JP2000053769A - Polyorganosiloxane emulsion and cosmetic containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyorganosiloxane emulsion having an enlarged mol.wt. and improved stability by mixing a specific silanol group-terminated polydiorganosiloxane, an anionic surfactant, a polymerization catalyst and water and polymerizing the polydiorganosiloxane. SOLUTION: This polyorganosiloxane emulsion having a viscosity of 2,000,000-50,000,000 cSt at 25 deg.C is obtained by mixing (A) a silanol group- terminated polydiorganosiloxane of the formula: HO[(R1)2SiO]mH (R1 is a monovalent hydrocarbon; (m) is a value giving a viscosity of 10-3,000 cSt at 25 deg.C to the component A], (B) an anionic surfactant preferably in an amount of 2-10 pts.wt. (converted into an acid) per 100 pts.wt. of the component A, (C) a polymerization catalyst for the component A preferably in an amount of 0.1-5 pts.wt., and (D) water in an amount of 30-1,000 pts.wt. The temperature condition of the polymerization is preferably the freezing point of the emulsion to 20 deg.C.

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.

However, in the above prior art, the viscosity of the base polymer at 25 ° C. is at most 1,
An emulsion having a higher viscosity is desired, considering that the obtained emulsion is used for cosmetics and the like. In addition, in consideration of use in cosmetics and the like, it is also important that the obtained emulsion has high stability.

[0005] Furthermore, in a conventional similar emulsion,
As a low molecular weight siloxane used for emulsion polymerization, a cyclic siloxane oligomer such as octamethylcyclotetrasiloxane is used because it is easily available and easily emulsified and ring-opening-polymerized. However, the ring-opening polymerization of the cyclic siloxane oligomer is an equilibrium reaction, and the emulsion after emulsion polymerization usually contains 5 to 10% by weight of the cyclic siloxane oligomer in the polysiloxane. For this reason, when a very homogeneous emulsion is required, the oligomer may volatilize from the emulsion during storage or use, thereby impairing the physical stability of the emulsified system. In addition, when such an emulsion is used in a large amount as a hair cosmetic in a hairdressing salon, for example, in the treatment of hair, particularly when accompanied by a heat blow treatment, the volatilized oligomer contaminates the surrounding environment. In particular, the surrounding ventilation fan system may be soiled, and contact failures of various electric devices such as a fan heater may be caused. Further, when such an emulsion is used for skin cosmetics or the like, the low-molecular-weight cyclic siloxane oligomer contained therein may impair touch due to its volatilization characteristics. Therefore, when used in applications such as cosmetics, it is required to suppress the amount of the cyclic siloxane oligomer present in the emulsion.

As a method for preparing a high molecular weight polyorganosiloxane emulsion, besides a method using emulsion polymerization,
A method of mechanically emulsifying a high-molecular-weight polyorganosiloxane to obtain an emulsion is known, but it is difficult to obtain an emulsion having a small particle size by this method, and the obtained emulsion has insufficient stability. In many cases, there is a problem that separation easily occurs with time. Furthermore, when mechanically emulsifying, the viscosity of the high-molecular-weight polyorganosiloxane is high, so that it is necessary to dissolve it in a solvent or the like in advance, and it cannot be used for applications where the compounding of the solvent or the like is not preferable, and the resulting product is obtained. There is also a problem that the use of the emulsion is greatly restricted.

[0007]

[Summary of the Invention] An object of the present invention is to solve the above-mentioned problems involved in the prior art. Specifically, an anionic surfactant is used as an emulsifier, Then, in a system in which emulsion polymerization is carried out, the viscosity at 25 ° C. of 2,000,000 to 50,000,000 cSt is obtained by increasing the stability of the emulsion and suppressing the amount of the cyclic siloxane oligomer present in the emulsion.
Is to provide a stable emulsion which typically contains a high concentration of high molecular weight polyorganosiloxanes.
Another object of the present invention is to provide a cosmetic comprising such an emulsion.

[0008]

SUMMARY OF THE INVENTION <Summary> The present invention provides a method for emulsifying a polydiorganosiloxane having a molecular chain terminal blocked with a silanol group in water with an anionic surfactant, where the polydiorganosiloxane is subjected to a polycondensation reaction. It is based on the finding that it is possible to achieve the object.

