has particularly improved water resistance as compared with the compound represented by the formula (II).

The compound represented by the formula (I) or the formula (II) of the present invention can be produced by a known method. For example, 3-methyl-3-buten-1-ol is present as a catalyst. Below, alkyl glycidyl ether or α-olefin epoxide was added to give 1-O-alkyl-3-O.
1-mol addition product of 3- (3-methyl-3-butenyl) glycerin or olefin epoxide to 3-methyl-3-buten-1-ol was obtained, and the obtained compound had 2 to 2 carbon atoms.
Alkylene oxide of 4 is added according to a conventional method, or
Alternatively, 3-methyl-3-buten-1-ol has 2 to 2 carbon atoms.
After adding the alkylene oxide of 4, the adduct 1
Alkyl glycidyl ether or α-
It is obtained by adding 1 mol of olefin epoxide to obtain an ether alcohol, sulfating this with a sulfating agent, and neutralizing with a basic substance. Examples of the sulfating agent include chlorosulfonic acid, sulfuric anhydride, and amidosulfuric acid, but from the viewpoint of reducing side reactions such as addition reaction of a sulfuric acid group to a double bond group and isomerization of a double bond group, amido sulfuric acid is used. Is preferably used.

When the compound represented by the above formula (IV) or formula (V) is subjected to sulfuric acid esterification, amide sulfuric acid is treated at a temperature of 60 in the presence of an amide compound (excluding a sulfonic acid amide compound) or an amine compound. By reacting at ~ 140 ° C, the double bond group is sufficiently protected, and side reactions such as isomerization of the terminal double bond group to the internal double bond group and addition of a sulfate group to the double bond group are almost eliminated. This can be completely prevented, whereby a highly purified terminal unsaturated compound sulfate ester salt represented by the formula (I-1) or (II-1) can be produced.

Examples of the amide compound used in the present invention include urea, urea derivatives such as methylurea, 1,1-dimethylurea, ethylurea, butylurea and acetylurea, acetamide, formamide, propionic amide, butylamide, Examples thereof include acid amide compounds such as diacetamide and succinic acid amide.

However, since a sulfonic acid amide compound such as toluenesulfonic acid amide has no effect of preventing double bond group isomerization and addition of a sulfonic acid group to a double bond group, it can be used in the present invention. Can not.

Examples of the amine compound used in the present invention include morpholine, triethylamine, tributylamine, isopropylamine and diisopropylamine. The amide compound and amine compound used in the present invention are effective when used in a small amount when the molecular weight is small, and the molecular weight is 150 or less, preferably 100 or less.

The amount of the amide compound or amine compound used is 1 with respect to the compound represented by the formula (IV) or the formula (V).
-50 mol% is preferable, 3-30 mol% is more preferable, and 5-20 mol% is particularly preferable.

The amido-sulfuric acid used in the present invention may be a commercially available product. The charging ratio (molar ratio) of the compound represented by formula (IV) or formula (V) and amidosulfuric acid is not particularly limited, but from the viewpoint of increasing the degree of sulfate esterification, it is 1/1 to 1 / 1.3. Range is preferred, especially 1/1
It is more preferable that it is in the range of 1 / 1.1.

In the case of sulfuric acid esterification with amido-sulfuric acid, if water is mixed in the raw material, the amido-sulfuric acid is decomposed to cause a decrease in the degree of sulfuric acid esterification and an increase in side reactions. Water contained in the compound represented by V) is preferably completely removed by a method such as vacuum dehydration prior to the reaction.

The sulfuric acid esterification reaction with amidosulfuric acid
From the viewpoint of preventing oxidation and coloration, it is preferably carried out in an atmosphere of an inert gas such as nitrogen gas, in the presence of an amide compound or an amine compound, at a temperature of 60 to 140 ° C, preferably 90 to 120 ° C. After the reaction is completed, excess substances such as amido sulfuric acid and amide compounds which are not dissolved in the reaction system can be removed by filtration.

The sulfuric acid esterified product with amidosulfuric acid is an ammonium salt, but it is also possible to replace the ammonium salt with another salt by a method such as addition of an aqueous sodium hydroxide solution, if necessary.

