JPH09137062A - Cationic stable silicone emulsion and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a stable cationic silicone emulsion suitable for treatment of hair, etc., useful as a cleansing article in good production efficiency by carrying out anion emulsion polymerization having large polymerization rate by using plural specific surfactants.

SOLUTION: This emulsion contains (A) a silicone polymer having 10,000-10,000,000cSt viscosity, (B) an anionic surfactant selected from a group comprising a 1-20C aliphatic hydrocarbon sulfonic acid and aliphatic hydrocarbon sulfate which may be substituted by hydroxyl group, a 6-30C arylsulfonic acid and a 7-50C alkylarylsulfonic acid, (C) a compatibilizing surfactant having 9-25 ratio of hydrophilicity to lipophilicity and (D) a cationic surfactant such as a bis(polyoxyethylene)hydrocarbylmethylquaternary ammonium halide or sulfate. Furthermore, a silicone is preferably mixed with water and the component B and the mixture is heated at 75-98°C for 3-24hr and the mixture is cooled to 0-25°C and the components C and D are added thereto to stabilize the emulsion.

COPYRIGHT: (C)1997,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for selecting precursors and preparing emulsion-polymerized silicones, which are polymerized in the presence of an anionic surfactant to give a silicone emulsion and The silicone emulsion is miscible with the cationic surfactant. Such silicone emulsions are useful in a variety of personal care products.

[0002]

BACKGROUND OF THE INVENTION It is well known in the art to prepare high molecular weight emulsified silicone polymers by emulsion polymerization of silicone oligomers. The earliest of such techniques was described, for example, in US Pat.
No. 920, teaches polymerizing octamethylcyclotetrasiloxane (D ₄ ) and other silicone oligomers in the presence of quaternary ammonium compounds using a strong base. . As taught in US Pat. No. 3,294,725,
This technique was extended to include using sulfonic acids to effect polymerization of silicone oligomers. Polymerization of silicone oligomers in the presence of sulfonic acid is particularly effective in producing high molecular weight silicone polymers.

It is a well recognized feature in the polymerization mechanism of silicone oligomers that low molecular weight polymers are obtained by early stage ring opening polymerization. It has been found that controlling the cooling step after heating the reaction mixture containing the silicone oligomer so as to achieve the initial polymerization can consequently control the degree of polymerization of the silicone. By approaching equilibrium, the degree of polymerization is
It is also kinetically controlled by the temperature at which equilibrium is established. In general, the use of anionic polymerization catalysts, in contrast to cationic polymerization catalysts which reach equilibrium significantly slower,
Equilibrium can be reached quickly at any temperature. As a result, commercial production of silicone polymers relies on anionic polymerization catalysts when higher molecular weight polymers are desired.

[0004] In particular, the use of anionic polymerization catalysts in emulsion polymerization has the advantage of achieving rapid reaction rates, but limits the applications in which the resulting polymerized silicone emulsions can be used. These emulsions are generally
It can be used for various purposes such as cosmetics, but when the ion balance of the emulsion changes, the emulsion is broken. Therefore, when an emulsion-polymerized silicone emulsion polymerized in the presence of an anionic polymerization catalyst is treated with, for example, a cationic surfactant, the emulsion usually disintegrates. Because human hair is weakly anionic, hair care products typically need to be cationic. This makes it extremely difficult to formulate human hair cosmetics and personal care products using emulsion polymerized high molecular weight silicone emulsions. In hair care applications, it is advantageous to use cationic polymer-containing silicone emulsions to improve deposition on the hair surface. Also, because high molecular weight silicone polymers have excellent conditioning properties, as opposed to low molecular weight silicone polymers, it is desirable to deposit high molecular weight silicone polymers on the hair.

A typical means for solving this problem is to polymerize in the presence of a cationic polymerization catalyst to produce an emulsion-polymerized silicone emulsion. However, when an emulsion is produced by this method, a long residence time is required to obtain a silicone polymer having a desired molecular weight. Thus, ideally, a high molecular weight silicone polymer can be prepared by emulsion polymerization using an anionic surfactant, which then provides the desired cationic properties, which can give beneficial results to hair care formulations. As such, it may be desirable to modify the product in some way.

