JP3248709B2 - Emulsion composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an emulsified composition of a paste-like silicone composition comprising a polymerization product of an organohydrogenpolysiloxane and a vinyl-containing organopolysiloxane, and a low-viscosity organopolysiloxane. The present invention relates to an emulsified composition having excellent storage stability by using polyvinyl alcohol and an anionic emulsifier instead of the aliphatic derivative emulsifier.

[0002]

2. Description of the Related Art Conventionally, silicone oil has been used as a base for various compositions in various fields such as medical and cosmetics due to its excellent safety. Tokuhei 6-5589
The silicone composition disclosed in Japanese Patent Publication No. 7 is a paste-like or powdery composition comprising a polymerization product of an organohydrogenpolysiloxane and a vinyl-containing organopolysiloxane, and a low-viscosity silicone oil. In the form of a low-viscosity silicone oil, it is useful as a base for cosmetics or polishes, making full use of the characteristics of the low-viscosity silicone oil such as refreshing properties, extensibility, and slipperiness. (JP-A-1-
207354, 1-230511, 1-250305, 1-250306
Nos. 1-250307, 2-83308, 2-172906, 3
-79669, 3-115207, 3-127721, 4-9323,
See Japanese Patent Publication No. 7-767. On the other hand, in order to add and mix as a base to aqueous materials such as cosmetics and glazes, it is preferable that this is an O / W type emulsified composition. No proposal has been made yet.

[0003] As an emulsifying composition of silicone oil, there is generally known an emulsifying composition using fatty acids, aliphatic alcohols, aliphatic amines, glycerin and their derivatives as emulsifiers from natural fats and oils. It is also possible to use a hydrophilic polymer compound as an emulsifier. JP-A-59-142273 discloses an example of emulsifying a silicone material using polyvinyl alcohol as an emulsifier.
JP-A-61-228064, JP-A-2-248463, JP-A-5-1326
No. 22, JP-A-5-125281, JP-A-6-32984, etc., which are all emulsified general liquid silicone oil, as described above When used as a base for cosmetics or polishes, compared to liquid silicone oils, silicone oils with lower viscosity have the characteristics of refreshing, extensibility, slipperiness, etc. An O / W emulsion composition obtained by emulsifying and dispersing a paste-like silicone composition has not been proposed at all.

[0004]

The present invention relates to an O / W type emulsified composition obtained by emulsifying and dispersing a paste-like silicone composition which was not found in the prior art. It is intended to provide an emulsified composition useful as a base for cosmetics, polishes and the like. The present invention relates to an emulsified composition used for cosmetics, polishes, etc., and particularly when used for cosmetics, is excellent in safety to hair and skin, and has a refreshing feeling and extensibility peculiar to silicone oil. In addition, the present invention can provide an emulsified composition having good storage stability, which can impart lubricity and the like thereto.

[0005]

That is, the present invention provides an emulsified composition comprising the following four components (A), (B), (C) and (D). (A) organohydrogenpolysiloxane (A ₁₎ with the following organopolysiloxane (A ₂₎ and the total amount of 100 parts by weight, low-viscosity silicone oils of the following the following (A ₃₎ 1
In the presence of 0 to 1,000 parts by weight, the mixture is stirred for addition polymerization,
100 parts by weight of the obtained polymerization product and (A ₃ ) 10 to 1,000
The mixture of parts by weight, pasty silicone composition obtained by processing under shear 30
60% by weight, [where (A ₁ ) is HSiO _3/2 units and R ¹ SiO _3/2
Unit, R ¹ HSiO _2/2 unit, R ¹ ₂ SiO _2/2 unit, R ¹ ₂ HSiO _1/2 unit, R ¹ ₃ SiO _1/2 unit (where R ¹ is ^{one other} than an aliphatic unsaturated group) An organohydrogenpolysiloxane which is composed of structural units selected from the group consisting of: and which contains, on average, at least 1.5 hydrogen atoms bonded to silicon atoms in the molecule. (A ₂ ) is (CH ₂ = CH) SiO _3/2 units, R ² SiO _3/2 units, R ² (CH ₂ = CH) SiO _2/2 units, R ² ₂ SiO _2/2
Units, R ² ₃ SiO _{1/2 ^{units, R 2 2 (CH 2 =}} CH) SiO 1/2 units (wherein R ² represents a monovalent hydrocarbon group, excluding aliphatic unsaturated group)
An organopolysiloxane comprising a structural unit selected from the group consisting of and having an average of 1.5 or more vinyl groups bonded to silicon atoms in the molecule. However (A ₁₎
At least one of (A ₂ ) and (A ₂ ) has a silicon-bonded hydrogen atom or vinyl group content of less than 20 mol% with respect to the total amount of organic groups and hydrogen atoms bonded to silicon atoms. (A ₃ ) is a low-viscosity silicone oil having a viscosity at 25 ° C. of 50 centistokes or less. (B) 0.3 to 10% by weight of polyvinyl alcohol , (C) 0.3 to 10% by weight of an anionic emulsifier , and (D) the balance of water.

