JP2002020490A - Polyorganosiloxane emulsion and cosmetic containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an emulsion which is extremely excellent in controllability of an emulsion polymerization reaction, has no coloring, does not affect the environment, and has excellent emulsion stability. SOLUTION: (A) A general formula HO [(R ¹ ) ₂ Si
O] _m H (I) (wherein, R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group which may be the same or different, and m
Represents the viscosity of the component (A) at 25 ° C. of 10 to 3,000.
cSt) is selected from (B) (B1) polyoxyethylene alkyl ether sulfuric acid, (B2) polyoxyethylene alkyl ether phosphoric acid, and (B3) alkyl sulfuric acid. At least two anionic surfactants (provided that the mixing ratio is 1/20 to
20/1, and (1-20) / (1-2)
0) / (1-20)) and (C) emulsion polymerization in the presence of water to form a polyorganosiloxane emulsion.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an emulsion containing a high molecular weight polyorganosiloxane obtained by emulsion polymerization. More specifically, the present invention relates to a method for producing a stable, high-molecular-weight silanol-terminated polydiorganosiloxane obtained by emulsifying a polydiorganosiloxane having a relatively low molecular weight in water with an anionic surfactant, followed by emulsion polymerization of the polydiorganosiloxane. It relates to a molecular weight polyorganosiloxane emulsion. The present invention also relates to cosmetics using the high molecular weight polyorganosiloxane emulsion thus obtained.

[0002]

2. Description of the Related Art A low molecular weight siloxane, particularly a cyclic siloxane oligomer, is dispersed in an emulsified state together with a surfactant, a polymerization catalyst and water and subjected to ring-opening polymerization to produce a high molecular weight polystyrene having a wide viscosity range from silicone oil to silicone raw rubber. Emulsions containing organosiloxanes can be prepared. For example, a method in which a low molecular weight siloxane is emulsified and then a strong acid or a strong alkali catalyst is added to carry out emulsion polymerization (Japanese Patent Publication No. 34-2041), by emulsifying a low molecular weight siloxane using a surfactant having catalytic activity. And polymerization method (Japanese Patent Publication No. Sho 43-
No. 18800). Japanese Patent Publication No. 54-19440 discloses that an organosiloxane is added to an aqueous solution of a salt type anionic surfactant and emulsified, and the obtained emulsion is brought into contact with an acetic acid type cation exchange resin to obtain a surfactant. By converting the agent to the acid form,
A method for polymerizing the polyorganosiloxanes is disclosed.

Further, JP-B-41-1399 and JP-B-44-20116 disclose benzenesulfonic acid and naphthalenesulfonic acid substituted with an aliphatic hydrocarbon group, aliphatic hydrocarbonsulfonic acid and silylalkylsulfonic acid. A method is disclosed in which an organosiloxane and a silanol group-containing disilcarbane are emulsion-polymerized in an aqueous solvent in the presence of a sulfonic acid catalyst having surface activity selected from acids. It is also disclosed that a polydiorganosiloxane having a molecular chain terminal blocked with a silanol group is emulsified with a high-pressure homogenizer together with a catalyst having such a surface activity, and then left at room temperature for polymerization. In JP-A-63-265924 and JP-A-4-178429, a polydiorganosiloxane having a molecular chain end blocked with a silanol group is used as a starting material and contains a high molecular weight polyorganosiloxane by emulsion polymerization. It has been disclosed to produce emulsions of this type.

In the case of producing an emulsion containing a high molecular weight polyorganosiloxane by such emulsion polymerization, dodecylbenzenesulfonic acid is typified as a polymerization catalyst also serving as a surfactant because it is easily emulsified and easily available. Alkyl benzene sulfonic acids are commonly used.

However, when alkylbenzene sulfonic acid is used, even if neutralization is performed after polymerization, the alkylbenzene sulfonic acid salt remains in the emulsion, and depending on the application, it is colored by ultraviolet rays and has low biodegradability. However, there is a problem that the impact on the environment is great. In particular, when the emulsion thus obtained is used as it is as a raw material for cosmetics, the alkylbenzene sulfonate is not preferred because it reduces the feeling of use of the cosmetic.

Japanese Patent Application Laid-Open No. 2-147632 discloses that the use of aliphatic benzenesulfonic acid and trihalogenated acetic acid in combination reduces the amount of aliphatic benzenesulfonic acid as much as possible to suppress yellow coloring and reduce yellow coloring. A method for producing a polyorganosiloxane emulsion which avoids a decrease in the degree of polymerization of a molecular weight siloxane is disclosed. However, there are some problems, such as complicated handling due to the use of solid hexamethylcyclotrisiloxane as the low molecular weight siloxane as a raw material, and a slight deterioration in emulsion stability.

On the other hand, a cyclic siloxane oligomer such as octamethylcyclotetrasiloxane has been used because it is easily available as a low molecular weight siloxane to be subjected to such emulsion polymerization, and is easy to emulsify and ring-opening polymerization. I have. However, ring-opening polymerization of a cyclic siloxane oligomer is an equilibrium reaction, and an emulsion after emulsion polymerization usually contains a cyclic siloxane oligomer such as octamethylcyclotetrasiloxane in polysiloxane.
-15% by weight, typically about 10% by weight. Therefore, for use as a very homogeneous emulsion, the oligomer may volatilize from the emulsion and impair the physical stability of the emulsified system. Further, such an emulsion is used in a large amount as a hair cosmetic in a hairdressing salon, for example, for hair treatment and the like, particularly when accompanied by a heat blow treatment, the volatilized oligomers contaminate the surrounding environment, and particularly, The ventilation fan system may be contaminated or contact failures of various electric devices such as a fan heater may occur. Furthermore, when such an emulsion is used for skin cosmetics or the like, the cyclic siloxane oligomer contained therein may impair the feel of cosmetics depending on the purpose of use due to its volatile properties. Therefore, when used in such applications, it has been required to suppress the amount of the cyclic siloxane oligomer in the emulsion. However, it is difficult to remove the cyclic siloxane present in the emulsion without breaking the emulsion after emulsion polymerization.