That is, the polyorganosiloxane emulsion according to the present invention is obtained by subjecting an emulsion containing the following components (A) to (D) to polymerization of the component (A). The viscosity is 2,000,000 to 50,000 at 25 ° C.
000 cSt. (A) General formula HO [(R ¹ ) ₂ SiO] _m H (I) (wherein, R ¹ may be the same or different and each is a substituted or unsubstituted monovalent hydrocarbon group. And m
Represents the viscosity of the component (A) at 25 ° C. of 10 to 3,000.
cSt), a silanol-terminated polydiorganosiloxane, (B) an anionic surfactant, and (C) a polymerization catalyst for component (A) (provided that component (B) has a catalytic action) When an anionic surfactant is used, at least a part of the component (C) can be omitted), and (D) water. Further, in one embodiment of the polyorganosiloxane emulsion according to the present invention, the temperature condition at the time of polymerization is from the emulsion freezing point to
It is also characterized by a temperature of 20 ° C. Furthermore, the cosmetic according to the present invention is characterized by comprising the above-mentioned polyorganosiloxane emulsion.

<Effect> To produce a polyorganosiloxane emulsion by subjecting the polyorganosiloxane to a specific polymerization of a specific monomer, ie, a polydiorganosiloxane terminated with a silanol group, ie, an aqueous emulsion polymerization using an anionic surfactant. Thereby, the above-mentioned problems of the prior art, particularly, the problems of increasing the molecular weight of the polyorganosiloxane, the stability of the emulsion, and the amount of the cyclic siloxane oligomer in the emulsion are improved. The emulsion thus obtained is a fine emulsion having a small particle size. Furthermore, by incorporating the emulsion according to the present invention into a cosmetic, it becomes possible to impart to the cosmetic the properties inherent to silicone, such as the extensibility, good touch and gloss.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION <Raw Materials for Polyorganosiloxane Emulsion> The emulsion of the present invention relates to a polyorganosiloxane produced by a specific method. Starting from components (A) to (D).

<< Component (A) / Polydiorganosiloxane >> The component (A) used as a monomer which gives a polyorganosiloxane in the present invention is a polydiorganosiloxane having a molecular chain terminal blocked with a silanol group, and has a general formula (I). This polydiorganosiloxane may be hereinafter referred to as α, ω-dihydroxypolydiorganosiloxane. In addition, since this polydiorganosiloxane 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 is well spread when the surface tension was coated low elongation, 85 of water-repellent, since it is excellent also no physiological activities such as gloss, R ¹ in the molecule % Or more 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.

[0015] 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.

<< Component (B) / Anionic Surfactant >> Component (B) used in the present invention is a component necessary for emulsifying component (A) in water. Activator. 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 as the component (A) in the component (D), 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.

Examples of the anionic surfactant include alkylbenzenesulfonic acid or a salt thereof, alkylsulfuric acid or a salt thereof, unsaturated aliphatic sulfonic acid or a salt thereof, hydroxylated aliphatic sulfonic acid or a salt thereof, and polyoxyethylene monoalkyl. Sulfuric esters of ether or salts thereof are exemplified as typical examples. Specifically, examples of the acid-type anionic surfactant include the following.

(1) Alkyl (alkyl group is generally of long chain) benzenesulfonic acid, for example, hexylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, tetradecylbenzene And sulfonic acid, hexadecylbenzenesulfonic acid, and octadecylbenzenesulfonic acid, and (2) alkyl sulfate such as octyl sulfate, dodecyl sulfate, tetradecyl sulfate, hexadecyl sulfate, and octadecyl sulfate.

Other anionic surfactants that can be used in the present invention include unsaturated and / or hydroxylated aliphatic sulfonic acids, and water-soluble or neutralized salts thereof. . Representative examples of these sulfonic acids are represented by the following formulas [1] and [2]. (3) R ² CH = CH (CH ₂ ) _m SO ₃ H [1] (4) R ² CH ₂ CH (OH) (CH ₂ ) _m SO ₃ H [2] (where R ² is a hydrogen atom Or m represents a monovalent aliphatic hydrocarbon group, and m is an integer having 6 to 32 carbon atoms in the molecule). Specifically, R ² has 6 to 3 carbon atoms.
And a linear or branched alkyl group, alkenyl group and aliphatic dienyl group having 0 to 6 carbon atoms.
8 is more preferred. Specifically, such R
^{As 2} , hexyl, octyl, decyl, dodecyl,
Illustrative are alkyl groups such as tetradecyl, hexadecyl, octadecyl and melisyl, alkenyl groups such as octenyl, nonenyl, oleyl and phytyl, and aliphatic dienyl groups such as pentadecadienyl.