R ¹ in the organohydrogenpolysiloxane (A ₁ ) constituting the emulsion composition of the present invention is a monovalent hydrocarbon group excluding an aliphatic unsaturated group.
Alkyl groups such as methyl, ethyl, propyl and butyl; aryl groups such as phenyl and tolyl; monovalent hydrocarbon groups such as cycloalkyl groups such as cyclohexyl, and one or more of these monovalent hydrocarbon groups Examples thereof include a substituted hydrocarbon group in which a hydrogen atom is substituted by a halogen atom such as chlorine, bromine, and fluorine, a cyano group, and the like, such as a γ-trifluoropropyl group and a chloromethyl group. The organohydrogenpolysiloxane (A ₁ ) may be linear, branched or cyclic, but is preferably linear in order to smoothly carry out addition polymerization. The organohydrogenpolysiloxane contains, on average, 1.5 or more, preferably 2 to 5, hydrogen atoms bonded to silicon atoms (Si-H bonds) in one molecule.

The proportion of hydrogen atoms bonded to silicon atoms in the molecule is usually 0.5 to 50 mol%, preferably 1 to 50 mol%, based on the total amount of hydrogen atoms bonded to silicon atoms and organic groups.
Desirably, it is 20 mol%. The (A ₁₎ as described above as the organic group contained in component (which was expressed as R ^1), is a variously, preferably a methyl group, in particular more than 50 mol% of R ¹ Is preferably a methyl group. A typical example of the organohydrogenpolysiloxane of the above (A ₁ ) is a compound represented by the formula [(CH ₃ ) ₃ SiO _1/2 ] _a [(CH ₃ )
₂ HSiO _1/2 ] _b [(CH ₃ ) ₂ SiO _2/2 ] _c [(CH ₃ ) HSiO _2/2 ] _d (where a and b are integers of 0 to 2, provided that a + b = 2 and c is 0 to
D is an integer of 0 to 50; )).

Further, R ² in the vinyl group-containing organopolysiloxane (A ₂ ) used in the present invention is selected from the same as the above-mentioned R ^1, and an average of 1.5 vinyl groups bonded to a silicon atom in the molecule. As described above, preferably 2 to 5 are contained. The molecular structure of the organopolysiloxane (A ₂ ) may be linear, branched or cyclic, but is preferably linear in order to promote the addition polymerization smoothly. The content of the vinyl group in the molecule is desirably 0.5 to 50 mol%, preferably 1 to 20 mol%, based on the total amount of the organic groups bonded to the silicon atom. Preferred as an organic group other than a vinyl group are, for example, a methyl group and the like.
It is desirable that at least 50 mol% be methyl groups.

A typical example of the organopolysiloxane of (A ₂ ) is a compound represented by the formula [(CH ₂ = CH) (CH ₃ ) ₂ SiO _1/2 ] _e [(CH ₃ ) ₃ Si
O _1/2 ] _f [(CH ₃ ) ₂ SiO _2/2 ] _g [(CH ₂ = CH) CH ₃ SiO _2/2 ] _h (where e and f are each an integer of 0 to 2, provided that e + f =
2, g is an integer of 0 to 500, and h is an integer of 0 to 50. )
Methyl vinyl polysiloxane represented by
These may be a mixture and can be suitably used in the present invention.