It has been found that a simple means of adding a cationic surfactant to a high molecular weight silicone polymer emulsion prepared with an anionic surfactant is to break the emulsion. The addition of surfactants of opposite conjugate nature is generally recognized as a technique of breaking emulsions. This is exemplified by the method of coagulating a grafted rubber compound as disclosed in US Pat. No. 4,831,116. In this example, an emulsion is prepared by a polymerization process in the presence of an anionic surfactant, and the emulsion is broken and coagulated by the addition of a cationic surfactant.

There are several recent developments showing that emulsions can be retained in certain isolated systems even when both cationic and anionic surfactants are present. U.S. Pat. No. 4,40
The vinylidene latex system prepared by emulsion polymerization in the presence of anionic surfactants, as disclosed in 1,788, allows the addition of cationic surfactants. However, this particular system had a limited stability of the resulting emulsion. Anionic asphalt emulsions are made cationic by the addition of a cationic surfactant in combination with a so-called steric stabilizer that prevents the emulsion from collapsing or breaking, as disclosed in US Pat. No. 5,045,576. Can be converted to an emulsion. None of these systems handle silicone polymer emulsions, and it makes no sense to expect that the techniques available in latex or asphalt can be transferred directly to silicone emulsions.

[0008]

DISCLOSURE OF THE INVENTION The present inventors have solved these problems of the prior art by first mixing them with a cationic surfactant prepared using an anionic surfactant. It is disclosed herein that a possible high molecular weight silicone polymer emulsion can be prepared. These emulsions are achieved by limiting the choice of reagents within a narrow range, which choice allows the use of certain cationic surfactants after the emulsion is prepared.

[0009]

That is, according to the present invention, (a) a silicone polymer having a viscosity in the range of 10,000 to 10,000,000 cSt; (b) substituted with a hydroxyl group having 1 to 20 carbon atoms. An anionic surfactant selected from the group consisting of an aliphatic hydrocarbon sulfonic acid and an aliphatic hydrocarbon sulfuric acid which may be contained, an arylsulfonic acid having 6 to 30 carbon atoms, and an alkylarylsulfonic acid having 7 to 50 carbon atoms. (C) a compatibilizing surfactant having a hydrophilic / lipophilic ratio of 9 to 25; and (d) a bis (polyoxyethylene) hydrocarbyl quaternary ammonium halide or sulfate; and an alkyl group. Having 8 to 30 carbon atoms of alkyltrimethylammonium or benzylalkyldimethylammonium Provided is a stable cationic silicone oil-in-water emulsion containing a cationic surfactant selected from the group consisting of rogenides or sulfates.

Further according to the present invention, 1) one or more silicones selected from the group consisting of 1) cyclic silicone oligomers, mixed silicone hydrolysates, silanol terminated oligomers, high molecular weight silicone polymers, and silicones having functional groups. Is mixed with 2) water, and 3) an anionic surfactant; 4) heating the mixture to a temperature of 75-98 ° C. for 1-5 hours; 5) heating the mixture to 3- Cooling to a temperature of 0 to 25 ° C. for 24 hours; 6) adding a miscible surfactant having a hydrophilic lipophilicity ratio (HLB) of 9 to 25; and 7) adding a cationic surfactant. There is provided a method for producing a stable cationic silicone oil-in-water emulsion.

The compositions and methods of the present invention are useful in preparing personal care compositions and products. Such products include cleansing products, lotions, shampoos, hair dye compositions, conditioners,
Rinse, neutral lotion, cream, gel, mousse,
It includes, but is not limited to, aerosols, pump sprays and the like.

[0012]

The present invention is based on the following discoveries. That is, some cationic and anionic surfactants were miscible with each other in the presence of some other stabilizing surfactants and were prepared by anionic catalyzed emulsion polymerization. It is based on the discovery that emulsions can be converted to cationic emulsions by utilizing these special types of surfactants without breaking or breaking the emulsion. The significant advantage of this discovery is that it is possible to rapidly polymerize silicones and subsequently convert them into cationic emulsions by anionic emulsion polymerizations, which belong to a reaction class with significantly faster polymerization rates than cationic emulsion polymerizations. It is a point. The resulting benefit of this discovery is that certain ingredients, especially silicones,
In many cosmetics, it is easier to deposit on the hair or skin when it is a cationic emulsion.
It is preferable to use a cationic emulsion.