The method for producing the polymer emulsion of the present invention is a method of emulsion-polymerizing a vinyl monomer using the reactive surfactant of the present invention as an emulsifier. In the method for producing a polymer emulsion of the present invention, other anionic surfactants or nonionic surfactants can be used together as an emulsifier, but the ratio of the reactive surfactant according to the present invention is 5 relative to the total amount of the emulsifier. ~ 100 wt% is preferred, 2
0 to 100% by weight is more preferable. In the emulsion polymerization according to the present invention, the amount of the emulsifier used is preferably 0.1 to 10% by weight based on the total amount of vinyl monomers.

The vinyl-based monomer used in the present invention includes aromatic vinyl monomers such as styrene, α-methylstyrene and chlorostyrene; methyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic acid 2
-(Meth) acrylic acid esters such as ethylhexyl;
(Meth) acrylic acid; vinyl halides such as vinyl chloride, vinyl bromide, vinylidene chloride and vinylidene halides; vinyl esters such as vinyl acetate and vinyl propionate; nitriles such as (meth) acrylonitrile; butadiene, isoprene And the like, and these monomers may be polymerized alone or may be copolymerized with two or more kinds. The amount of the vinyl-based monomer used is preferably 40 to 60% by weight based on the whole system.

Examples of the initiator used in the emulsion polymerization in the present invention include inorganic peroxides such as potassium persulfate, ammonium persulfate and hydrogen peroxide, t-butyl peroxide, cumene hydroxyperoxide and paramenthane peroxide. Examples thereof include azo compounds such as organic peroxides, azobisdiisobutylnitrile, and 2,2′-azobis (2-amidinopropane) dihydrochloride, and persulfates such as potassium persulfate and ammonium persulfate are preferable. Further, sodium bisulfite, ferrous ammonium sulfate, etc. can be used as the polymerization accelerator.

The monomer is added by the monomer dropping method,
Although a batch charging method of monomers or a pre-emulsion method can be used, the pre-emulsion method is preferable from the viewpoint of polymerization stability. The dropping time is preferably 1 to 8 hours, and the aging time is preferably 1 to 5 hours. The polymerization temperature is adjusted by the decomposition temperature of the initiator, but in the case of persulfate, it is preferably 70 to 80 ° C.

The average particle size of the polymer emulsion of the present invention obtained by the above method varies depending on the use,
30 to 500 nm is preferable, and 80 to 300 nm is more preferable. Moreover, the viscosity is 50,000 to 10 mPa · s.
Is preferable, and 10,000 to 50 mPa · s is more preferable. Here, the average particle size and viscosity of the polymer emulsion are values measured by the methods shown in the following examples.

The polymer coating film prepared from the polymer emulsion of the present invention has excellent water resistance and can be preferably used in paints, especially in the field of water-based paints and adhesive products.

The method for preparing the polymer coating film of the present invention varies depending on the use. For example, in adhesive applications, polymer Tg such as 2-ethylhexyl acrylate and n-butyl acrylate can be obtained by emulsion polymerization using the reactive surfactant of the present invention.
To produce low polymer emulsions of the present invention. This polymer emulsion of the present invention may optionally contain a thickener,
When a material such as a tackifier is coated on a substrate such as paper or film and dried with hot air to form a polymer coating film with a thickness of about 20 μm, an adhesive product with excellent water resistance and adhesive performance is obtained. be able to.

Further, in the application of coating materials, by emulsion polymerization using the reactive activator of the present invention, n-butyl acrylate /
A polymer emulsion of the invention, such as a methyl methacrylate copolymer, is prepared. If necessary, the polymer emulsion of the present invention, which is mixed with a film forming aid, a pigment or the like, is applied to a building wall material or the like so that the dry film thickness is about 100 μm, and this is naturally dried or hot air dried. By doing so, a coating film having excellent water resistance and weather resistance can be obtained.

[0039]

EXAMPLES In the examples,% is weight% unless otherwise specified.