As described above, in both the organohydrogenpolysiloxane of (A ₁ ) and the organopolysiloxane of (A ₂ ), a hydrogen atom or a vinyl group bonded to a silicon atom as a reactive group is used. The number in one molecule must be 1.5 or more on average. If any one of them is less than 1.5, it becomes difficult to form a three-dimensional structure in a polymer obtained by addition polymerization, and the intended low-viscosity silicone oil lacks a thickening effect. The content of these reactive groups is preferably 0.5 to 50 mol% in each polysiloxane. If this content exceeds 50 mol%, the crosslinking density of the three-dimensional structure formed by addition polymerization becomes too high,
The low-viscosity silicone oil of (A ₃ ) is less likely to be embedded in the three-dimensional structure, bleeds easily on the surface, and the stability is reduced. When the content is less than 0.5 mol%, the formation of the three-dimensional structure becomes insufficient, and the low-viscosity silicone oil (A ₃ ) is also difficult to be included in the three-dimensional structure. In addition, when the amount of the low viscosity silicone oil (A ₃ ) used is relatively large, or when the obtained polymerization product is used under shearing force and used together with the low viscosity silicone oil (A ₃ ) as described below. In
Since the polymerization product is easily dissolved in the low-viscosity oil (A ₃ ), the resulting silicone composition (A) cannot obtain a sufficient viscosity increase.

In the present invention, at least one of the organohydrogenpolysiloxane (A ₁ ) and the vinyl group-containing organopolysiloxane (A ₂ ) has a reactive group (a hydrogen atom bonded to a silicon atom and a vinyl group). ) The content is selected to be less than 20 mol%, based on the total amount of organic groups and hydrogen atoms bonded to silicon atoms. Thereby, the degree of crosslinking of the polymer obtained by the addition polymerization is in a suitable state, and a low-viscosity (A ₃ ) silicone oil is less likely to bleed on the surface. Further, in order to obtain a paste-like silicone composition, the swelling with the (A ₃ ) low-viscosity silicone oil which is treated together under shearing force is good, and the separation and discharge of the low-viscosity silicone oil are particularly unlikely to occur. An extremely stable polymerization product is obtained.

Next, as the low-viscosity silicone oil (A ₃ ) used in the present invention, those having a viscosity at 25 ° C. of 50 cSt or less, particularly 10 cSt or less, are used. This viscosity is 5
If it exceeds 0 cSt, the polymerization product becomes poor in viscosity increase, and the finally obtained paste-like silicone composition becomes low in stability. Also, a sticky feeling appears,
Refreshing feeling is reduced. Examples of the low-viscosity silicone oil (A ₃ ) include linear or branched methyl polysiloxane, methyl phenyl polysiloxane, ethyl polysiloxane, ethyl methyl polysiloxane, ethyl phenyl polysiloxane, cyclic Octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and the like can be mentioned, and one or more of these can be appropriately selected and used as needed.

The preparation of the composition (A) according to the present invention comprises:
Although the organopolysiloxane (A ₃₎ in the presence of a low viscosity silicone oil and organohydrogenpolysiloxane of (A ₁₎ (A ₂₎ is carried out by addition polymerization under stirring, at this time (A ₃ ) The proportion of the low-viscosity silicone oil is in the range of 10 to 1,000 parts by weight, preferably 100 to 100 parts by weight of the total amount of the organohydrogenpolysiloxane (A ₁ ) and the organopolysiloxane (A ₂ ). 20-5
It is in the range of 00 parts by weight. When the proportion of the low-viscosity silicone oil is less than 10 parts by weight, the effect of coexistence is reduced, and the viscosity of the obtained composition is low. Furthermore, the transparency of a composition obtained by treating the obtained polymerization product with a low-viscosity silicone oil of (A ₃ ) under shearing force tends to be lost. When the proportion of the low viscosity silicone oil (A ₃ ) exceeds 1,000 parts by weight, the reaction rate between the organo hydrogen polysiloxane (A ₁ ) and the organo polysiloxane (A ₂ ) decreases, and A polymerization product having a high viscosity cannot be obtained.