Accordingly, examples of the unsaturated aliphatic sulfonic acid (ie, (3)) represented by the formula [1] include dodecenesulfonic acid, tetradecenesulfonic acid, and hexadecenesulfonic acid. Examples of the hydroxylated aliphatic sulfonic acid (that is, (4)) represented by [2] include hydroxydodecanesulfonic acid, hydroxytetradecanesulfonic acid, and hydroxyhexadecanesulfonic acid.

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. In particular,
(1) Examples of the alkylbenzene sulfonate include sodium alkylbenzene sulfonates such as sodium decylbenzenesulfonate, sodium dodecylbenzenesulfonate, and sodium tetradecylbenzenesulfonate; and corresponding potassium salts, ammonium salts, and triethanolamine. And (2) alkyl sulfates such as sodium octyl sulfate, sodium dodecyl sulfate, sodium octadecyl sulfate and the like;
Corresponding potassium salts, ammonium salts, triethanolamine salts and the like are exemplified. Among them, a sodium salt and a triethanolamine salt are preferably used.

As the unsaturated aliphatic sulfonic acid salt and / or the hydroxylated aliphatic sulfonic acid salt, there are sulfonic acid salts represented by the above formulas [1] and / or [2]. Specifically, (3) unsaturated aliphatic sulfonates include sodium dodecenesulfonate, sodium tetradecenesulfonate and sodium hexadecenesulfonate, and corresponding potassium salts, ammonium salts, triethanolamine salts and the like. And (4) the hydroxyaliphatic sulfonate includes:
Examples include sodium hydroxydodecanesulfonate, sodium hydroxytetradecanesulfonate and sodium hydroxyhexadecanesulfonate, and the corresponding potassium, ammonium, triethanolamine salts and the like.

The above-mentioned component (B) may be mixed with the components (A) and (D) 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) contains
It is preferable to use at first to act as a surfactant and then to act as a polymerization catalyst. 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.

In the present invention, among the anionic surfactants, one of the acid-type surfactants may be used alone, or several of them may be used in combination. When used in the form of a salt, they may be used alone or in combination of several kinds. For example, a sodium salt and an ammonium salt may be used in combination. That is, the above-mentioned acid-type and salt-type anionic surfactants can be used together in each group and / or between each group. The amount of component (B) used can be any suitable one, considering both 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 amount of the anionic surfactant of an acid type or a salt thereof is preferably 0.5 to 100 parts by weight, and preferably 1 to 50 parts by weight in terms of acid, based on 100 parts by weight of the component (A). And more preferably 2 to 10 parts by weight. 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.

<< Component (C) / Catalyst for polymerization >> Component (C)
Is a catalyst for polymerizing the component (A). The polymerization of the component (A) belongs to the category of polymerization involving dehydration of terminal hydroxyl groups, that is, polycondensation. Such components (C) 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 acids, sulfamic acids, sulfuric acid monoesters, and others. Among organic acids, sulfonic acid and / or
Alternatively, the sulfuric acid monoester includes those having a large contribution of the organic group, and therefore those having surface activity. Accordingly, sulfonic acid and sulfuric acid monoesters having surface activity, that is, anionic surfactants are useful as catalysts for polymerization of component (C). Specific examples of suitable anionic surfactants as the component (C) can be found in the above-mentioned << Component (B) >>. Therefore, when an anionic surfactant having a catalytic action is used as the component (B), at least a part of the component (C) can be omitted.

Anionic surfactants having a hydrophilic part as a salt are generally good in emulsifying properties. In view of this point, an anionic surfactant in a salt form is used as an emulsifier (component (B) It can be said that the use as)) is advantageous in that sense. Although such salts often do not exhibit polymerization activity, the free acid that functions as a catalyst by converting such a salt at least partially into the acid form after emulsion formation and, optionally, during polymerization, is preferred. It is also possible to use That is, as described above, the polymerization catalyst of the component (C) 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. Can also be obtained. 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. Such acids include:
Examples thereof 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 the acid is used in combination as described above, the amount of the acid is not particularly limited, but is preferably 0.1 to 100 parts by weight of the component (A).
The amount is preferably from 05 to 10 parts by weight, particularly preferably from 0.1 to 5 parts by weight.