[0008] In order to solve such a problem, the applicant of the present invention has disclosed in Japanese Patent Application Laid-Open No. 11-71522 a method using an unsaturated aliphatic sulfonic acid and / or a hydroxylated aliphatic sulfonic acid as a surfactant. Kaihei 11-222554
JP-A-2000-53 discloses a method using alkylbenzenesulfonic acid and alkylsulfuric acid as surfactants.
No. 769 proposes a method using alkylbenzenesulfonic acid or unsaturated aliphatic sulfonic acid.

However, when producing a high molecular weight polyorganosiloxane by the above method, the reaction time is relatively long. On the other hand, when obtaining a low molecular weight polyorganosiloxane, it is difficult to control the polymerization reaction. There was a point. Further, at present, there is no product which satisfies all of coloring, influence on environment, and stability of emulsion.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide an emulsion polymerization reaction which is extremely excellent in controllability and has no coloring.
An object of the present invention is to provide an emulsion which does not affect the environment and has excellent emulsion stability. Another object of the present invention is to provide a cosmetic comprising such an emulsion.

[0011]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that it is extremely effective to use two or three specific anionic surfactants in combination. And completed the present invention.

That is, the present invention relates to (A) a compound represented by the general formula HO [(R ¹ ) ₂ SiO] _m H (I) wherein R ¹ may be the same or different, substituted or unsubstituted Represents a substituted monovalent hydrocarbon group;
Represents the viscosity of the component (A) at 25 ° C. of 10 to 3,000.
cSt) is selected from (B) (B1) polyoxyethylene alkyl ether sulfuric acid, (B2) polyoxyethylene alkyl ether phosphoric acid, and (B3) alkyl sulfuric acid. At least two anionic surfactants (provided that the mixing ratio is 1/20 to
20/1, and (1-20) / (1-2)
0) / (1-20)), and (C) a polyorganosiloxane emulsion obtained by emulsion polymerization in the presence of water, and a cosmetic comprising the polyorganosiloxane emulsion.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The component (A) used as a monomer to give a polyorganosiloxane in the present invention is a polydiorganosiloxane having a molecular chain terminal blocked with a silanol group, and is represented by the general formula (I). This polydiorganosiloxane may be hereinafter referred to as α, ω-dihydroxypolydiorganosiloxane. In addition, since this polyorganosiloxane is in a monomer relationship with respect to the final polycondensation reaction product polyorganosiloxane, its degree of polymerization is lower than that of the final polycondensation product, and it can be said that it is an oligodiorganosiloxane. .

The component (A), a polydiorganosiloxane having a molecular chain terminal blocked with a silanol group, is a main raw material for emulsion polymerization. The molecular structure is linear as shown by the general formula (I), but may have a branched structure in part as long as the molecular chain end is blocked with a silanol group. . m is such that the viscosity of the polydiorganosiloxane at 25 ° C. is 10 to 3,000 cSt, preferably 15 to 1,000 cSt, particularly preferably 20 to 30 cSt.
It is a value within the range of 0 cSt. That is, if the silanol-terminated polydiorganosiloxane has a viscosity of less than 10 cSt, it is difficult to synthesize and purify it stably, and if it exceeds 3000 cSt, it becomes difficult to emulsify. In addition,
m also varies depending on the types of R ¹ bonded to the silicon atom and their mutual ratio. For example, for the most preferred polydimethylsiloxane, m ranges from 8 to 500.

In the formula (I), R ¹ bonded to a silicon atom is (1) a carbon atom having 1 to 30, preferably 1 to 30 carbon atoms.
10, alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, etc.
(2) a cycloalkyl group having 4 to 7, preferably 6, carbon atoms such as cyclohexyl;
8, preferably 2 to 3, alkenyl groups, e.g., vinyl, allyl, (4) an aralkyl group, especially an aryl moiety is a phenyl or lower alkyl (up to C ₄ about) substituted phenyl, the alkyl moiety up to about C ₄ those, for example, 2-phenylethyl, 2-phenylpropyl, (5) aryl group, especially phenyl or substituted phenyl (substituents include an alkyl group of up to about C _4),
Examples thereof include a phenyl group, a tolyl group and the like, and (6) a substituted hydrocarbon group, particularly those in which the substituent is a halogen, such as 3,3,3-trifluoropropyl. High molecular weight polyorganosiloxane obtained by emulsion polymerization has low surface tension, spreads well when coated, has excellent elongation, water repellency, gloss, etc., and has no physiological activity. The above is preferably a methyl group, and it is particularly preferable that substantially all of them are methyl groups. Accordingly, preferred as the component (A) are α, ω-dihydroxypoly (dimethylsiloxane), and a part of the dimethylsiloxane unit is a methylethylsiloxane unit, a methylhexylsiloxane unit, a methylphenylsiloxane unit, a diphenylsiloxane unit, or the like. Is a copolymerized polysiloxane substituted by Of these, α, ω-dihydroxypoly (dimethylsiloxane) is particularly preferred.

Such a silanol group-terminated polydiorganosiloxane is preferably synthesized, for example, by hydrolyzing dimethyldichlorosilane and subjecting it to polycondensation. If desired, for example, the corresponding cyclic siloxane oligomer is subjected to ring-opening polymerization in the presence of an acidic catalyst such as sulfuric acid, or an alkaline catalyst such as potassium hydroxide or potassium silanolate using water as a terminator. It may be a synthesized one.

