JPH1171522A - Polyorganosiloxane emulsion and cosmetic using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject stable emulsion that contains a macromolecular polyorganosiloxane in a high concentration by polycondensation reaction of a specific polydiorganosiloxane in the presence of a specific surfactant. SOLUTION: The objective emulsion is obtained by emulsion-polymerization of (A) 100 pts.wt. of a silanol group-terminated polydiorganosiloxane of the formula HO[(R<1> )2 SiO]m H [R<1> is (an) (un)substituted monovalent hydrocarbon; (m) is the value that adjusts the viscosity of the component A to 10-3,000 cSt at 25 deg.C] [for example, α,ω-dihydroxy-poly(dimethylsiloxane)] in the presence of (B) 1-100 pts.wt. of an unsaturated aliphatic sulfonic acid and/or a hydroxylated aliphatic sulfonic acid in the presence of (C) 30-1,000 pts.wt. of water. The resultant emulsion contains silanol groups on the terminals of the molecular chain of the high-molecular polyorganosiloxane, a viscosity of >=10,000 cSt, and preferably <=3.5 wt.% of cyclic siloxane oligomers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an emulsion containing a polyorganosiloxane obtained by emulsion polymerization, and more particularly to a polydiorganosiloxane having a relatively low molecular weight and having a molecular chain end blocked by a silanol group. And an emulsion containing a high molecular weight polyorganosiloxane obtained by emulsion polymerization of The present invention also relates to a cosmetic using the 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 polyorganopolymer having a wide viscosity range from silicone oil to silicone raw rubber. Emulsions containing siloxanes 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. (Japanese Patent Publication No. 43-1)
No. 8800).

In Japanese Patent Publication No. 54-19440, an organosiloxane is added to an aqueous solution of a salt type anionic surfactant and emulsified, and the resulting emulsion is contacted with an acetic acid type cation exchange resin. A method is disclosed in which a surfactant is converted into an acid form to polymerize the polyorganosiloxane.

Further, JP-B-41-1399 and JP-B-44-20116 disclose benzene sulfonic acid and naphthalene sulfonic acid substituted with an aliphatic hydrocarbon group, aliphatic hydrocarbon sulfonic acid and silyl alkyl sulfone. A method is disclosed in which an organosiloxane and a silanol group-containing disilcarbane are emulsion-polymerized in an aqueous medium 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.

When an emulsion containing a high-molecular-weight polyorganosiloxane is produced by such emulsion polymerization, dodecylbenzenesulfonic acid is typified by dodecylbenzene sulfonic acid because it is easily emulsified and easily available as a polymerization catalyst also serving as a surfactant. Alkylbenzene sulfonic acid is commonly used.

However, when alkylbenzenesulfonic acid is used, the alkylbenzenesulfonic acid salt remains in the emulsion even if neutralization is carried out after polymerization, 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 of a cosmetic, the alkylbenzene sulfonate is not preferred because it reduces the feeling of use of the cosmetic.

[0007] 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 used as much as possible to suppress yellow coloring and to reduce yellow coloring. A method for producing a polyorganosiloxane emulsion is disclosed which avoids a decrease in the conversion of the molecular weight siloxane and the degree of polymerization of the resulting polyorganosiloxane. However, handling is complicated because a solid hexamethylcyclotrisiloxane is used in combination as a low molecular weight siloxane as a raw material, and
There were several problems, such as the slightly poor stability of the emulsion.

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. In addition, such an emulsion, for example, a large amount used in hair treatment and the like as hair cosmetics in a beauty salon,
In particular, when a heat blow treatment is involved, the volatilized oligomer may contaminate the surrounding environment, and in particular, may contaminate the surrounding ventilation fan system, or may cause contact failure of various electric devices such as a fan heater. 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.

[0010] JP-A-63-265924 and JP-A-4-178429 disclose that a polydiorganosiloxane having a molecular chain terminal capped with a silanol group as a starting material, and a high molecular weight polyorganosiloxane is prepared by emulsion polymerization. It is disclosed to make emulsions containing the same. However, the anionic surfactants used for these are dodecylbenzenesulfonic acid and the like, and the effects on the feeling of use as cosmetics and on the environment as described above have not been solved.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems involved in the prior art. Specifically, as a surfactant, itself and / or a salt thereof is contained in an emulsion. Even if it is present, use one that does not cause a feeling of use as a cosmetic and environmental pollution,
An object of the present invention is to provide a stable emulsion containing a high-molecular-weight polyorganosiloxane at a high concentration in which the amount of the cyclic siloxane oligomer present in the emulsion is suppressed.

Another object of the present invention is to provide a cosmetic composition which is excellent in stability and feels good by using such an emulsion.