The inventors refer to the polymerization, in particular the polymerization of cyclic silicones or other silicone oligomers under the conditions of anionic emulsion polymerization. The emulsion polymerization of silicone oligomer or cyclic silicone is 75
It occurs rapidly at temperatures in the range of ~ 98 ° C. If the initial polymerization at this temperature is completed and a polymer with an intermediate molecular chain length having a silanol end is generated, 0-25 ° C
By cooling to 1, it is possible to cause further condensation of silanol and subsequently increase the molecular weight. In general, this low temperature silanol condensation occurs much faster under anionic conditions than under cationic conditions. To date, this has presented a dilemma to the cosmetics industry, since emulsions are preferably cationic and they are usually prepared by slow-reacting polymerization processes. Techniques of anionic polymerization, such as anionic emulsion polymerization, show a rapid reaction rate, but when attempting to convert the resulting anionic emulsion to a cationic emulsion, conventionally, emulsion disintegration generally resulted. In anionic emulsion polymerization, 10,000 to 10, when isolated as a separated, pure, homogeneous phase,
This gives a polymer with a viscosity in the range of, 000,000 cSt. High molecular weight silicone polymer is defined herein to mean a polymer having a viscosity in the range of 10,000 to 10,000,000 cSt.

Our findings relate to the stability of the emulsions produced. Stability is defined herein to mean the absence of rake due to separation, creaming or sedimentation. Stability is determined by ASTM test method D3716 (15:04), 199.
It was measured using a procedure similar to the method defined in 1.
In addition, stable emulsions are defined as emulsions that are unaffected by storage for at least 3 days at temperatures in the range of about 50 to about 60 ° C.

In one embodiment of the method of the present invention,
Preferred emulsions have the following procedures: 1) Cyclic silicone oligomers (eg trimers, tetramers, pentamers and hexamers), mixed silicone hydrolysates, silanol terminated oligomers, high molecular weight silicone polymers and functional groups. 1 or 2 or more silicones selected from the group consisting of silicones having a group, 2) water, and 3) an aliphatic hydrocarbon sulfonic acid having 1 to 20 carbon atoms, which may be substituted with a hydroxyl group, and Mixing with an anionic surfactant selected from the group consisting of aliphatic hydrocarbon sulfuric acid, arylsulfonic acid having 6 to 30 carbon atoms, and alkylarylsulfonic acid having 7 to 50 carbon atoms; 4) the silicone, water and Heating the mixture obtained by mixing the surfactants to a temperature of 75-98 ° C for 1-5 hours; 5) intermediate The emulsion-polymerized silicone to 3-24
Cooling to a temperature of 0 to 25 ° C for 6 hours; 6) adding a miscible surfactant having a hydrophilic lipophilicity ratio (HLB) of 9 to 25; 7) bis (polyoxyethylene) hydrocarbylmethyl A quaternary ammonium halide or sulfate; and a cationic surfactant selected from the group consisting of alkyltrimethylammonium or benzylalkyldimethylammonium halide or sulfate having an alkyl group having 8 to 30 carbon atoms are added. It is obtained by preparing an emulsion-polymerized silicone.