The component (B) used in the present invention is a component necessary for emulsifying the component (A) in water. In the present invention, the component (B) is an anionic surfactant. The component (B) is a component that can function as a polymerization catalyst for the component (A), as described later, in addition to functioning as such an emulsifier. That is, the component (B) acts as a surfactant for dispersing and emulsifying the silanol-terminated polydiorganosiloxane, which is the component (A), in the component (C), and also serves as a catalyst for the dehydration polycondensation reaction of the silanol group of the component (A). It is a component that can function as.

The anionic surfactant used as component (B) in the present invention includes at least one selected from (B1) polyoxyethylene alkyl ether sulfate, (B2) polyoxyethylene alkyl ether phosphate, and (B3) alkyl sulfate. There are two types.

In the above anionic surfactants, the number of carbon atoms in the alkyl group, the average number of moles of ethylene oxide added, and the like are not particularly limited, and any of commercially available compounds can be used. Specifically, examples of (B1) include polyoxyethylene (2) octyl ether sulfate, polyoxyethylene (8) decyl ether sulfate, polyoxyethylene (3) lauryl ether sulfate, and the like.
(B2) includes dipolyoxyethylene (10) lauryl ether phosphoric acid, tripolyoxyethylene (4) lauryl ether phosphoric acid, tripolyoxyethylene (5)
Examples of (B3) include cetyl ether phosphoric acid and the like, and examples thereof include lauryl sulfate, myristyl sulfate, and cetyl sulfate.

The anionic surfactants used in the present invention also include those which are salts of the above-mentioned acid type component (B), ie, salt type anionic surfactants. As the kind of such a salt, an amine salt such as a sodium salt, a potassium salt, an ammonium salt and triethanolamine is preferable from the viewpoint of an emulsifying effect. Specifically, (B
Examples of 1) are polyoxyethylene (2) sodium octyl ether sulfate, polyoxyethylene (8) sodium decyl ether sulfate, polyoxyethylene (3) sodium lauryl ether sulfate, and (B2)
Dipolyoxyethylene (10) sodium lauryl ether phosphate, tripolyoxyethylene (4) sodium lauryl ether phosphate, tripolyoxyethylene (5) sodium cetyl ether phosphate, etc. (B3) include sodium lauryl sulfate, myristyl sulfate Examples thereof include sodium, sodium cetyl sulfate and the like, and corresponding potassium salts, ammonium salts and triethanolamine salts.

The above-mentioned component (B) may be mixed with components (A) and (C) in the form of an acid and subjected to emulsification, but may be used as an emulsifier in the form of a water-soluble salt or a neutralized salt. After use, an acid may be added to generate an acid-type component (B) in the reaction system to function as an emulsion polymerization catalyst.
In particular, when the emulsification is carried out at a high temperature or when the temperature rises during the emulsification, the component (B) first acts as a surfactant and then acts as a polymerization catalyst, as in the latter case. It is preferred to use That is, in these cases, the emulsion polymerization conditions can be easily controlled, the emulsion state is good, and the high-molecular-weight polyorganosiloxane does not float during storage, and an emulsion with excellent stability can be obtained. Because. Further, the content of the cyclic siloxane oligomer in the obtained emulsion can be further reduced.

The present invention is characterized in that two or more of the above (B1) polyoxyethylene alkyl ether sulfate, (B2) polyoxyethylene alkyl ether phosphate, and (B3) alkyl sulfate are used in combination. The mixing ratio is two cases, that is, (B1) / (B
2), (B1) / (B3) or (B2) / (B3)
In the case of the above, they are respectively 1/20 to 20/1, preferably 1/10 to 10/1. If the ratio is outside the range of 1/20 to 20/1, the stability will be poor, and a sufficient effect will not be obtained.

Also, (B1) / (B2) / (B3)
The ratio in the case of species is (1-20) / (1-20) / (1
To 20), and preferably (1 to 10) / (1 to 1).
0) / (1-10).

These anionic surfactants, (B
When 1), (B2) and (B3) are used alone, the reaction rate of the emulsion polymerization depends on each anionic surfactant, and the reaction rates in the order of (B2) <(B1) <(B3) Becomes larger. For this reason, it is important to select the type of anionic surfactant and adjust the blending ratio in accordance with the desired viscosity of the polyorganosiloxane. For example, when a high molecular weight polyorganosiloxane is desired, (B1)
The reaction can be completed in a relatively short time by using the combined system of / (B3). On the other hand, when efficiently obtaining a low molecular weight polyorganosiloxane, (B1) /
It is preferable to use a combined system of (B2) and (B2) / (B3), but the method of use is not limited thereto.

The amount of component (B) to be used can be any suitable one in consideration of the case where it is used as a surfactant and the case where it is used as a polymerization catalyst. Typical examples of the used amount are as follows. That is, the total amount of the anionic surfactants in the acid form or a salt thereof is preferably 0.5 to 100 parts by weight in terms of acid with respect to 100 parts by weight of the component (A). 50 parts by weight is more preferable, and 2 to 10 parts by weight.
Part by weight is particularly preferred. If the amount is less than 0.5 part by weight, the emulsion may have poor stability and may be separated, while if it exceeds 100 parts by weight, the emulsion may be thickened and the fluidity may be deteriorated.

In the present invention, a polymerization catalyst may be used.
The polymerization of the component (A) belongs to the category of polymerization involving dehydration of terminal hydroxyl groups, that is, polycondensation. Such components include inorganic acids and organic acids. Inorganic acids include hydrochloric acid, sulfuric acid, phosphoric acid, sulfamic acid, and others. Organic acids include carboxylic acids (including formic acid),
Sulfonic acid, sulfamic acid, sulfuric acid monoester, and others. Among the organic acids, sulfonic acid and / or sulfuric acid monoester include those having a large contribution of the organic group and therefore those having surface activity. Therefore, when an anionic surfactant having a catalytic action is used as the component (B), at least a part of the polymerization catalyst can be omitted.