Production Example 1 In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux tube, 2,583 g of 3-methyl-3-buten-1-ol (30 g)
10.8 g of powdered sodium methoxide (0.
2 mol) was charged, 390 g (3 mol) of n-butyl glycidyl ether was added dropwise over 2 hours at 85 ° C. under a nitrogen atmosphere, and the mixture was aged at this temperature for 8 hours. After phosphoric acid was added to the reaction product to neutralize sodium methoxide, unreacted 3-methyl-3-buten-1-ol was removed under reduced pressure to remove sodium phosphate contained in the reaction product. Removed by filtration. This reaction product was purified by distillation under reduced pressure to give 1-O-n.
460 g of -butyl-3-O- (3-methyl-3-butenyl) glycerin were obtained. 432.2 g of this distilled purified product
(2 mol) and KOH (3.4 g) were charged in an autoclave, and 881 g (20 mol) of ethylene oxide was added under the conditions of 120 ° C. and 0.3 MPa. Next, 328.3 g (0.5 mol) of this ethylene oxide adduct, 51.5 g (0.53 mol) of amido-sulfuric acid, and 3 g of urea were charged into a reaction vessel equipped with a stirrer and a thermometer, and the mixture was placed under a nitrogen atmosphere at 1
After reacting at 10 ° C. for 4 hours for sulfation, unreacted amido-sulfuric acid was removed by pressure filtration to obtain a reactive surfactant [A-1] represented by the following formula. The ¹ H-NMR spectrum of the obtained reactive surfactant [A-1] is shown in FIG.

[0041]

[Chemical 9]

Production Example 2 3-Methyl-3-butene-was placed in the same reaction vessel as in Production Example 1.
1-ol 1937 g (22.5 mol) and powdered sodium methoxide 8.1 g (0.15 mol) were charged, and 2-ethylhexyl glycidyl ether 279.4 g (1.5 mol) was added for 2 hours at 85 ° C. under a nitrogen atmosphere. It dripped over, and aged at this temperature for 8 hours. After phosphoric acid was added to the reaction product to neutralize sodium methoxide, unreacted 3-methyl-3-buten-1-ol was removed under reduced pressure to remove sodium phosphate contained in the reaction product. Removed by filtration. This reaction product was purified by distillation under reduced pressure to give 1-O-
(2-Ethylhexyl) -3-O- (3-methyl-3-
304 g of butenyl) glycerin were obtained. 299.6 g (1.1 mol) of this distilled purified product and 1.85 g of KOH were charged into an autoclave, and 484.5 g (11 mol) of ethylene oxide was added under the conditions of 120 ° C. and 0.3 MPa. Next, 200 g of this ethylene oxide adduct
(0.28 mol), 32.7 g of amidosulfuric acid (0.336
Mol) and 1.68 g of urea were charged into a reaction vessel equipped with a stirrer and a thermometer, reacted at 110 ° C. for 4 hours in a nitrogen atmosphere to perform sulfation, and unreacted amido-sulfuric acid was removed by pressure filtration. , A reactive surfactant represented by the following formula [A-
2] was obtained.

[0043]

[Chemical 10]

Production Example 3 In the same manner as in Production Example 1 except that 398 g (2 mol) of a mixture of n-octyl glycidyl ether and n-decyl glycidyl ether was used in place of n-butyl glycidyl ether, 1-O- Mixture of n-octyl-3-O- (3-methyl-3-butenyl) glycerin and 1-O-n-decyl-3-O- (3-methyl-3-butenyl) glycerin (50.2 wt% / 47.8 wt%) was obtained. 465.6 g (1.6 mol) of this distilled purified product and K
2.69 g of OH was charged into the autoclave, and 120
Ethylene oxide 704.
8 g (16 mol) was added. Next, 200 g (0.273 mol) of this ethylene oxide adduct, 29.2 g (0.3 mol) of amidosulfuric acid and 1.69 g of urea were stirred with a stirrer,
A reaction vessel equipped with a thermometer was charged and placed under a nitrogen atmosphere.
After reacting at 3 ° C for 3 hours for sulfation, unreacted amido-sulfuric acid was removed by pressure filtration to obtain a reactive surfactant [A-3] represented by the following formula.

[0045]

[Chemical 11]

Production Example 4 1-O-n-octyl-3-O- (3-methyl-3-butenyl) glycerin was produced in the same manner as in Production Example 3 except that 1057 g (24 mol) of ethylene oxide was added. Mixture of 1-O-n-decyl-3-O- (3-methyl-3-butenyl) glycerin (50.2 wt% / 47.8).
wt%) ethylene oxide 15 mol adduct was obtained.
Next, 200 g of this ethylene oxide adduct (0.2
101 mol), 22.5 g (0.231 mol) of amido-sulfuric acid and 1.26 g of urea were charged into a reaction vessel equipped with a stirrer and a thermometer, and reacted at 105 ° C. for 3 hours under a nitrogen atmosphere to perform sulfation. , Unreacted amido-sulfuric acid is removed by pressure filtration, and the reactive surfactant [A-
4] was obtained.