The ratio of the organohydrogenpolysiloxane (A ₁ ) and the organopolysiloxane (A ₂ ) to be subjected to the above addition polymerization is such that the hydrogen atom bonded to the silicon atom contained in (A ₁ ) / ( The molar ratio of the vinyl group bonded to the silicon atom in A ₂ ) is preferably in the range of 1/3 to 3/1, particularly preferably in the range of 1/2 to 2/1. Even if this ratio is too large or too small, the hydrogen atom bonded to the unreacted component (silicon atom) or the vinyl group coexists in the reaction product, so that the paste-form silicone composition finally obtained is Stability is impaired.

In the addition polymerization, an organic solvent such as aliphatic alcohols such as methanol, ethanol, 2-propanol and butanol; aromatic hydrocarbons such as benzene, toluene and xylene; n-pentane, n-hexane and cyclohexane. Aliphatic or alicyclic hydrocarbons; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, trichloroethane, trichloroethylene, fluorinated or chlorinated hydrocarbons, and platinum compounds soluble therein (for example, chloroplatinic acid, alcohol) Modified chloroplatinic acid,
Chloroplatinic acid-vinylsiloxane complex, etc.) or rhodium compound, at room temperature or under heating (about 50-150 ° C)
The reaction may be carried out.

As the catalyst, particularly preferred are chloroplatinic acid and US Pat. Nos. 3,159,601, 3,159,662 and 3,159,662.
Platinum compounds used in the hydrosilylation reaction described in each specification such as 3,775,452, such as (Pt (PPh ₃ ) ₃ ), and the like, for example, a complex compound of a vinyl siloxane and a platinum compound Further, those obtained by denaturing this with alcohol are preferred. Among them, chloroplatinic acid or a complex compound of vinylsiloxane and chloroplatinic acid described in JP-B-33-9969 is more preferable.

The specific operation of the polymerization is, for example, using a reactor such as a planetary mixer equipped with a suitable stirring device, and using the required amounts of each of the organopolysiloxanes (A ₁ ) and (A ₂ ) and (A ₂ ). ₃ ) After compounding, add a catalyst and add about 50
The stirring may be performed at a temperature of about 150 ° C. As a result, a polymerization product having the property of being insoluble in the low-viscosity silicone oil of (A ₃ ) but swelling satisfactorily therein contains the (A ₃ ) low-viscosity organopolysiloxane coexisting therein. It is obtained as a polymerization product in a state of being decomposed. With the progress of the polymerization reaction, the reaction mixture gradually changes from a liquid state to a soft mass, and then becomes a coarse powder by collapse. Next, the polymerization product thus produced can be used as it is in the state of being mixed with the component (A ₃ ), but it may be used after further treating it under a shearing force. By this treatment, the polymerization product in the form of a coarse powder is further pulverized, and the polymerization product is obtained in the form of a fine powder. This fine powder is a generally white powder having a uniform composition, no bleeding of the component (A ₃ ) on the surface, and a smooth feel and moderate flexibility.

Further, in order to obtain the desired paste-like silicone composition, the bulk or powdery polymerization product obtained above is mixed with 10 to 1,000 parts by weight per 100 parts by weight of the polymerization product.
Parts by weight, preferably together with a low viscosity silicone oil of from 20 to 500 parts by weight (A _3), performs processing under shear. By this treatment, the objects to be treated are kneaded to obtain a uniform target composition. At this time, if the amount of the low-viscosity silicone oil (A ₃ ) to be treated together is less than 10 parts by weight with respect to 100 parts by weight of the polymerization product, a uniform paste cannot be obtained.
If the amount is more than 00 parts by weight, the obtained composition cannot acquire a sufficient viscosity, and does not become a good paste. Treating under shearing force is also indispensable for obtaining a paste-like composition having a relatively high viscosity, uniform, and smooth appearance. If this shearing force is not applied or is insufficient, the resulting product is not homogeneous because the polymerization product is insufficiently dissolved in the low-viscosity silicone oil and both components are present without being mixed. , Itself has low viscosity and cannot obtain sufficient thickening. In addition, a polymer product with insufficient swelling remains in the composition, so that the composition has a rough feel and a smooth appearance.