That is, as described above, the polymerization catalyst is obtained by converting a salt-type anionic surfactant added as an emulsifier into an acid-type anionic surfactant by adding an acid after emulsification. You can also. In this case, the acid added after the emulsification has a function of converting at least a part of the salt-type anionic surfactant into an acid form and acting as a polymerization catalyst. Examples of such an acid include sulfuric acid, hydrochloric acid, phosphoric acid, and formic acid. Of these, sulfuric acid and hydrochloric acid are preferred because they themselves function as a catalyst for the dehydration polycondensation reaction of the silanol group of the component (A) and can obtain a high polymerization rate even at a low temperature. When an acid is used in combination as described above, the amount of the acid is not particularly limited, but may be 0.05 to 10 parts by weight based on 100 parts by weight of the component (A).
Part by weight is preferred, and 0.1 to 5 parts by weight is particularly preferred.

Water as the component (C) is a medium for dispersing and emulsifying the component (A). Component (C) is used in an amount of usually 30 to 1,000 based on 100 parts by weight of component (A).
Parts by weight, and the concentration of the component (A) in the emulsion is 1
An amount that will be 0 to 70% by weight is preferred. Since the emulsion of the present invention takes advantage of the feature that a high concentration emulsion has good stability, the amount of the component (C) used is such that the concentration of the component (A) in the emulsion is 40 to 70% by weight. Is particularly preferred. In addition, component (A)
As a medium in which is dispersed, various solvents such as an aliphatic hydrocarbon, an aromatic hydrocarbon and a cyclic siloxane may be included in addition to the component (C). However, in the present invention, it is desirable not to include these solvents before the emulsion polymerization, that is, to use a solvent-free medium.

The polyorganosiloxane emulsion of the present invention is obtained by subjecting the emulsion containing the above components (A) to (C) to polymerization of the component (A). As long as it contains (A) to (C) as essential components, various auxiliary components may be dissolved or dispersed therein as long as the gist of the present invention is not impaired. Such an auxiliary component may be added to the emulsion before or during the polymerization, or may be added to the emulsion after the polymerization. As long as the auxiliary component does not inhibit the polymerization of component (A), it is usually better to add these auxiliary components before or during the polymerization to improve the dispersibility.

The polyorganosiloxane emulsion of the present invention can be produced as follows. That is, a polydiorganosiloxane (component (A)) whose molecular chain terminals are blocked with silanol groups, an anionic surfactant (component (B)) and water (component (C)) are premixed. The mixing order is arbitrary, but, for example, the component (B) is mixed and dissolved in the component (C) in a stirring tank, and the component (A) is added thereto with stirring. Then, a homogenizer,
Pass through an emulsifier such as a colloid mill, line mixer, or sonolator. It is preferable to carry out coarse emulsification using an emulsifier such as a homomixer, a colloid mill or a line mixer, and further to emulsify through a emulsifier such as a pressure homogenizer or an ultrasonic homogenizer. If necessary, water is further added to uniformly emulsify and disperse. When a salt is used as the component (B) at the time of emulsification, an acid is added and dispersed to produce the component (B) alkylsulfuric acid or the like. As described above, these function as a catalyst for emulsion polymerization, and thus, the polymerization catalyst is used in the "in s
Itu) "can also be formed as described above.

When the stirring is continued, a high molecular weight polyorganosiloxane is synthesized by a polycondensation reaction of the silanol group at the molecular chain end of the component (A), and an emulsion containing the same is formed. In order to obtain a polyorganosiloxane having a higher degree of polymerization and to reduce the cracking reaction, the temperature of the polycondensation reaction is preferably as low as possible. On the other hand, if the cooling is excessive, the stability of the resulting emulsion is impaired. Therefore, in consideration of these, the preferable condensation conditions are the emulsion freezing point to 30 ° C, more preferably the emulsion freezing point to 20 ° C, and further more preferably the emulsion freezing point. ~ 2
It is 2 to 48 hours at 0 ° C., but if necessary, a longer time may be used. Particularly preferred condensation conditions are from the emulsion freezing point to less than 5 ° C.

In emulsion polymerization of a polyorganosiloxane emulsion, it is generally known that a higher molecular weight can be obtained by lowering the temperature of the polycondensation reaction. However, generally, in order to increase the polymerization rate and increase the efficiency of the polymerization reaction, heating is performed at the beginning of the reaction, and under such conditions, the amount of the low molecular weight siloxane oligomer in the obtained emulsion is reduced. It was difficult. . In the present invention, from the beginning to the end of the polycondensation reaction, preferably from the emulsion freezing point to
By performing the reaction at 30 ° C., the amount of the low-molecular-weight siloxane oligomer is small, so that a higher-molecular-weight polyorganosiloxane emulsion can be obtained.
Further, by setting the emulsion freezing point to less than 5 ° C., a higher molecular weight and a smaller particle size, for example, 280
It is characterized in that a polyorganosiloxane emulsion having a size of not more than nm can be obtained.

When the desired degree of polymerization has been reached, an alkaline substance is added to neutralize the acid-type anionic surfactant as a catalyst and the added acid, thereby terminating the polymerization reaction. . Examples of the alkaline substance include inorganic substances such as sodium hydroxide, potassium hydroxide, ammonia, sodium carbonate, potassium carbonate, ammonium carbonate, and potassium acetate, and amines such as triethanolamine.

In this manner, a stable emulsion containing a high molecular weight polyorganosiloxane can be produced.
Polyorganosiloxane obtained by emulsion polymerization,
It has a silanol group at the terminal of the molecular chain and has a viscosity at 25 ° C. of preferably 500 cSt or more, more preferably 1 cSt or more.
It is between 000 and 30,000,000 cSt.