[0047]

[Chemical 12]

Production Example 5 3-Methyl-3-butene-was placed in the same reaction vessel as in Production Example 1.
1-ol 861 g (10 mol) and powdered sodium methoxide 3.11 g (0.0576 mol) were charged, and α-olefin epoxide having 12 and 14 carbon atoms (AOE X24, Daicel Chemical Industries, Ltd.) at 130 ° C. under a nitrogen atmosphere. )) 236.7 g (1.15 mol) was added dropwise over 4 hours, and the mixture was aged at this temperature for 12 hours. After adding phosphoric acid to the reaction product to neutralize sodium methoxide,
Unreacted 3-methyl-3-buten-1-ol was removed under reduced pressure, and sodium phosphate salt contained in the reaction product was removed by filtration. This reaction product was purified by distillation under reduced pressure to obtain 265 g of an olefin epoxide 3-methyl-3-buten-1-ol adduct represented by the following formula (VII).

[0049]

[Chemical 13]

250 g of 3-methyl-3-buten-1-ol adduct of the above-mentioned olefin epoxide (VII)
(0.856 mol) and 1.44 g of KOH were charged into an autoclave, and 565.6 g (12.84 mol) of ethylene oxide was added under the conditions of 130 ° C. and 0.3 MPa. Next, 200 g (0.2 parts) of the obtained reaction mixture was used.
1 mol), amide-sulfuric acid 22.45 g (0.231 mol) and urea 1.26 g were charged into a reaction vessel equipped with a stirrer and a thermometer, and reacted at 115 ° C. for 4 hours under a nitrogen atmosphere to perform sulfation. , Unreacted amido-sulfuric acid is removed by pressure filtration, and the reactive surfactant [A-
5] was obtained.

[0051]

[Chemical 14]

Production Example 6 1-O-n-dodecyl-3-O was prepared in the same manner as in Production Example 1 except that 726 g (3 mol) of n-dodecyl glycidyl ether was used instead of n-butyl glycidyl ether.
697 g of-(3-methyl-3-butenyl) glycerin was obtained. In the same manner as in Production Example 1, 881 g (20 mol) of ethylene oxide was added to 656.2 g (2 mol) of this distilled purified product, and then this ethylene oxide adduct 3
Similarly, 84.3 g (0.5 mol) was sulphated to obtain a reactive surfactant [A-6] represented by the following formula.

[0053]

[Chemical 15]

Production Example 7 1-O-n-tetradecyl-3-O- was prepared in the same manner as in Production Example 1 except that 810 g (3 mol) of n-tetradecyl glycidyl ether was used instead of n-butyl glycidyl ether. 735 g of (3-methyl-3-butenyl) glycerin was obtained. In the same manner as in Production Example 1, ethylene oxide 88 was added to 712.2 g (2 mol) of this distilled purified product.
1 g (20 mol) was added, and then 398.3 g (0.5 mol) of this ethylene oxide adduct was similarly sulfated to obtain a reactive surfactant [A-7] represented by the following formula. It was

[0055]

[Chemical 16]

Production Example 8 3-Methyl-3-butene-was placed in the same reaction vessel as in Production Example 1.
1-ol 2583 g (30 mol) and powdered sodium methoxide 8.1 g (0.15 mol) were charged, and n-octadecyl glycidyl ether 6 was prepared at 85 ° C. under a nitrogen atmosphere.
52.0 g (2 mol) was added dropwise over 2 hours, and the mixture was aged at this temperature for 8 hours. Phosphoric acid was added to this reaction product to neutralize sodium methoxide, and then unreacted 3-
Methyl-3-buten-1-ol was removed, and the sodium phosphate salt contained in the reaction product was removed by filtration. This reaction product was purified by distillation under reduced pressure to give 1-O-n-octadecyl-3-O- (3-methyl-3-butenyl) glycerin 5
26 g were obtained. 412.1 g (1 mol) of this distilled purified product
And 1.7g of KOH was charged into the autoclave, and 120
Ethylene oxide 440.
5 g (10 mol) was added. Next, 341.0 g (0.4 mol) of this ethylene oxide adduct, 42.8 g (0.44 mol) of amido sulfuric acid, and 2.4 g of urea were stirred with a stirrer,
A reaction vessel equipped with a thermometer was charged, and under a nitrogen atmosphere, 110
After reacting at 4 ° C. for 4 hours for sulfation, unreacted amido sulfuric acid was removed by pressure filtration to obtain a reactive surfactant [A-8] represented by the following formula.