<< Component (D) / Water >> Water as the component (D) is a medium for dispersing and emulsifying the component (A). Component (D) is used in an amount of 100 parts by weight of component (A).
Usually, the amount is 30 to 1,000 parts by weight, and the amount is preferably such that the concentration of the component (A) in the emulsion becomes 10 to 70% by weight. 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 (D) used is such that the concentration of the component (A) in the emulsion is 40 to 70% by weight. Is particularly preferred. The medium in which the component (A) is dispersed may include various solvents such as an aliphatic hydrocarbon, an aromatic hydrocarbon, and a cyclic siloxane in addition to the component (D). 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.

<< Component (E) / Auxiliary Component >> The polyorganosiloxane emulsion of the present invention comprises the above component (A)
To (D), the component (A)
Is obtained by carrying out the polymerization of
As long as the emulsion contains the components (A) to (D) as essential components, the emulsion may contain various auxiliary components dissolved or dispersed as long as the gist of the present invention is not impaired. Good. In addition, such an auxiliary component is
It 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. For such auxiliary components, see the section <Modification> below.

<Polymerization><< Formation of Emulsion >> The polyorganosiloxane emulsion of the present invention can be produced as follows. That is, a polydiorganosiloxane (component (A)) whose molecular chain ends are blocked with silanol groups, an anionic surfactant (component (B)), and water (component (D)) are premixed. The mixing order is arbitrary, but, for example, the component (B) is mixed and dissolved in the component (D) in a stirring tank, and the component (A) is added thereto while stirring. Then, the mixture is passed through an emulsifier such as a homogenizer, a colloid mill, a line mixer, and a 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, and the component (B) such as alkylbenzenesulfonic acid, alkylsulfuric acid, unsaturated aliphatic sulfonic acid and / or
Produces hydroxylated aliphatic sulfonic acid and the like. They are,
As described above, it functions as a catalyst for emulsion polymerization.
u) "can also be formed as described above.

<< Polymerization >> When stirring is continued, a high molecular weight polyorganosiloxane is synthesized by a polycondensation reaction of a silanol group at a molecular chain terminal 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.
Emulsion freezing point to 30 ° C, more preferably emulsion freezing point to 20 ° C, and still more preferably emulsion freezing point to 20 ° C for 2 to 48 hours, but if necessary, 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 product 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 to terminate 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 molecular chain end, and has a viscosity at 25 ° C. of preferably 2,000,000 cSt or more, more preferably 3,000,000 to 50,000,000.
cSt, more preferably from 10,000,000 to 50,
Million cSt.

<Modification> The polyorganosiloxane emulsion obtained by such a production method can be subjected to various modifications as required. Modifications can be made to the emulsion before and / or during polymerization, but also to the resulting emulsion after polymerization. Some examples of such modifications are as follows.

In addition to the component (B) used in the present invention,
In order to improve the stability of the polyorganosiloxane emulsion of the present invention, one or more other anionic and / or nonionic surfactants may be added first without impairing the object of the present invention. Can be blended at any other stage after the emulsification of the above or after the polycondensation reaction of the component (A). As described above, examples of other anionic surfactants used in combination with the component (B) include polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl ether phosphate, and polyoxyethylene alkyl ether carboxylate. You.

The nonionic surfactants include H
LB of 6-19, preferably 8-18, or 2
At least one additive HLB of 6 to 19, preferably 8 to 18
Are preferred. Such materials include polyoxyalkylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene phytosterol ether, polyethylene glycol fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid Examples thereof include esters, polyoxyethylene sorbite fatty acid esters, polyoxyethylene fatty acid amines, glycerin fatty acid esters, polyglycerin fatty acid esters, sorbitan fatty acid esters, and sucrose fatty acid esters. These are examples,
Nonionic surfactants that can be used in combination in the present invention are not limited to these.

When the thus optionally added anionic and / or nonionic surfactant is blended before the emulsion polymerization, the amount of the blended surfactant is determined by the amount of the component (B) ) Is required to be within a range that does not impair the catalytic ability of the acid generated from the component (B), and specifically, is not more than 5 times the weight of the component (B) to be blended. 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.

[0038] The polyorganosiloxane emulsion obtained by emulsion polymerization is used for surface treatment of various substrates to form a strong film. 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, a water-soluble alkylene glycol, a water-soluble polyalkylene glycol, or the like 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.

<Producted polyorganosiloxane emulsion> The polyorganosiloxane emulsion of the present invention comprises:
The state of the emulsion and its stability are extremely excellent as compared with an emulsion obtained by mechanically emulsifying such a polyorganosiloxane while containing a high molecular weight polyorganosiloxane as a main component. further,
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. is there. 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.