Alternatively, depending on the purpose, a compound having a triorganosilyl group, for example, a trimethylsilyl group at the molecular chain terminal and having a viscosity at 25 ° C. of 500 to 10,000,000 cSt can be prepared by blending a terminal terminator described below. A polyorganosiloxane can be obtained with good control.

The polyorganosiloxane contained in the emulsion uses the component (A) as a starting material.
The amount of the cyclic siloxane oligomer contained therein is almost governed by the content of the cyclic siloxane oligomer in the component (A) used, and is 1.0% by weight by-produced during the emulsion polymerization.
Only the following cyclic siloxane oligomers are added.
Accordingly, the content of the cyclic siloxane oligomer in the polyorganosiloxane after the emulsion polymerization can be controlled to 3.5% by weight or less, more preferably 1.0% by controlling the content in the component (A) as described above. % By weight or less.

In addition to the component (B) and / or its salt used in the present invention, in order to improve the stability of the polyorganosiloxane emulsion of the present invention, other anions may be used as long as the object of the present invention is not impaired. One or more kinds of nonionic and / or nonionic surfactants may be added at any other stage during the initial emulsification or after the polycondensation reaction of the component (A). Thus, (B)
Other anionic surfactants used in combination with the component and / or its salt include polyoxyethylene alkyl ether carboxylate, N-acyl amino acid salt, N-acyl taurate and the like. Further, as the nonionic surfactant, those having an HLB of 6 to 16 or a combination of two or more kinds having an additive HLB of 6 to 16 are preferable. Examples of such a nonionic surfactant include polyoxyalkylene alkyl ethers. , Polyoxyethylene phytosterol ether, polyethylene glycol fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester, polyoxyethylene fatty acid amine, glycerin fatty acid ester, Examples thereof include sorbitan fatty acid esters and sucrose fatty acid esters, but are not limited thereto.

As described above, the amount of the anionic and / or nonionic surfactant arbitrarily added is as follows: (B)
When the component (B) is blended before the emulsion polymerization using the catalyst, it is necessary that the component (B) does not impair the catalytic ability of the component (B). Not more than 5 times the amount of the salt to be blended.

In order to block the silanol group at the molecular end of the high molecular weight polyorganosiloxane obtained by emulsion polymerization with a stable triorganosilyl group, or to control the average degree of polymerization of the polyorganosiloxane to a desired value. At the time of emulsification, a small amount of the siloxane oligomer having a triorganosilyl group can be added as a terminal stopper. When the triorganosilyl group is a trimethylsilyl group, the added siloxane oligomer includes:
Hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, etc. are exemplified. In the temperature range from the freezing point of the emulsion to 30 ° C., the reaction rate by the acidic catalyst is excellent. Hexamethyldisiloxane is preferred because it can be easily removed by volatilization. Further, a siloxane oligomer having a vinyl group, such as 1,3-divinyltetramethyldisiloxane, is added, and a vinyldimethylsilyl group is introduced as a triorganosilyl group at a molecular terminal to utilize the reactivity of the vinyl group. Thus, an emulsion of a crosslinkable high molecular weight base polymer can be obtained.

The polyorganosiloxane emulsion obtained by emulsion polymerization is used for surface treatment of various substrates, and in order to form a strong film, methyldimethoxysilane, methyltrimethoxysilane, dimethyldiethoxysilane, 3-methacrylic Reactive silanes such as roxypropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyl
-(2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,
Reactive silanes such as 3-aminopropyltris (trimethylsiloxy) silane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropylmethyldimethoxysilane are added in small amounts during or after emulsion polymerization. It can also be added. In order to stabilize the polyorganosiloxane emulsion thus obtained, glycerin, water-soluble alkylene glycol or water-soluble polyalkylene glycol may be added. Further, a preservative, a fungicide, a rust inhibitor for preventing metal corrosion, and the like for preserving the emulsion may be added.

The polyorganosiloxane emulsion of the present invention contains a high-molecular-weight polyorganosiloxane as a main component, and is compared with an emulsion obtained by mechanically emulsifying such a polyorganosiloxane. Its stability is very good.
Furthermore, since the content of the cyclic siloxane oligomer in the emulsion is low, the stability of the emulsion is not impaired by the oligomer, and there is no environmental pollution. Good. Therefore, the polyorganosiloxane emulsion of the present invention can be used for cosmetics and the like to give a unique stretch, touch, and luster to silicone. In addition, it is useful as a protective material for furniture, miscellaneous goods, interior and exterior of automobiles, a polishing agent for improving the appearance of these materials, and a fiber treatment agent for fabrics, interior decoration materials, hanging cloths and the like.

The polyorganosiloxane emulsion of the present invention obtained as described above can itself be used as a cosmetic such as a hand cream or an anti-branch agent. In addition, various types of cosmetics are prepared by mixing the emulsion in an amount of 0.1% by weight or more and other optional components (cosmetic preparation components described below) within a range not to impair the object of the present invention. Can be. Such cosmetics include hair oil, hair dye, skim oil, set lotion,
Hair cosmetics such as tics, bottled oils, hair creams, hair tonics, hair liquids, hair sprays, pomades, shampoos, hair rinses, hair conditioners, hair lotions, anti-split agents, as well as hand creams, hand lotions and skins Examples include creams, foundations, eye shadows, eye liners, mascaras, facial cleansers, and skin cosmetics such as antiperspirants. Examples of the form of the cosmetic include solid, gel, liquid, and paste forms.