In the step of anionic emulsion polymerization, the acid catalyst is an aliphatic hydrocarbon sulfonic acid having 1 to 20 carbon atoms and optionally substituted with a hydroxyl group and aliphatic hydrocarbon sulfuric acid, and 6 to 30 carbon atoms. It is selected from the group consisting of aryl sulfonic acids and alkyl aryl sulfonic acids having 7 to 50 carbon atoms. In the above-mentioned aliphatic hydrocarbon sulfonic acid and aliphatic hydrocarbon sulfuric acid which may be substituted with a hydroxyl group, the aliphatic hydrocarbon group may be a saturated hydrocarbon group such as an alkyl group or an alkenyl group. Such unsaturated hydrocarbon group may be used. The acid catalyst is selected from the group consisting of benzenesulfonic acid, xylenesulfonic acid, dodecylbenzenesulfonic acid, alkyl and alkenylsulfonic acids having 12 to 18 carbon atoms, hydroxytetradecanesulfonic acid, octylsulfate, laurylsulfate, cetylsulfate and oleylsulfate. It is preferably selected. Such an acid catalyst may be added in the form of an anionic surfactant which is an acid, and an anionic surfactant which is a salt such as a sodium salt may be added together with an acid such as sulfuric acid to obtain an emulsifying agent. May form a free acid.

Upon completion of the polymerization, the silicone emulsion obtained as a result of anionic emulsion polymerization will have an HLB of 9 to 25, preferably 10 to 25, more preferably 11.
-20, most preferably 12-18, of miscible surfactant is added. Miscible surfactants which give particularly good results are nonionic surfactants. Preferred nonionic surfactants are polyglycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene castor oil, and alkyl group having carbon atoms. Polyoxyethylene alkyl ether having 6 to 40 primary or secondary alkyl groups, polyoxyethylene alkylphenyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkyl having 6 to 40 carbon atoms in the alkyl group It is selected from the group consisting of amines, polyoxyethylene alkylamides having 6 to 40 carbon atoms in the alkyl group, and polyoxyethylene lanolin. A particularly preferred group of nonionic surfactants is POE (4) lauryl ether, POE
(9) Lauryl ether, POE (23) lauryl ether, POE (15) cetyl ether, POE (23)
Cetyl ether, POE (20) stearyl ether,
It is a group consisting of POE (20) oleyl ether, POE (18) nonylphenyl ether and POE (20) sorbitan monopalmitate. Another preferred group of miscible surfactants that can be used to make anionic emulsions miscible with cationic surfactants is:
Amphoteric betaine surfactants such as betaine lauryldimethylaminoacetate, coconut oil fatty acid amidopropyldimethylaminoacetate betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine; N-lauroylsarcosine sodium; It is a group consisting of lanolin derivatives of quaternary ammonium salts. Each of these groups of surfactants serves to make the anionic emulsion miscible with the cationic surfactant.

To the anionic emulsion polymerized silicone emulsion, a miscible surfactant having an HLB of 9 to 25 was added, and then the emulsion was treated with bis (polyoxyethylene) hydrocarbylmethyl quaternary ammonium. , Chlorides such as chlorides or sulfates; the number of carbon atoms of the alkyl group is 8 to 30, preferably 9 to
Chloride halides or sulphates of 30 alkyltrimethylammonium; and 8 to 1 carbon atoms
One of the cationic surfactants selected from the group consisting of halides such as chlorides or sulphates of 6, preferably 9 to 14 benzylalkyldimethylammonium.
It is converted to a cationic emulsion by adding one kind or two or more kinds. Particularly preferable groups as the cationic surfactant are cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, benzylalkylammonium chloride (having 12 to 12 carbon atoms in the alkyl group).
14 mixture) and polyoxyethylene (15) palm alkylmethylammonium chloride (methylpolyoxye)
thylene (15) cocammonium chloride, eg Ethoquad
C / 25, registered trademark).

It should be noted that in the process of the present invention, strongly basic anionic surfactants such as carboxylates do not give satisfactory results. The method of the present invention relies at the same time on the beneficial interaction of the properties of the anionic, miscible and cationic surfactants.

All US patent specifications cited above or below are hereby specifically incorporated by reference.

[0021]

According to the present invention, a stable cationic silicone oil-in-water emulsion obtained by converting a stable high molecular weight silicone polymer obtained in the form of anionic emulsion with high production efficiency by anionic emulsion polymerization and then converting A manufacturing method can be provided. The cationic silicone emulsion obtained according to the present invention is suitable for treating hair and the like, cleansing products,
It is useful as an ingredient in personal care products such as lotions, shampoos, hair dye compositions, conditioners, rinses, neutral lotions, creams, gels, mousses, aerosols and pump sprays.