The treatment performed under the above-mentioned shearing force includes, for example,
It can be performed by a three-roll mill, a two-roll mill, a sand grinder, a colloid mill, a Gaulin homogenizer, or the like, and these may be selected according to the properties of the material to be treated. Among them, a method using a three-roll mill is preferable. This paste-like silicone composition of component (A)
If the viscosity at 25 ° C. is less than 1,000 cp, the effect of imparting a moist feeling, slipperiness and luster is not sufficient, and if it exceeds 1 million cp, emulsification and dispersion become difficult.
A range of 1,000 to 1,000,000 cp is suitable, but a range of 10,000 to 100,000 cp is more preferable.

If the amount of the component (A) of the present invention is less than 10% by weight, it does not show a sufficient effect as a cosmetic or a polishing agent. If it exceeds 80% by weight, the viscosity becomes too high, and Since it becomes difficult to emulsify and disperse with alcohol, 10 to 80% by weight is suitable, but more preferably 30 to 80% by weight.
It is in the range of ~ 60% by weight. As the polyvinyl alcohol as the component (B) of the present invention, those having various degrees of saponification are mentioned.
A partially saponified material having an average degree of saponification of about 88% containing
Intermediate saponified products having an average saponification degree of about 96 to 97%, and completely saponified products having an average saponification degree of about 99% or more, among these, partially saponified products are preferable.

The polyvinyl alcohol which can be used in the present invention is commercially available in various molecular weights, but is most preferably represented by the viscosity of a 4% by weight aqueous solution of polyvinyl alcohol. That is, they are classified into low viscosity (3 to 15 cp), medium viscosity (16 to 30 cp) and high viscosity (40 cp or more). Among them, those having low viscosity and medium viscosity are preferable. The blending amount of this polyvinyl alcohol is 0.1 to 30% by weight with respect to the whole system, but if it is less than 0.1% by weight, it is difficult to emulsify and disperse the component (A). And the workability is impaired, the content is set to 0.1 to 30% by weight, but a more preferable range is 0.3 to 10% by weight.

The anionic emulsifier (C) used in the present invention is for improving the storage stability of the emulsified composition of the present invention. Preferred examples of the component (C) include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecyl sulfate, ammonium dodecyl sulfate, sodium dodecylbenzenesulfonate, sodium dialkylsulfosuccinate, potassium alkyl phosphate, and sodium polyoxyethylene lauryl ether sulfate. And sodium polyoxyethylene alkylphenyl ether sulfate and sodium polyoxyethylene dodecyl ether sulfate. Preferably, it is an alkyl sulfate. The blending amount of the anionic emulsifier of the component (C) is preferably in the range of 0.1 to 30% by weight.
If the amount is less than 30% by weight or less than 30% by weight, the storage stability of the emulsified composition is reduced. More preferably 0.3 to 10
% By weight.

The emulsified composition of the present invention is obtained by mixing the paste-like silicone composition (A), the polyvinyl alcohol (B) and the anionic emulsifier (C), and adding thereto the water (D). Is added, and phase inversion and dilution are performed to obtain an O / W emulsion composition. At this time, it is optional to add a nonionic emulsifier for the purpose of further improving the storage stability of the emulsified composition.

Examples of the nonionic emulsifier include polyoxyethylene higher alcohol ether, polyoxyethylene alkylphenyl ether, sorbitan monoalkylate, sorbitan trialkylate, polyoxyethylene sorbitan monoalkylate, polyoxyethylene sorbitan trialkylate, polyoxyethylene sorbitan Examples thereof include ethylene sorbitan tetraalkylate and glycerol monoalkylate. These may be used alone or in combination of two or more. In addition to these general nonionic emulsifiers, a fluorine-based emulsifier or a silicone-based emulsifier may be used. Nonionic emulsifiers can also be used. Further, it is optional to add a preservative, an antistatic agent, and the like to the emulsion composition of the present invention without significantly departing from the scope of the present invention.