Other components (cosmetic preparation components) used for blending the polyorganosiloxane emulsion of the present invention and using the same to prepare cosmetics include the following. That is, the components include (1) hydrocarbons such as liquid paraffin, vaseline, solid paraffin, squalane and olefin oligomers, and (2) esters such as isopropyl palmitate, stearyl stearate, octyldodecyl myristate. Octyldodecyl oleate, lanolin acetate, and 2-ethylhexanoic acid triglyceride,
(3) Higher alcohols such as lauryl alcohol, cetyl alcohol, stearyl alcohol, lanolin alcohol, and beeswax; (4) higher fatty acids such as palmitic acid and stearic acid; and amines such as diethanolamine to neutralize the same. , (5)
Humectants such as ethylene glycol, propylene glycol, 1,3-butylene glycol, glycerin,
And (6) inorganic powders such as sorbitol,
Titanium oxide, carbon black, iron oxide, sericite,
(7) organic polymer powders such as talc, kaolin, and mica, such as nylon, polyethylene, and poly (meth) acrylate; (8) solvents, such as water and ethanol; Anionic and nonionic surfactants exemplified as surfactants arbitrarily incorporated in the emulsion polymerization of polyorganosiloxane, amphoteric surfactants such as betaine, (10) preservatives, (11) Coloring agent, and (1
2) Perfume and the like are exemplified, but not limited thereto.

To blend these components, the polyorganosiloxane emulsion of the present invention and other components are
Simply mix uniformly, or emulsify components other than the emulsion in advance with an emulsifier such as a homogenizer, a colloid mill, or a line mixer, or mix uniformly with a stirrer, and then add the emulsion to this and disperse. For example, various methods can be adopted. Since the cosmetic thus obtained contains the emulsion according to the present invention, it has excellent properties such as spreadability, elongation, water repellency and gloss when applied, and has good stability. And, since the excellent properties such as good feel to the skin and the like can be maintained even when the cosmetic is made, the resulting cosmetic has a silicone-specific extension, good touch, and It is possible to exhibit excellent properties such as luster.

[0045]

EFFECTS OF THE INVENTION The polyorganosiloxane emulsion according to the present invention is free from the problems of the prior art, has no coloring, does not affect the environment, has a high molecular weight polyorganosiloxane,
The present invention has solved the problems of the stability of the emulsion and the amount of the cyclic siloxane oligomer in the emulsion, and the cosmetic according to the present invention exhibits excellent properties such as silicone-specific stretch, touch, and luster. Can be performed as described above.

[0046]

The following examples and comparative examples further illustrate the present invention. Parts and% in Examples
Are by weight unless otherwise indicated, and the viscosities are values at 25 ° C. The present invention is not limited by these examples.