[0057]

[Chemical 17]

Production Example 9 In an autoclave, 3-methyl-3-buten-1-ol 344.4 g (4 mol) and KOH 6.73 g (0.1 mol) were added.
2 mol) was charged, and 881 g (20 mol) of ethylene oxide was added under the conditions of 120 ° C. and 0.3 MPa. In a reaction vessel equipped with a stirrer, thermometer, dropping funnel, reflux tube,
612.7 g (2 mol) of this ethylene oxide adduct
Was charged, 242 g (1 mol) of n-dodecyl glycidyl ether was added dropwise over 2 hours at 85 ° C. under a nitrogen atmosphere, and the mixture was aged at the same temperature for 8 hours. After neutralizing this reaction product with phosphoric acid, it was purified by distillation using a Smith-type molecular distillation machine, and the following formula (V
A compound represented by III) was obtained.

[0059]

[Chemical 18]

Next, 137.1 g of this compound (VIII)
(0.25 mol), 26.2 g (0.27 mol) of amido-sulfuric acid, and 1.5 g of urea were charged into a reaction vessel equipped with a stirrer and a thermometer, and reacted at 115 ° C. for 4 hours under a nitrogen atmosphere to perform sulfation. After that, unreacted amido-sulfuric acid is removed by pressure filtration, and the reactive surfactant represented by the following formula [A-9]
Got

[0061]

[Chemical 19]

Examples 1 to 12 and Comparative Examples 1 to 3 Using the reactive surfactants of the present invention obtained in Production Examples 1 to 9 and the conventional anionic surfactants shown in Table 1 as emulsifiers, The emulsion polymerization was carried out by the method described in 1 above and the performance was evaluated by the following method. The results are shown in Table 1.

<Emulsion Polymerization Method> In 104.1 g of deionized water weighed in a beaker, 5.83 g of an emulsifier and 0.39 g of potassium persulfate were dissolved, and 2.4 g of acrylic acid, 120.3 g of butyl acrylate and methacrylic acid were dissolved. Methyl acid 12
0.3g was added, and 5000r / min with a homomixer
Emulsified for 10 minutes to obtain a monomer emulsion. Ion-exchanged water 178.6 g, emulsifier 1.35 in a separable flask
g, 0.09 g of potassium persulfate, and 16.4 g of the above monomer emulsion, and the mixture was stirred in a nitrogen stream for 15 minutes. Next, while stirring in a nitrogen stream, the inner temperature of the flask was raised to 80 ° C. in a water bath to carry out a polymerization reaction for 30 minutes, and 310.8 g of the above monomer emulsion was added from a dropping funnel over 3 hours. After dripping and aging for 1 hour, it was cooled to room temperature to obtain a polymer emulsion. The temperature in the flask was kept at 80 ± 2 ° C during the dropping and aging. Further, when the monomer emulsion to be dropped was separated in the dropping funnel, a small stirrer was inserted in the dropping funnel to maintain the uniformity.

<Performance Evaluation Method> (1) Polymerization Stability The polymer emulsion was filtered through a 200-mesh stainless steel wire net, and aggregates adhering to the reactor wall, stirring blades, etc. after polymerization were collected and filtered in the same manner. 26.6kP after washing with water
a, dried and weighed at 105 ° C. for 2 hours to determine the amount of aggregates. Aggregate weight% based on total monomer used
Is the polymerization stability. The smaller the value, the better the polymerization stability, and it is judged to be particularly good when the value is 0.15% or less.