In the emulsifying operation of the present invention, it is necessary to carry out high shear stirring, and as an emulsifying apparatus, a homomixer, an azihomomixer, a combimix emulsifier and the like can be used. The emulsified composition of the present invention produced as described above is used as it is or after appropriately diluted with water, and then added to and mixed with aqueous cosmetics, polishes and the like. In particular, when these are used as cosmetic bases, they are applied to hair and skin and wiped off to exhibit the properties of low-viscosity silicone oil, such as refreshing feeling, extensibility, slipperiness and the like.

[0026]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The embodiments of the present invention will be described below with reference to examples, but the present invention is not limited thereto. In the following, the viscosity is a value at 25 ° C. unless otherwise specified. (Examples) First, four kinds of silicone compositions (A) were prepared, and these were blended with water of (B), (C) and (D) to prepare five kinds of emulsified compositions. 3 as an example
Various types of emulsion compositions were prepared, and the average particle size, viscosity, and storage stability of the emulsion were examined. [Preparation of Paste Silicone Composition (A-1)] A trimethylsiloxy end-blocked dimethylsiloxane methylhydrogensiloxane copolymer (average molecular weight 2,280, Si-H content) was placed in a planetary mixer having an internal volume of about 5 liters.
3.1 mol%) 600 g and dimethylvinylsiloxy end-blocked dimethylpolysiloxane (average molecular weight 930, vinyl group
7.7 mol%) and 1,300 g of trimethylsiloxy end-blocked dimethylpolysiloxane (viscosity 6 cSt) were stirred and mixed. To the obtained mixed solution, 0.5 g of a 2% by weight solution of chloroplatinic acid in isopropanol was added, and stirring was continued at 70 to 80 ° C. for 2 hours to obtain a white powder polymerization product. 100 parts by weight of this polymerization product and 150 parts by weight of trimethylsiloxy end-blocked dimethylpolysiloxane (viscosity: 6 cSt) are dispersed and mixed, and sufficiently kneaded with a three-roll mill under shearing force.
It was swollen to prepare a paste-like silicone composition (A-1). This pasty silicone composition (A-1)
Was colorless and transparent, and had a viscosity of 40,000 cp.

[Pastey silicone composition (A-2)
Preparation] As feed materials, 250 g of trimethylsiloxy-endblocked dimethylsiloxymethylhydrogensiloxane copolymer (average molecular weight 2,280, Si-H content 3.1 mol%) and dimethylvinylsiloxy-endblocked dimethylpolysiloxane (average molecular weight 5,000, vinyl group Content 1.5mol%) 61
3g and phenyltris (trimethylsiloxy) silane 1,
294 g was blended, and the operation was the same as that of the paste-form silicone composition (A-1) except that 0.5 g of a 2% solution of chloroplatinic acid in isopropanol was added to obtain a powdery polymerization product. The procedure other than the blending of 100 parts by weight of this polymerization product and 270 parts by weight of phenyltris (trimethylsiloxy) silane was the same as that of the paste-form silicone composition (A
In the same manner as in 1), a paste-like silicone composition (A-2) was obtained. The appearance of this paste-like silicone composition (A-2) was smooth and excellent in extensibility, and the viscosity was 66,000 cp.

[Paste Silicone Composition (A-3)
Preparation of dimethylhydrogensiloxy end-blocked dimethylpolysiloxane (average molecular weight 2,87
0, 320 g of trimethylsiloxy end-blocked dimethylsiloxymethylvinylsiloxane copolymer (average molecular weight 5,000, vinyl group content 1.5 mol%)
616 g and 1,405 g of octamethylcyclotetrasiloxane are mixed, and 0.5 g of a 2% solution of chloroplatinic acid in isopropanol is added.
The operations other than the addition were performed in the same manner as in the case of the paste-form silicone composition (A-1) to obtain a powdery polymerization product. Except for mixing 100 parts by weight of this polymerization product and 300 parts by weight of methyltris (trimethylsiloxy) silane, the same operation as in the case of the paste-form silicone composition (A-1) was performed, and the paste-form silicone composition ( A
-3) was obtained. This paste-form silicone composition (A-
The appearance of 3) was colorless and transparent, and the viscosity was 100,000 cp.