[0022]

【Example】

Example 1 Anionic Polymerization with Dodecylbenzene Sulfonic Acid (DDBSA) Into a 6 liter stainless steel beaker, octamethylcyclotetrasiloxane (D ₄ or tetramer) 1,500
g, 2,250 g of water and 15 g of dodecylbenzenesulfonic acid were charged. The mixture of octamethylcyclotetrasiloxane, water and acid was mixed using a high shear "Willems Polyton®" mixer to ensure homogenization. Gaullin
It should be noted that other high shear mixers, such as the K., Colloid Mill, are suitable. The mixture was then homogenized at 7,500 psig using a Gaullin Homogenizer®. After the homogenization is complete, the heating mantle,
The mixture was transferred to a 5 liter three neck round bottom flask equipped with a thermometer, condenser, temperature controller and stirrer. The mixture was kept at a temperature of 86 ° C. for 3 hours to cause polymerization. When the reaction mixture was analyzed after the polymerization, the solid content was 35.4%. The reaction mixture was cooled to a temperature of 22-23 ° C. and held at that temperature for 13 hours in order to increase the polymer molecular weight and thereby the polymer viscosity. The reaction mixture, which is an emulsion, was cooled while the acid catalyst was still active, stabilizing the polymer viscosity at about 1 million cP. The average particle size of this emulsion was less than 0.3 μm. Dodecylbenzene sulfonic acid was neutralized with 36 g of a base, a 10% by weight aqueous solution of sodium carbonate, to bring the pH of the final emulsion to about 7.

Example 2 Various polymer viscosities By the polymerization procedure outlined in Example 1, ie using a proportion of 100 parts octamethylcyclotetrasiloxane, 1 part dodecylbenzenesulfonic acid and 150 parts water,
Then, the solution was neutralized with an aqueous solution of sodium carbonate, maintained at an initial polymerization temperature of 85 ° C. for 3 hours, and then the polymerization temperature of the second step was changed so as to change the molecular weight of the resulting polymer during a residence time of 24 hours. And as a result,
Various polymer viscosities shown in Table 1 were obtained.

[0024]

[Table 1]

The results in Table 1 show that the second stage polymerization temperature has a significant effect on the polymer viscosity, and that the polymer viscosity increases as the second stage polymerization temperature decreases.

Example 3 Anionic Polymerization Using Xylene Sulfonic Acid and Surfactant Using the procedure of Example 1, 400 g octamethylcyclotetrasiloxane, 40% sodium xylene sulfonate.
Polymerization was tried using 30 g of an aqueous solution, 600 g of water and 0.54 g of sulfuric acid. This mixture did not form a uniform emulsion under conditions of high shear mixing and separated when mixing was stopped. When a further 11 g of anionic surfactant sodium lauryl sulfate was added, a stable emulsion could be formed. The polymerization conditions of the first stage are
As a result of initially 4 hours at 86 ℃, the average particle size is 0.2
At 3 μm, a solids content of 15.4% was obtained.
Heating was continued for another 7 hours. After this time this was undesirable as there was significant free oil on the surface of the reaction mixture and the mixture was discarded.

Example 4 Anionic Polymerization Using Aliphatic Hydrocarbon Sulfonic Acid and Surfactant Using the method and apparatus described in Example 1, sodium tetradecene sulfonate and sodium hydroxytetradecane sulfonate in a weight ratio of 75:25. 40% of the mixture
Aqueous solution 30 g, octamethylcyclotetrasiloxane 4
An emulsion was prepared from 00 g, 600 g water and 0.75 g sulfuric acid. This mixture is mixed vigorously for 7,5
Homogenized at 00 psig. During this process, sulfuric acid produced the free acid of the incorporated anionic surfactant. In this state, polymerization was carried out at 86 ° C. for 7 hours, and the temperature was cooled to 22 to 23 ° C. for 14 hours. The viscosity of the obtained polymer was about 1,000,000 cP, and the emulsion had a solid content of 35.6% by weight and an average particle size of 0.2 μm. No free oil was observed.