<Cosmetic> 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, tic, bottled oil, hair cream, hair tonic, hair liquid, hair spray, pomade, shampoo, hair rinse, hair conditioner, hair lotion, Examples include hair cosmetics such as anti-branch agents, and skin cosmetics such as hand creams, hand lotions, skin creams, foundations, eye shadows, eye liners, mascaras, facial cleansers, and antiperspirants. Examples of the form of the cosmetic include solid, gel, liquid, and paste forms.

<< Cosmetic preparation components >> Other components used to prepare the cosmetics by blending the polyorganosiloxane emulsion of the present invention (cosmetic preparation components)
Examples thereof include the following. That is, the component includes (1) hydrocarbons such as liquid paraffin, petrolatum, solid paraffin, squalane and olefin oligomer, and (2) esters such as
Isopropyl palmitate, stearyl stearate,
(3) higher alcohols such as octyldodecyl myristate, octyldodecyl oleate, lanolin acetate, and triglyceride 2-ethylhexanoate;
Lauryl alcohol, cetyl alcohol, stearyl alcohol, lanolin alcohol, and beeswax, etc.
(4) higher fatty acids such as palmitic acid and stearic acid and amines such as diethanolamine for neutralizing the same; (5) humectants such as ethylene glycol, propylene glycol, 1,3-butylene glycol, glycerin, (6) inorganic powders such as titanium oxide, carbon black, iron oxide, sericite, talc, kaolin, and mica; (7) organic polymer powders such as nylon, polyethylene, and poly. (8) solvents such as (meth) acrylates, for example water and ethanol,
(9) Anionic surfactants and nonionic surfactants exemplified as surfactants optionally incorporated in the above-mentioned emulsion polymerization of polyorganosiloxane, and amphoteric surfactants such as betaine; (10) Preservatives Examples include, but are not limited to, agents, (11) coloring agents, and (12) fragrances.

<< Preparation of Cosmetics >> To mix these components, the polyorganosiloxane emulsion of the present invention and other components are simply mixed uniformly, or components other than the emulsion are previously mixed with a homogenizer, a colloid mill. And various methods such as emulsifying with an emulsifier such as a line mixer, or mixing uniformly with a stirrer, and adding and dispersing the emulsion thereto. 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.

[0043]

The polyorganosiloxane emulsion according to the invention solves the problems of the prior art, in particular the problems of increasing the molecular weight of the polyorganosiloxane, the stability of the emulsion and the amount of cyclic siloxane oligomer in the emulsion. And the fact that the cosmetic according to the present invention can exhibit excellent properties such as silicone-extensive, tactile sensation, and luster, as described above in the section of [Summary of the Invention].

[0044]

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 viscosity of the high molecular weight polyorganosiloxane contained in the emulsion obtained by the emulsion polymerization, the storage stability test, and the content of the cyclic siloxane oligomer were measured or carried out as follows.

(1) Viscosity of polyorganosiloxane 20 parts of isopropyl alcohol was added to 100 parts of the emulsion.
Add 0 parts, stir well, let stand for 24 hours to separate into two layers, then transfer only the oil layer to a Petri dish,
The resulting mixture was placed in an oven at 45 ° C. for 45 minutes to completely evaporate the remaining isopropyl alcohol and water to obtain a polyorganosiloxane. This was cooled to 25 ° C., and the viscosity was measured using a rotational viscometer.

(2) Storage stability The storage stability of the emulsion was evaluated as described above from the change in appearance when the emulsion was stored in a dryer at 50 ° C. for 30 days. : No change in appearance. Δ: Oil slightly floats. ×: Oil layer is visible

(3) Content of cyclic siloxane oligomer 5 parts by volume of the emulsion were collected, and methanol
Volume part, 100 parts by volume of n-hexane and 50 parts by volume of water were added, and the mixture was shaken vigorously and allowed to stand for 24 hours to be separated into two layers. Then, the n-hexane layer was collected with a microphone syringe and subjected to gas chromatography. The amount of cyclic siloxane oligomer in the sample was determined. From this value and the amount of the polyorganosiloxane obtained by volatilizing n-hexane from the n-hexane layer separately, the content of the cyclic siloxane oligomer in the polyorganosiloxane was calculated. Was calculated.