The emulsion obtained by emulsion polymerization
Viscosity and stability of high molecular weight polyorganosiloxane contained
The content and the cyclic siloxane oligomer content are as follows:
It was measured or implemented as follows. (1) Viscosity Polyorganosiloxane viscosity emulsion 100 parts
Add 200 parts of isopropyl alcohol and stir well
And let stand for 24 hours to separate into two layers.
Transfer the mixture to a Petri dish and place in an oven at 150 ° C for 45 minutes
And completely remove residual isopropyl alcohol and moisture
Evaporation gave the polyorganosiloxane. This is 2
After cooling to 5 ° C., the viscosity was measured using a rotational viscometer. (2) Stability (separated state) Put the emulsion in a dryer at 50 ° C.
The state of separation when stored for 0 days is evaluated according to the following criteria.
Was. ：: No separation △: Oil floating slightly observed ×: Oil layer observed (colored state) Emulsion stored under direct sunlight for 3 months
The degree of coloring in this case was evaluated according to the following criteria. : No coloring △: Slight yellowing is observed ×: Yellowing (3) Content of cyclic siloxane oligomer 5 parts by volume of the emulsion was collected, and methanol was added to 50 parts by volume.
Volume part, n-hexane 100 volume part and water 50 volume part
And shake vigorously, and let stand for 24 hours to separate into two layers.
After that, the n-hexane layer was collected with a microphone syringe and
Chromatograph the cyclic siloxane oligos in the sample.
The mer was quantified. From this value, separately from the n-hexane layer
Polyorganosiloxane obtained by volatilizing n-hexane
From the amount of the cyclic siloxane in the polyorganosiloxane
Calculate the oligomer content and calculate the
Of the cyclic siloxane oligomer was calculated. Example 1 Polyoxyethylene (2) lauryl ether sulfate
3 parts and dipolyoxyethylene (10) lauryllate
12 parts of sodium tellurate in 455 parts of deionized water
Was dispersed uniformly. It has a viscosity of 85 cSt,
Α, ω-Dihydride containing 1.3% of oxane oligomer
Add 500 parts of roxypoly (dimethylsiloxane),
After pre-mixing by stirring, pressurized homogenizer (pressure
500kgf / cm^Two) Twice.
Contains α, ω-dihydroxypoly (dimethylsiloxane)
The resulting emulsion was obtained. To this emulsion, add sulfuric acid 1.
5 parts were added, and the reaction was carried out at 25 ° C. for 5 hours while stirring.
Was. Then, while continuing stirring, 10% sodium carbonate
The polymerization is carried out by dropping the aqueous solution until the pH becomes 7.
Stop the reaction and remove the emulsion containing polyorganosiloxane.
Rejon E-1 was produced. Example 2 Polyoxyethylene (2) lauryl ether sulfate
15 parts of sodium and 15 parts of sodium lauryl sulfate
And uniformly dispersed in 440 parts of water. This has a viscosity of 85
Contains 1.3% of cyclic siloxane oligomer by cSt
α, ω-dihydroxypoly (dimethylsiloxane) 50
0 parts, and premixed by stirring.
Niser (pressure 500kgf / cm^Two) Twice
Thus, α, ω-dihydroxypoly (dimethylsilo)
Xan) was obtained. This emulsion
, 1.5 parts of sulfuric acid was added thereto, and stirred at 25 ° C for 1 hour.
The reaction was performed for 5 hours. Then, 10% while continuing to stir
Add sodium carbonate solution dropwise until the pH becomes 7.
To stop the polymerization reaction, and the polyorganosiloxane
An emulsion E-2 containing sun was prepared. Example 3 Tripolyoxyethylene (5) cetyl ether phosphate
Remove 4 parts of thorium and 36 parts of sodium lauryl sulfate
It was uniformly dispersed in 430 parts of ON water. This has a viscosity of 8
At 5 cSt, contains 1.3% of cyclic siloxane oligomer
Α, ω-dihydroxypoly (dimethylsiloxane) 5
Of the mixture, and premixed by stirring.
Jinizer (pressure 500kgf / cm^Two) Twice
To obtain α, ω-dihydroxypoly (dimethyl
Oxane). This emuljo
1.5 parts of sulfuric acid was added to the mixture, and the mixture was stirred at 15 ° C.
The reaction was performed for 15 hours. Then, with continuous stirring, 10
% Sodium carbonate aqueous solution until pH 7
By stopping the polymerization reaction, the polyorganosiloxane
An emulsion E-3 containing a xan was prepared. Example 4 Polyoxyethylene (2) lauryl ether sulfate
15 parts and tripolyoxyethylene (4) laurylue
-5 parts of sodium tellurate and sodium lauryl sulfate
5 parts were uniformly dispersed in 440 parts of deionized water. This
In addition, a cyclic siloxane oligomer having a viscosity of 85 cSt
Α, ω-dihydroxy poly (dimethyl containing 1.3%
(Siloxane) and 500 parts of hexamethyldisiloxane.
After adding 5 parts and pre-mixing by stirring, pressurized homogen
Niser (pressure 500kgf / cm ^Two) Twice
Thus, α, ω-dihydroxypoly (dimethylsilo)
Xan) was obtained. This emulsion
, 1.5 parts of sulfuric acid was added thereto, and stirred at 25 ° C. for 5 hours.
A time reaction was performed. Then, while stirring, 10% charcoal
Drop the aqueous solution of sodium acid until the pH becomes 7.
To stop the polymerization reaction, and the polyorganosiloxane
E-4 was prepared. Example 5 Polyoxyethylene (2) lauryl ether sulfate
8 parts of sodium, 20 parts of sodium lauryl sulfate and polyoxy
2 parts of ethylene (4) lauryl ether is added to deionized water 3
It was dispersed uniformly in 40 parts. This has a viscosity of 15 cSt
A, containing 2.5% of a cyclic siloxane oligomer,
600 parts of ω-dihydroxy poly (dimethylsiloxane)
And pre-mixed by stirring.
(With pressure 1000kgf / cm^Two) Twice
And α, ω-dihydroxypoly (dimethylsiloxy)
An emulsion was obtained. This emulsion
, 1.5 parts of sulfuric acid was added thereto and stirred at 5 ° C. for 48 hours.
A time reaction was performed. Then, while stirring, 10% charcoal
Drop the aqueous solution of sodium acid until the pH becomes 7.
To stop the polymerization reaction, and the polyorganosiloxane
An emulsion E-5 was prepared. Example 6 Polyoxyethylene (2) lauryl ether sulfate
7.5 parts of sodium and 7.5 parts of sodium lauryl sulfate were removed.
It was uniformly dispersed in 660 parts of ion water. In addition, the viscosity
At 700 cSt, 0.25% of cyclic siloxane oligomer
Containing α, ω-dihydroxypoly (dimethylsiloxa
3) Add 300 parts and premix by stirring.
Pressure homogenizer (pressure 1000kgf / cm^Two) In 2
Times, α, ω-dihydroxypoly (di-
An emulsion containing methylsiloxane) was obtained. This d
1.5 parts of sulfuric acid is added to the marjon, and while stirring, 2 parts are added.
The reaction was performed at 5 ° C. for 5 hours. Next, continue stirring.
10% aqueous sodium carbonate solution until pH 7
By lowering, the polymerization reaction was stopped. To this
5 parts of polyoxyethylene (23) lauryl ether
Was added. Thus, the polyorganosiloxane is
An emulsion E-6 was prepared. Comparative Example 1 Dodecylbenzenesulfonic acid (30 parts) was mixed with deionized water (45).
It was dispersed uniformly in 5 parts. In addition to this,
Add 500 parts of rotetrasiloxane and reserve by stirring
After mixing, a pressurized homogenizer (pressure 500 kgf /
cm^Two) Twice.
An emulsion containing rotetrasiloxane was obtained. This d
Hold the marjon at 85 ° C. for 3 hours while stirring,
After cooling to 25 ° C over time,
The reaction was performed at 25 ° C. for 5 hours. Then, continue stirring.
Then add 10% aqueous solution of sodium carbonate until the pH becomes 7.
The polymerization reaction is stopped by dropping,
Preparation of emulsion EC-1 containing ganosiloxane
Was. Comparative Example 2 75% sodium tetradecenesulfonate and hydroxy
Mixture 30 of 25% sodium tetradecanesulfonate
Parts were evenly dispersed in 440 parts of deionized water. this
And a cyclic siloxane oligomer having a viscosity of 85 cSt.
Α, ω-dihydroxy poly (dimethylsilo containing 3%
Xane) was added and premixed by stirring.
After that, a pressure homogenizer (pressure 500 kgf / cm^Two)
Α, ω-dihydroxypoly
An emulsion containing (dimethylsiloxane) was obtained. This
1.5 parts of sulfuric acid was added to the emulsion and stirred.
At 25 ° C. for 24 hours. Then continue stirring.
PH of the 10% aqueous solution of sodium carbonate becomes 7
To stop the polymerization reaction,
Production of emulsion EC-2 containing organosiloxane
did. Comparative Example 3 Polyoxyethylene (2) lauryl ether sulfate
30 parts of chromium in 440 parts of deionized water.
Was. To this, a cyclic siloxane oligomer having a viscosity of 85 cSt
Α, ω-dihydroxypoly (dimer) containing 1.3%
Siloxane), and premix by stirring.
After combining, pressurized homogenizer (pressure 500 kgf / c
m^Two) Twice to obtain α, ω-dihydroxy
Obtain emulsion containing poly (dimethylsiloxane)
Was. Add 1.5 parts of sulfuric acid to this emulsion and stir
The reaction was carried out at 25 ° C. for 24 hours. Then, stir
While continuing the stirring, a 10% aqueous solution of sodium carbonate was added to pH 7
To stop the polymerization reaction.
Emulsion EC- containing polyorganosiloxane
3 was produced. Comparative Example 4 Triethanolamine dodecylbenzenesulfonate 30
Parts were evenly dispersed in 440 parts of deionized water. this
And a cyclic siloxane oligomer having a viscosity of 85 cSt.
Α, ω-dihydroxy poly (dimethylsilo containing 3%
Xane) was added and premixed by stirring.
After that, a pressure homogenizer (pressure 500 kgf / cm^Two)
Α, ω-dihydroxypoly
An emulsion containing (dimethylsiloxane) was obtained. This
1.5 parts of sulfuric acid was added to the emulsion and stirred.
At 25 ° C. for 24 hours. Then continue stirring.
PH of the 10% aqueous solution of sodium carbonate becomes 7
To stop the polymerization reaction,
Production of emulsion EC-4 containing organosiloxane
did.