Example 5 High Solid Content Anionic Emulsion Polymerization with Dodecylbenzene Sulfonic Acid Using the method and apparatus described in Example 1, 1.2 parts by weight of dodecylbenzenesulfonic acid, 40 parts by weight of water and octamethylcyclotetra An emulsion was prepared from 54 parts by weight of siloxane. The initial polymerization was carried out at a temperature of 85 to 88 ° C. for 3 hours. The second polymerization stage is 16-2
It was carried out at a temperature of 2 ° C. for 5 to 7 hours. This emulsion was neutralized with a 10% by weight aqueous sodium hydroxide solution. The viscosity of the prepared polymer is about 1 to 2,000,
It was in the range of 000 cP. The emulsion obtained from this high solids content synthesis has a solids content of about 54%, an average particle size of 0.23 to 0.28 μm, an emulsion viscosity of less than about 7,000 cP and a pH of about 7 to It was about 9.

Emulsions prepared by this method are compatible with Germaben® II (Sutton laborator).
ies), Glycacil (registered trademark) -L (Lonza)
And Kathon (registered trademark) II / ICP (Rohm &
It has been found to be miscible with preservatives such as Haas). Witco (registered trademark) 1250 (Witco Ch
The use of emical Co.) surfactants can control the emulsion viscosity.

Examples 6 and 7 represent experiments in which the anionic polymerized emulsion polymer was found to be convertible to a cationic emulsion by appropriate choice of surfactant.

Example 6 Anionic Polymerization with Dodecyl Benzene Sulfonic Acid with Emulsion Stabilizer 100 parts by weight of octamethylcyclotetrasiloxane, 1 part by weight of dodecyl benzene sulfonic acid and 150 parts by weight of water were used, and a 10% by weight aqueous solution of sodium carbonate 2 .4
An emulsion having a polymer viscosity of about 1,000,000 cP, obtained by neutralizing with 1 part by weight and prepared as in Example 1,
Polyoxyethylene (15) palm alkylmethyl ammonium chloride (Ethoquad C / made by Armak)
25) 2 parts by weight and 2 parts by weight of POE (18) nonylphenyl ether were added. The emulsion was stirred for 1 hour, then 2 parts by weight of 30% aqueous cetyltrimethylammonium chloride solution was added. This emulsion was stabilized by the use of a nonionic-cationic surfactant mixture.

Example 7 Anionic Polymerization with Dodecylbenzene Sulfonic Acid with Emulsion Stabilizer Polymer viscosity prepared as in Example 1, about 100
POE to base emulsion with 20,000 cP
(18) 4 parts by weight of nonylphenyl ether was added, followed by stirring for 1 hour, and subsequently, 2 parts by weight of cetyltrimethylammonium chloride (6.6 parts by weight of 30% aqueous solution) was added. This emulsion was stabilized by the use of a nonionic-cationic surfactant mixture.

Example 8 Evaluation and Selection of Miscible Surfactants Other surfactant mixtures were evaluated for preparing stable cationic emulsions from emulsions prepared by anionic polymerization. Surfactants that allow the conversion of so-called anionic emulsions to cationic emulsions are known as miscible surfactants (medium surfactan
Enter the category of t). The evaluated surfactants were as follows.

Amphoteric surfactant Lauryl dimethylaminoacetic acid betaine Palm oil fatty acid amide propyldimethylaminoacetic acid betaine 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine anionic surfactant N-lauroyl sarcosine N-lauroyl Sarcosine sodium cationic surfactant quaternary ammonium salt lanolin derivative methylbis (2-hydroxyethyl) oleylammonium chloride nonionic surfactant (POE = polyoxyethylene) POE (4) lauryl ether POE (9) lauryl ether POE ( 23) Lauryl ether POE (6) Stearyl ether POE (20) Stearyl ether POE (6) Sorbitan monooleate POE (6) Sorbitan monosteara Doo POE (20) sorbitan monopalmitate

Prepared by anionic polymerization as described in Example 1 and have an approximate polymer viscosity of about 1.0.
To the 0,000 cP polymer emulsion was added 4 parts by weight of a miscible surfactant selected from the above list. The emulsion was mixed for about 1 hour. If a satisfactory dispersion is achieved, then follow
2 parts by weight of cetyltrimethylammonium chloride (6.6 parts by weight of 30% aqueous solution) were added.