Example 1 3 parts of sodium dodecylbenzenesulfonate and 5 parts of sodium dodecyl sulfate (the above-mentioned components (B) (salt type)) were uniformly mixed in 100 parts of deionized water (component (D)). Dispersed. To this dispersion, a cyclic siloxane oligomer having a viscosity of 83 cSt and a total of 0.70
% Of α, ω-dihydroxy (dimethylsiloxane) (component (A)), and premixed by stirring.
/ Cm ² to give an emulsion containing α, ω-dihydroxy (dimethylsiloxane). To this emulsion was added 0.2 parts of sulfuric acid (component (C), which can be said to convert component (B) into a catalyst), and the mixture was kept at 1 ° C. for 24 hours with stirring. Then
The polymerization reaction was stopped by dropping a 10% aqueous sodium carbonate solution until the pH reached 7 while continuing stirring, thereby producing an emulsion E-1 containing high-molecular-weight polydimethylsiloxane.

Example 2 Emulsion containing α, ω-dihydroxy (dimethylsiloxane) using the same surfactant and α, ω-dihydroxy (dimethylsiloxane) as in Example 1 and under the same blending ratio and conditions. I got 0.2 part of hydrochloric acid was added to this emulsion, and the mixture was kept at 4 ° C. for 24 hours with stirring. Then, the polymerization reaction was stopped by dropping a 10% aqueous sodium carbonate solution until the pH reached 7 while continuing stirring, and the emulsion E- containing high molecular weight polydimethylsiloxane was added.
2 was produced.

Example 3 8 parts of an anionic surfactant, which is a mixture of 75% sodium tetradecenesulfonate and 25% sodium hydroxytetradecanesulfonate, were uniformly dispersed in 100 parts of deionized water. To this dispersion, 100 parts of α, ω-dihydroxy (dimethylsiloxane) having a viscosity of 155 cSt and containing a total of 1.01% of a cyclic siloxane oligomer were added and premixed by stirring, and then a pressure of 500 kgf / c was applied to a pressure homogenizer.
By passing twice with m ² , an emulsion containing α, ω-dihydroxy (dimethylsiloxane) was obtained. To this emulsion, 0.5 part of sulfuric acid is added, and while stirring, 1 part is added.
C. for 48 hours. Then, while stirring, 1
The polymerization reaction was stopped by dropping a 0% aqueous solution of sodium carbonate until the pH reached 7, thereby producing an emulsion containing high-molecular-weight polydimethylsiloxane. To this, 3 parts of polyoxyethylene (7) secondary dodecyl ether was further added and mixed to obtain Emulsion E-3.

Example 4 3 parts of triethanolamine dodecylbenzenesulfonate and 2 parts of triethanolamine dodecyl sulfate were uniformly dispersed in 100 parts of deionized water. To this dispersion was added 100 parts of α, ω-dihydroxy (dimethylsiloxane) having a viscosity of 15 cSt and a total of 2.73% of cyclic siloxane oligomer, and premixed by stirring.
By passing twice at 00 kgf / cm ² , an emulsion containing α, ω-dihydroxy (dimethylsiloxane) was obtained. To this emulsion was added 0.5 part of phosphoric acid, and the mixture was kept at 3 ° C. for 6 hours with stirring. Then, the polymerization reaction was stopped by dropping triethanolamine until the pH became 7 while continuing stirring, and the emulsion E- containing high molecular weight polydimethylsiloxane was added.
4 was produced.

Example 5 5 parts of sodium dodecylbenzenesulfonate and 5 parts of sodium octadecyl sulfate were uniformly dispersed in 100 parts of deionized water. To this dispersion, 100 parts of α, ω-dihydroxy (dimethylsiloxane) having a viscosity of 700 cSt and a total of 1.80% of a cyclic siloxane oligomer was added, and preliminarily mixed by stirring. Then, a pressure of 1000 kgf / kg was applied to a pressure homogenizer.
An emulsion containing α, ω-dihydroxy (dimethylsiloxane) was obtained by passing twice through cm ² . 0.1 part of sulfuric acid was added to this emulsion, and the mixture was kept at 5 ° C. for 24 hours with stirring. Subsequently, the polymerization reaction was stopped by dropping a 10% aqueous solution of sodium carbonate until the pH reached 7 while continuing stirring, thereby producing E-5 containing high-molecular-weight polydimethylsiloxane.