[Paste silicone composition (A-4)
Preparation of 30 g of trimethylsiloxy end-blocked dimethylsiloxymethylhydrogensiloxane copolymer (average molecular weight 11,200, Si-H content 18.4 mol%) as a charge material,
Dimethylvinylsiloxy end-blocked dimethylpolysiloxane (average molecular weight 14,200, vinyl group content 0.52 mol%) 1,
140 g, and 1,170 g of octamethylcyclotetrasiloxane
And add a 2% solution of chloroplatinic acid in isopropanol to 0.1%.
The operation other than the addition of 5 g was performed in the same manner as in the case of the paste-form silicone composition (A-1) to obtain a powdery polymerization product. Except for mixing 100 parts by weight of this polymerization product and 200 parts by weight of octamethyltrisiloxane, the same procedure as in the case of the paste-form silicone composition (A-1) was carried out, and the paste-form silicone composition (A- 4) was obtained.
The appearance of this paste-like silicone composition (A-4) was colorless and transparent, and the viscosity was 12,000 cp.

Example 1 500 g of a paste-form silicone composition (A-1) and 10 g of sodium lauryl sulfate were put into a 3 liter combimix emulsifier [manufactured by Tokushu Kika Kogyo Co., Ltd.]. While stirring the emulsifier with an anchor mixer at 5 rpm and a homodisper at 100 rpm, the polyvinyl alcohol (B-1) [average saponification degree: 88 mol%, viscosity of 4 wt% aqueous solution (20 ° C) 5.0 cp]
300 g of a 10% by weight aqueous solution was gradually added, and the addition was interrupted after phase inversion and thickening.
High shear stirring was performed for 30 minutes at 0 rpm. Thereafter, the rotation speed of the homodisper was reduced to 300 rpm, the remaining polyvinyl alcohol aqueous solution and 190 g of deionized water were added, and the mixture was stirred for 30 minutes and diluted to obtain a white emulsion oil-in-water emulsion composition. Was. This was excellent in storage stability, and no separation was observed even after standing at room temperature for 3 months.

Example 2 The amount of the pasty silicone composition (A-1) in Example 1 was changed to 600 g, and a 10% by weight aqueous solution of polyvinyl alcohol (B-1) was added to polyvinyl alcohol (B-2) [ The average saponification degree was 88 mol%, the viscosity of the 4 wt% aqueous solution (20 ° C) was 20 cp], the composition was changed to 100 g, the amount of sodium lauryl sulfate was changed to 3 g, and the amount of deionized water was changed to 100 g. The procedure of Example 1 was repeated, except that the amount was changed to 297 g, to obtain a white milky emulsion composition. This was excellent in storage stability, and no separation was observed even after standing at room temperature for 3 months.

(Example 3) The paste-form silicone composition (A-1) in Example 1 was changed to (A-2), the amount was changed to 300 g, polyvinyl alcohol was changed to (B-2), and 10% by weight thereof. % Aqueous solution to 30 g, sodium lauryl sulfate to triethanolamine lauryl sulfate,
A white emulsion emulsion composition was obtained in exactly the same manner as in Example 1 except that the amount was 10 g and the amount of deionized water was 660 g. This product was excellent in storage stability, and no separation was observed even after standing at room temperature for 3 months.

Example 4 The paste-form silicone composition (A-1) in Example 1 was changed to (A-3), the amount was 400 g, and a 10% by weight aqueous solution of polyvinyl alcohol (B-1) was used. The procedure of Example 1 was repeated, except that the amount was 500 g, the amount of sodium lauryl sulfate was 50 g, and the amount of deionized water was 50 g, to obtain a white emulsion emulsion composition. This one has excellent storage stability,
No separation was observed after 3 months at room temperature.

Example 5 The paste-form silicone composition (A-1) in Example 1 was changed to (A-4), the amount of sodium lauryl sulfate was changed to 100 g, and the amount of deionized water was changed to 100 g. Other operations were performed in the same manner as in Example 1 to obtain a white milky emulsion composition. This was excellent in storage stability, and no separation was observed even after standing at room temperature for 3 months.

Comparative Example 1 The procedure of Example 1 was repeated, except that sodium lauryl sulfate was not used, and the amount of deionized water was changed to 200 g. I got something. This product had poor storage stability and separated into two layers on the fifth day of standing at room temperature.