The following results were obtained. 1) POE (6) stearyl ether and POE
(6) Since it was difficult to dissolve sorbitan monostearate in the anionic emulsion, no cationic surfactant was added. 2) Methylbis (2-hydroxyethyl) oleylammonium chloride is not suitable for this purpose because the anionic emulsion was destroyed. 3) N-lauroyl sarcosine and POE (6) sorbitan monooleate were successfully added to the anionic emulsion, but when the cationic surfactant cetyltrimethylammonium chloride was added, the resulting emulsion was destroyed. As such, these two surfactants are not suitable for this intended use. 4) lauryl dimethylamino acetic acid betaine, coconut oil fatty acid amide propyl dimethyl amino acetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, N-lauroyl sarcosine sodium, quaternary ammonium salt lanolin derivative, P
OE (4) lauryl ether, POE (9) lauryl ether, POE (23) lauryl ether, POE (2
0) Stearyl ether and POE (20) sorbitan monopalmitate showed good dispersion and produced an acceptable cationic anionic emulsion polymerized emulsion with acceptable appearance and stability.

Example 9 Selection of Other Cationic Surfactants Using Miscible Surfactant The miscibility of the procedure of Example 8 and the emulsion prepared as in Example 1 with cetyltrimethylammonium chloride was determined. PE (20), a miscible surfactant found to exhibit
Other cationic surfactants have been evaluated using stearyl ether. The cationic surfactants evaluated were as follows. In addition, as a standard, an experiment under the same conditions was performed using the cetyltrimethylammonium chloride used in Example 8.

Cetyltrimethylammonium chloride Stearyltrimethylammonium chloride Distearyldimethylammonium chloride Benzylalkylammonium chloride (mixture of alkyl groups having 12 to 14 carbon atoms) Benzylstearyldimethylammonium chloride

The evaluation results are as follows. 1) Distearyldimethylammonium chloride and benzylstearyldimethylammonium chloride were considered unacceptable because they were difficult to dissolve in the mixture. 2) Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride and benzylalkylammonium chloride (mixtures of 12 to 14 carbon atoms of alkyl groups) exhibit good dispersion and have acceptable appearance and stability, acceptable cations. Anionic emulsion-polymerized emulsion having a positive polarity was produced.

In summary, anionic emulsion polymerized silicone polymer emulsions include lauryl dimethylamino acetic acid betaine, coconut oil fatty acid amidopropyl dimethylamino acetic acid betaine, 2-alkyl-N-carboxymethyl-
N-hydroxyethyl imidazolinium betaine, N-
Lauroyl sarcosine sodium, lanolin derivative of quaternary ammonium salt, POE (4) lauryl ether,
Treatment with an intermediate surfactant selected from the group consisting of POE (9) lauryl ether, POE (23) lauryl ether, POE (20) stearyl ether and POE (20) sorbitan monopalmitate, followed by cetyl trimethyl ammonium chloride , Stearyltrimethylammonium chloride and benzylalkylammonium chloride (a mixture of alkyl groups having 12 to 14 carbon atoms) can be converted into a cationic emulsion by treatment with a cationic surfactant selected from the group consisting of: .

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[Procedure amendment]

[Submission date] November 14, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication C08K 5/42 C08K 5/42 (72) Inventor James H. Merrifield United States, New York 12020, Ball Ston Spa, Thimbleberry Road 213 (72) Inventor Frank J. Traver New York, USA 12180-9527, Troy, Downey Road 1

Claims (8)