(2) Mechanical stability Polymer emulsion 5 neutralized with 25% aqueous ammonia
0g in a Maron stability tester at 10kgf, 1000r /
Rotate for 5 minutes under the condition of min to remove the generated aggregates for 20 minutes.
The mixture was filtered through a 0-mesh stainless steel wire net, and the filtration residue was washed with water, dried and weighed at 26.6 kPa and 105 ° C., and expressed as a weight% based on the polymer. The smaller this value is, the better the polymerization stability is. 0.35% or less, especially 0.15%.
It is judged to be good in the following cases.

(3) Average Particle Size The average particle size of the polymer emulsion particles neutralized with 25% aqueous ammonia was measured using a dynamic light scattering particle size analyzer Coulter N4 Plus manufactured by Beckman Coulter. .

(4) Viscosity Using a B-type viscometer, the viscosity of a polymer emulsion neutralized with 25% aqueous ammonia was measured at a temperature of 25 ° C. and a rotation speed of 12
It was measured at r / min.

(5) Water resistance of polymer film A polymer emulsion neutralized with 25% aqueous ammonia was coated on a transparent acrylic plate using an applicator to a dry film thickness of 150 μm, and then dried with a hot air dryer. 1
It was dried at 00 ° C for 10 minutes. After this acrylic plate was immersed in warm water at 60 ° C. for 16 hours, the haze value of the polymer film was measured using a haze meter. The smaller the haze value, the better the water resistance. When the haze value is 15% or less, the water resistance is judged to be particularly good.

[0069]

[Table 1]

[0070]

[Chemical 20]

[0071]

By using the reactive surfactant of the present invention as an emulsifying agent for emulsion polymerization, a polymer emulsion having excellent polymerization stability and mechanical stability can be produced. In addition, the polymer coating film prepared from this polymer emulsion has excellent water resistance and exhibits excellent effects in the fields of paints and adhesives.

[Brief description of drawings]

FIG. 1 ¹ H-NMR of reactive surfactant [A-1]
It is a spectrum.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08F 20/38 C08F 20/38 4J100 C09D 5/02 C09D 5/02 7/12 7/12 201/00 201 / 00 C09J 201/00 C09J 201/00 (72) Inventor Atsuto Mori 1334 Minato Minato, Wakayama, Wakayama Prefecture Kao Corporation Research Laboratory (72) Inventor Yasuo Ishii 1334 Minato Minato, Wakayama City Wakayama Laboratory F, Kao Corporation Term (Reference) 4D077 AB15 AC01 BA01 CA03 DC08Z DC12Z DC19Z DD29X DE29X 4H006 AA02 AB48 AB68 4J011 AA05 KA04 KA06 KA07 4J038 CE052 GA13 KA09 4J040 DJ042 QAQAQAQAQPQAQAQPQAQAQPQAQAQPQAQAQPQAQPQAQPQAQPQAQPQAQPQAQPQAQPQAQPQAQPQAQAQPQAQPQAQPQAQPQAQPQAQPQAQAQPQAQPQAQPQAQPQAQPQAQAQAQPQAQAQPQAQAQAQPQAQAQPQAQPQAQAQPQAQAQPQAQPQAQAQPQAQAQPQAQAQAQPQAQAQAQAQAQAQAQAQAQ there can be more than about you. FA20 JA01

Claims (5)

[Claims] 1. A reactive surfactant comprising at least one compound represented by formula (I) or formula (II). [Chemical 1] [Wherein A ₁ is a linear or branched alkylene group having 5 to 18 carbon atoms, or a compound represented by the formula (III): (In the formula, R represents a linear or branched alkyl group having 4 to 18 carbon atoms.), An alkoxymethylethylene group,
A ₂ is a linear or branched alkylene group having 2 to 4 carbon atoms, n
Is a number from 0 to 200, and M is a cation. ] 2. A method for producing a polymer emulsion, which comprises emulsion polymerization using the reactive surfactant according to claim 1. 3. A polymer emulsion prepared using the reactive surfactant according to claim 1. 4. A polymer coating prepared using the polymer emulsion of claim 3. 5. The formula (IV) or the formula (V): [In the formula, R, A ₂ and n have the above-mentioned meanings. A compound represented by the formula (I-1) or a compound represented by the formula (II-1), which is obtained by reacting a compound represented by the following formula with amidosulfuric acid in the presence of an amide compound (excluding a sulfonic acid amide compound) or an amine compound. Manufacturing method. [Chemical 4] [In the formula, R, A ₂ , n and M have the above-mentioned meanings. ]