Comparative Example 1 This is an example in which a cyclic siloxane (octamethylcyclotetrasiloxane) is used in place of the linear silanol-terminated polydiorganosiloxane of the component (A). That is, this is an example in which the component (A) does not fall within the scope of the present invention. 3 parts of sodium dodecylbenzenesulfonate and 5 parts of sodium dodecyl sulfate were uniformly dispersed in 100 parts of deionized water. After 100 parts of octamethylcyclotetrasiloxane was added to the dispersion and premixed by stirring, the mixture was passed through a pressure homogenizer once at a pressure of 1000 kgf / cm ² to obtain an emulsion containing octamethylcyclotetrasiloxane. . 0.2 parts of sulfuric acid was added to this emulsion, and the mixture was kept at 70 ° C. for 3 hours while stirring, and further kept at 1 ° C. for 24 hours. Then, the polymerization reaction was stopped by dropping a 10% aqueous sodium carbonate solution until the pH reached 7 while continuing stirring.
Emulsion E-C1 containing high molecular weight polysiloxane
Was manufactured.

[Comparative Example 2] This is an example in which the polymerization was carried out at a higher temperature than in Example 1. The same surfactant and α, ω-dihydroxy (dimethylsiloxane) as in Example 1 were used, and α,
An emulsion containing ω-dihydroxy (dimethylsiloxane) was obtained. 0.2 part of sulfuric acid was added to this emulsion, and the mixture was kept at 25 ° C. for 6 hours with stirring. Then, 10% aqueous sodium carbonate solution was added while stirring continuously.
The polymerization reaction was stopped by dropping until H became 7 to produce an emulsion E-C2 containing high-molecular-weight polydimethylsiloxane.

Comparative Example 3 This is an example in which the component (B) does not fall within the scope of the present invention. 10 parts of cetyltrimethylammonium chloride and 5 parts of polyoxyethene (12) lauryl ether were uniformly dispersed in 100 parts of deionized water. This dispersion had a viscosity of 83 cSt
Α, ω-dihydroxy (dimethylsiloxane) 100 containing a total of 0.70% of cyclic siloxane oligomers
Was added, and the mixture was premixed by stirring, and then passed once through a pressure homogenizer at a pressure of 1000 kgf / cm ² to obtain an emulsion containing α, ω-dihydroxy (dimethylsiloxane). Add 20% to this emulsion
One part of potassium hydroxide was added, and the mixture was kept at 85 ° C for 5 hours while stirring, and further kept at 1 ° C for 24 hours. Next, acetic acid was added dropwise until the pH reached 7 while stirring was continued to stop the polymerization reaction, and an emulsion E-C3 containing polydimethylsiloxane was produced.

[Evaluation Examples] The average particle diameters of the oil phases of the polydimethylsiloxane emulsions E-1 to E-5 and E-C1 to E-C3 obtained in Examples and Comparative Examples were measured. The viscosity of the polydimethylsiloxane contained in these emulsions was measured. Further, the storage stability of each emulsion and the content of the cyclic siloxane oligomer were evaluated. Table 1 shows the results.

Table 1 Emulsion Polydimethyl Stability Cyclic siloxanes No Average particle size Siloxane (50 ° C * 30 days) Oligomer (nm) Viscosity (25 ° C, cSt) Content (%) Example 1 E-1 265 10,800,000 ○ 0.76 Example 2 E-2 265 6,650,000 ○ 0.91 Example 3 E-3 230 19,800,000 ○ 1.14 Example 4 E-4 180 4,860,000 ○ 3.48 Example 5 E-5 450 5,490,000 ○ 2.46 Comparative Example 1 E-C1 205 1,320,000 ○ 9.12 Comparative Example 2 E-C2 265 350,000 ○ 1.85 Comparative Example 3 E-C3 210 850 ○ 1.02

From the results shown in Table 1 above, the polyorganosiloxane emulsion according to the present invention is excellent in stability, can control the viscosity of the polyorganosiloxane as the base polymer arbitrarily, and further has a cyclic siloxane oligomer. It was found that the content could be suppressed.

Example 6 (Hand lotion) A hand lotion was prepared using each of the polydimethylsiloxane emulsions E-1 to E-5. That is, 11.0 parts of the emulsion, cetyl alcohol 2.
0 parts, sorbitan monomyristate 1.2 parts, polyoxyethylene (25) monostearate 1.3 parts, lanolin acetate 2.0 parts, aluminum magnesium silicate 1.
5 parts, 0.5 part of perfume and 80.5 parts of deionized water were mixed to prepare a hand lotion. The obtained hand lotion is impregnated into a cotton cloth of 3 cm x 3 cm, fixed by tape to the inside of the base of the arm by 30 women, and a patch test that is changed every day for 3 days is conducted to check for itching and the like. Was. As a result, no abnormality such as itching was observed in any of the hand lotions using the polydimethylsiloxane emulsion.