[Claims] 1. (a) 10,000 to 10,000,0
A silicone polymer having a viscosity in the range of 00 cSt; (b) an aliphatic hydrocarbon sulfonic acid having 1 to 20 carbon atoms and optionally substituted by a hydroxyl group, an aliphatic hydrocarbon sulfuric acid, an aryl sulfone having 6 to 30 carbon atoms. Acid, and an anionic surfactant selected from the group consisting of alkyl aryl sulfonic acids having 7 to 50 carbon atoms; (c) a miscible surfactant having a hydrophilic-lipophilic ratio of 9 to 25; and (d) bis. (Polyoxyethylene) hydrocarbylmethyl quaternary ammonium halides or sulfates;
A cationic interface selected from the group consisting of an alkyltrimethylammonium halide or sulfate having an alkyl group having 8 to 30 carbon atoms; and a benzylalkyldimethylammonium halide or sulfate having an alkyl group having 8 to 16 carbon atoms. Stable cationic silicone oil-in-water emulsion containing an activator. 2. The method of claim 2, wherein (c) the miscible surfactant is polyglycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester,
Polyoxyethylene sorbite fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene castor oil, polyoxyethylene alkyl ether having 6 to 40 carbon atoms in the alkyl group, polyoxyethylene alkylphenyl ether, polyoxyethylene polyoxypropylene alkyl ether, 6 carbon atoms in the alkyl group
To 40 polyoxyethylene alkylamine, alkyl group having 6 to 40 carbon atoms, polyoxyethylene lanolin, lauryl dimethylamino acetic acid betaine, coconut oil fatty acid amide propyl dimethyl amino acetic acid betaine, 2-alkyl-N A stable cationic silicone oil-in-water emulsion according to claim 1, selected from the group consisting of: -carboxymethyl-N-hydroxyethyl imidazolinium betaine, N-lauroyl sarcosine sodium and quaternary ammonium salt lanolin derivatives. 3. One or more silicones selected from the group consisting of 1) cyclic silicone oligomers, mixed silicone hydrolysates, silanol-terminated oligomers, high molecular weight silicone polymers, and silicones having functional groups, 2) Water, and 3) mixing with anionic surfactant; 4) heating the mixture to a temperature of 75-98 ° C for 1-5 hours; 5) heating the mixture for 3-24 hours, 0 Cooling to a temperature of ~ 25 ° C; 6) adding a miscible surfactant having a hydrophilic lipophilicity ratio of 9-25; and 7) a stable cation comprising adding a cationic surfactant. Of a water-soluble silicone oil-in-water emulsion. 4. The (b) anionic surfactant is an aliphatic hydrocarbon sulfonic acid having 1 to 20 carbon atoms, which may be substituted with a hydroxyl group, and aliphatic hydrocarbon sulfuric acid, and 6 to 30 carbon atoms. Aryl sulfonic acid and carbon number 7
The method according to claim 3, wherein the method is selected from the group consisting of ˜50 alkylaryl sulfonic acids. 5. The (c) miscible surfactant is polyglycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester,
Polyoxyethylene sorbite fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene castor oil, polyoxyethylene alkyl ether having 6 to 40 carbon atoms in the alkyl group, polyoxyethylene alkylphenyl ether, polyoxyethylene polyoxypropylene alkyl ether, 6 carbon atoms in the alkyl group
To 40 polyoxyethylene alkylamine, alkyl group having 6 to 40 carbon atoms, polyoxyethylene lanolin, lauryl dimethylamino acetic acid betaine, coconut oil fatty acid amide propyl dimethyl amino acetic acid betaine, 2-alkyl-N The method according to claim 3 or 4, which is selected from the group consisting of -carboxymethyl-N-hydroxyethylimidazolinium betaine, N-lauroylsarcosine sodium and a quaternary ammonium salt lanolin derivative. 6. (d) The cationic surfactant is bis (polyoxyethylene) hydrocarbylmethyl quaternary ammonium halide or sulfate; an alkyltrimethylammonium halide whose alkyl group has 8 to 30 carbon atoms or Sulfate; and the production method according to any one of claims 3 to 5, which is selected from the group consisting of halides or sulfates of benzylalkyldimethylammonium whose alkyl group has 8 to 16 carbon atoms. 7. A personal care product comprising the emulsion of claim 1. 8. Personal care products include cleansing products, lotions, shampoos, hair dye compositions, conditioners, rinses, neutral lotions, creams, gels,
A personal care product according to claim 7 selected from the group consisting of mousses, aerosols and pump sprays.