The above evaluations were performed on the emulsions obtained in Examples 1 to 6 and Comparative Examples 1 to 4. Table 1 shows the results.

[0049]

[Table 1]

Examples 7 to 9, Comparative Example 5 (Shampoo) Emulsions E-1 to E-3 obtained in Examples 1 to 3 above,
A shampoo was prepared by mixing 5 parts of each of the emulsion EC-1 obtained in Comparative Example 1 with each of the components shown in Table 2.

The resulting shampoo was evaluated for stability and feeling of use. Table 2 shows the results. (Stability) ○: Stable even at 50 ° C. for 4 weeks △: Separated at 50 ° C. for 2 weeks ×: Separated at 50 ° C. for 1 week (Feeling of use) The following criteria by 20 female panelists for the feeling during hair washing And the average score was obtained. 3: Very good 2: Good 1: Normal

[0052]

[Table 2]

Examples 10 to 12, Comparative Example 6 (Rinse) Emulsions E-1 to E-3 obtained in Examples 1 to 3 above,
Then, 10 parts of each of the emulsion EC-1 obtained in Comparative Example 1 and each component shown in Table 3 were mixed to prepare a rinse.

The resulting rinse was evaluated for stability and feeling of use (smoothness, combability, feel, gloss) (the evaluation criteria were the same as for shampoo). Table 3 shows the results.

[0055]

[Table 3]

Examples 13 to 15, Comparative Example 7 (Hair Set Lotion) Emulsions E-1 to E-3 obtained in Examples 1 to 3 above,
Then, 5 parts each of the emulsion EC-1 obtained in Comparative Example 1 and each component shown in Table 4 were mixed to prepare a hair setting lotion.

About the obtained hair set lotion,
Stability and usability were evaluated. The method for evaluating stability is the same as that for shampoo. The usability was evaluated as follows. Table 4 shows the results. (Feeling of use) The stickiness during use was evaluated by 20 female panelists according to the following criteria, and the average score was obtained. 3: Excellent feeling without sticky feeling 2: Slightly sticky 1: Sticky feeling

[0058]

[Table 4]

Examples 16 to 18, Comparative Example 8 (Hand lotion) Emulsions E-1 to E-3 obtained in Examples 1 to 3 above,
Then, 11 parts of each of the emulsion EC-1 obtained in Comparative Example 1 and each component shown in Table 5 were mixed to prepare a hand lotion.

The obtained hand lotion was evaluated for stability and feeling of use. The stability evaluation method is the same as that for shampoo, and the usability evaluation method is the same as for hair set lotion. Table 5 shows the results.

[0061]

[Table 5]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 83/06 C08L 83/06 F term (Reference) 4C083 AB102 AB372 AC072 AC102 AC182 AC392 AC402 AC422 AC432 AC442 AC482 AC642 AC692 AC782 AD132 AD161 AD282 AD512 CC01 CC04 CC33 CC38 CC39 EE01 EE06 FF01 4J002 CH052 CP031 CP081 CP141 DE027 EV236 EW126 FD312 FD316 HA07 4J035 BA02 CA051 CA142 CA172 EB02 EB04 LA02 LB14

Claims (5)

[Claims] (A) General formula HO [(R ¹ ) ₂ SiO] _m H (I) (wherein R ¹ may be the same or different, substituted or unsubstituted 1 Represents a monovalent hydrocarbon group, m
Represents the viscosity of the component (A) at 25 ° C. of 10 to 3,000.
cSt) is selected from (B) (B1) polyoxyethylene alkyl ether sulfuric acid, (B2) polyoxyethylene alkyl ether phosphoric acid, and (B3) alkyl sulfuric acid. At least two anionic surfactants (provided that the mixing ratio is 1/20 to
20/1, and (1-20) / (1-2)
0) / (1 to 20)), and (C) a polyorganosiloxane emulsion obtained by emulsion polymerization in the presence of water. 2. The polyorganosiloxane emulsion according to claim 1, wherein said (B) is formed in a reaction system by reacting said sulfuric acid or phosphoric acid salt with an acid. 3. The polyorganosiloxane emulsion according to claim 1, wherein the amount of the cyclic siloxane oligomer having 20 or less silicon atoms in the polydiorganosiloxane (A) is 3.5% by weight or less. 4. The polydiorganosiloxane (A) 2
The viscosity at 5 ° C is 500 cSt or more.
The polyorganosiloxane emulsion according to any one of the above. 5. A cosmetic comprising the polyorganosiloxane emulsion according to claim 1.