[Example 7] (Hair setting lotion) Using polydimethylsiloxane emulsion E-3,
A hair set lotion was prepared. That is, 5.0 parts of the emulsion, 0.2 parts of hydroxyethyl cellulose
Parts, 10.0 parts of ethyl alcohol, 0.2 parts of fragrance and 84.6 parts of deionized water were mixed to prepare a hair setting lotion. The obtained lotion was subjected to the same patch test as in Example 6 except that the test period was set to 7 days, and no abnormality was found.

Example 8 (Rinse in shampoo) Polydimethylsiloxane emulsions E-1 to E-5,
A rinse-in shampoo was prepared using E-C2.
That is, the emulsion was added to the rinse-in shampoo formulation as shown in Table 2 below so that the silicone content was 3%.

Table 2 (Rinse-in shampoo) 2-Alkyl-N-carboxymethyl-N-human peroxyethyl imitasorinium heptane 35.0 (%) Lauryl dimethylaminoacetic acid betaine 15.0 Lauric acid diethanolamide (1: 2 type) 4.5 O- [2-humanperoxy-3- (trimethylammonio) fluoropropyl] humanperoxyethylcellulose 4.3 propylene glycol 3.0 phenoxyethanol 1.0 edetate 0.1 benzoate 0.1 E-1 E-5, E-C2 (in terms of silicone) 3.0 Citric acid Purified water for pH adjustment

The obtained rinse-in shampoo was tested by 30 women for one week. As a result, when the emulsion was not added, 100% of the subjects felt pastsuki, and when E-C2 was added, 16% of the subjects felt sticky. On the other hand, in the case of E-1 to E-5 addition, except for 3% of the subjects, neither pastsuki nor stickiness was felt,
A good feel was obtained. The artificial hair was treated with the obtained rinse-in shampoo, and the average friction coefficient (MI) was measured with a friction tester KES-SE-STP (manufactured by Kato Tech Co., Ltd.).
U) and the variation of the average coefficient of friction (MMD) was measured. The results are shown in Table 3.

Table 3 MID MMD untreated 1.52 0.76 Rinse-in shampoo with E-4 added 0.72 0.32 Rinse-in shampoo with E-C2 added 1.11 0.37

From the results shown in Table 3 above, the rinse-in shampoo using the emulsion according to the present invention showed a small average friction coefficient (MIU) and a small variation in average friction coefficient (MMD) with respect to artificial hair. As a result, it was found that the slip property was improved.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) B01J 13/00 B01J 13/00 A F-term (Reference) 4C083 AB051 AB372 AC072 AC102 AC122 AC152 AC302 AC402 AC442 AC472 AC532 AC642 AC712 AC792 AD132 AD152 AD161 AD162 AD172 AD282 AD512 BB05 BB60 CC01 CC05 CC32 CC38 CC39 CC50 DD31 EE01 EE09 FF01 4G065 AA01 AA02 AA09 AB01Y AB02Y AB03X AB03Y AB05Y AB06X AB07Y AB09Y AB10Y AB18Y AB12Y AB12Y AB12Y AB12Y CA02 CA17 CA19 DA02 EA04 EA05 EA10 4J035 BA02 CA051 LA08 LB14

Claims (3)

[Claims] 1. An emulsion comprising the following components (A) to (D), which is obtained by polymerizing the component (A). The resulting polyorganosiloxane has a viscosity of 2,000, 000 to 50,000,000 cS
t. A polyorganosiloxane emulsion, wherein (A) General formula HO [(R ¹ ) ₂ SiO] _m H (I) (wherein, R ¹ may be the same or different and each is a substituted or unsubstituted monovalent hydrocarbon group. And m
Represents the viscosity of the component (A) at 25 ° C. of 10 to 3,000.
(a value to be cSt), a silanol group-terminated polydiorganosiloxane, (B) an anionic surfactant, (C) a polymerization catalyst for component (A) (provided that component (B) has a catalytic action) When an anionic surfactant is used, at least a part of the component (C) can be omitted), and (D) water. 2. The polyorganosiloxane emulsion according to claim 1, wherein the temperature condition for the polymerization is from the freezing point of the emulsion to 20 ° C. 3. A cosmetic comprising the polyorganosiloxane emulsion according to claim 1.