Comparative Example 2 The procedure of Example 1 was repeated except that the amount of the 10% by weight aqueous solution of polyvinyl alcohol (B-1) was changed to 5 g and the amount of deionized water was changed to 485 g.
Was carried out in exactly the same manner as in Example 1 to obtain a white emulsion emulsion composition.
This was inferior in storage stability because the amount of polyvinyl alcohol was too small, and when left at room temperature, it separated into two layers on the fifth day.

Comparative Example 3 The paste-form silicone composition (A-1) was added to the combimix emulsifier used in Example 1.
500 g, 80 g of polyoxyethylene lauryl ether (mol number of added EO = 7) and 40 g of a 25% by weight aqueous solution of sodium polyoxyethylene lauryl ether sulfate (mol number of added EO = 3) were charged, and 5 rpm with an anchor type mixer and homodisper. While stirring at 100 rpm, gradually add 380 g of deionized water, phase inversion, thickening, stop adding deionized water, and perform high shear stirring at 15 rpm for anchor mixer and 1,000 rpm for homodisper for 30 minutes. did. Thereafter, the rotation of the homodisper was set to 300 rpm, and the remaining deionized water was added for dilution to obtain a white emulsified emulsion composition. Although this emulsion had a small average particle size, it was inferior in storage stability. When left at room temperature, it separated into two layers on the third day.

The compositions of the emulsified compositions of Examples 1 to 5 and Comparative Examples 1 to 3, the measured values of the average particle size and viscosity of the emulsion, and the storage stability were examined and summarized in Table 1.

[0039]

[Table 1]

[0040]

EFFECT OF THE INVENTION The emulsion composition of the present invention is excellent in storage stability and shows no layer separation even after storage at room temperature for 3 months, so that it is useful as a base for cosmetics, polishes and the like.

Claims (1)

(57) [Claims] 1. The following (A), (B), (C) and (D)
An emulsified composition comprising the four components: (A) organohydrogenpolysiloxane (A ₁₎ with the following organopolysiloxane (A ₂₎ and the total amount of 100 parts by weight, low-viscosity silicone oils of the following the following (A ₃₎ 1
In the presence of 0 to 1,000 parts by weight, the mixture is stirred for addition polymerization,
100 parts by weight of the obtained polymerization product and (A ₃ ) 10 to 1,000
The mixture of parts by weight, pasty silicone composition obtained by processing under shear 30
60% by weight, [where (A ₁ ) is HSiO _3/2 units and R ¹ SiO _3/2
Unit, R ¹ HSiO _2/2 unit, R ¹ ₂ SiO _2/2 unit, R ¹ ₂ HSiO _1/2 unit, R ¹ ₃ SiO _1/2 unit (where R ¹ is ^{one other} than an aliphatic unsaturated group) An organohydrogenpolysiloxane which is composed of structural units selected from the group consisting of: and which contains, on average, at least 1.5 hydrogen atoms bonded to silicon atoms in the molecule. (A ₂ ) is (CH ₂ = CH) SiO _3/2 units, R ² SiO _3/2 units, R ² (CH ₂ = CH) SiO _2/2 units, R ² ₂ SiO _2/2
Unit, R ² ₃ SiO _1/2 unit, R ² ₂ (CH ₂ = CH) SiO _1/2 unit (where R ² represents a monovalent hydrocarbon group excluding an aliphatic unsaturated group)
An organopolysiloxane comprising a structural unit selected from the group consisting of and having an average of 1.5 or more vinyl groups bonded to silicon atoms in the molecule. However (A ₁₎
At least one of (A ₂ ) and (A ₂ ) has a silicon-bonded hydrogen atom or vinyl group content of less than 20 mol% with respect to the total amount of organic groups and hydrogen atoms bonded to silicon atoms. (A ₃ ) is a low-viscosity silicone oil having a viscosity at 25 ° C. of 50 centistokes or less. (B) 0.3 to 10% by weight of polyvinyl alcohol , (C) 0.3 to 10% by weight of an anionic emulsifier , and (D) the balance of water.