[0013]

Means for Solving the Problems As a result of repeated studies to achieve the above object, the present inventor has found that a polydiorganosiloxane having a molecular chain terminal capped with a silanol group is used and a specific surfactant system is used. The present inventors have found that the object of the present invention can be achieved by performing a polycondensation reaction using, and have 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 is a substituted or unsubstituted group which may be the same or different. Represents a monovalent hydrocarbon group, and m is (A)
(B) to give a viscosity of 10 to 3,000 cSt at 25 ° C.), (B) unsaturated aliphatic sulfonic acid and / or hydroxylated aliphatic sulfonic acid; A) a polyorganosiloxane emulsion obtained by emulsion polymerization in the presence of water; The present invention also relates to a cosmetic using such an emulsion.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The component (A), a polydiorganosiloxane whose molecular chain ends are blocked with silanol groups, 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 cS
t, preferably 15 to 1,000 cSt, particularly preferably 20 to 300 cSt. That is, in the case of the most preferred polydimethylsiloxane as described later, m is in the range of 8 to 500, but m also varies depending on the type of R ¹ bonded to the silicon atom and their mutual ratio. If the viscosity of the silanol-terminated polydiorganosiloxane is less than 10 cSt, it is difficult to stably synthesize and purify, and if it exceeds 3,000 cSt, emulsification becomes difficult.

As R ¹ bonded to a silicon atom, methyl, ethyl, propyl, butyl, hexyl, octyl,
Alkyl groups such as decyl; cycloalkyl groups such as cyclohexyl; alkenyl groups such as vinyl and allyl;
Aralkyl groups such as -phenylethyl and 2-phenylpropyl; aryl groups such as phenyl; and 3,3,3
A substituted hydrocarbon group such as -trifluoropropyl is exemplified, and a high molecular weight polyorganosiloxane obtained by emulsion polymerization has a low surface tension, a good spread,
It is preferable that 85% or more of R ^{1 in} the molecule is a methyl group, and it is particularly preferable that substantially all of R ^{1 in} the molecule is a methyl group because of its excellent water repellency and gloss and lack of physiological activity. As the component (A), α, ω-dihydroxypoly (dimethylsiloxane) and a part of the dimethylsiloxane unit were replaced with a methylethylsiloxane unit, a methylhexylsiloxane unit, a methylphenylsiloxane unit, a diphenylsiloxane unit, or the like. Copolymerized polysiloxanes are exemplified, and α, ω-dihydroxypoly (dimethylsiloxane) is particularly preferred.

Such a silanol group-terminated polydiorganosiloxane is, for example, prepared by using water as a terminal stopper in the presence of an acidic catalyst such as sulfuric acid or an alkaline catalyst such as potassium hydroxide or potassium silanolate. It is synthesized by ring-opening polymerization of a cyclic siloxane oligomer. Although unreacted cyclic siloxane oligomer is present in the product, in order to avoid the above-mentioned problem caused by the cyclic siloxane oligomer remaining after the emulsion polymerization obtained by the present invention, the cyclic siloxane oligomer in the component (A) is used. The content is preferably set to 2.5% by weight or less, more preferably 0.5% by weight or less. In order to control the cyclic siloxane oligomer of the component (A), for example, a polymer obtained by ring-opening polymerization is
This can be achieved by distilling off the cyclic siloxane oligomers present under reduced pressure.

The unsaturated aliphatic sulfonic acid and / or hydroxylated aliphatic sulfonic acid of the component (B) used in the present invention is typically represented by the formula (II) and / or the formula (III): R ² CH ＣＨCH (CH ₂ ) _m SO ₃ H (II) R ² CH ₂ CH (OH) (CH ₂ ) _m SO ₃ H (III) (wherein R ² is a hydrogen atom or a monovalent aliphatic hydrocarbon group) Wherein m is an integer having 6 to 32 carbon atoms in the molecule), and anionic surfactant for dispersing and emulsifying the silanol-terminated polyorganosiloxane as the component (A) in the component (C). (A)
It is a component that functions as a catalyst for the dehydration polycondensation reaction of the silanol group of the component. R ² is preferably a straight-chain or branched alkyl group, alkenyl group or aliphatic dienyl group having 6 to 30 carbon atoms, more preferably 6 to 18 carbon atoms. Examples of such R ² include alkyl groups such as hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and merylyl; alkenyl groups such as octynyl, nonenyl, oleyl, and phytyl; and pentadecadienyl. An aliphatic dienyl group is exemplified.

Examples of the anionic surfactant having such a catalytic function include dodecenesulfonic acid, tetradecenesulfonic acid, and hexadecenesulfonic acid as unsaturated aliphatic sulfonic acids represented by the formula (II). Examples of the hydroxylated aliphatic sulfonic acid represented by the formula (III) include hydroxydodecanesulfonic acid, hydroxytetradecanesulfonic acid, and hydroxyhexadecanesulfonic acid.

The component (B) may be subjected to emulsification together with the components (A) and (C) in the form of sulfonic acid, but may be an unsaturated aliphatic sulfonic acid salt and / or a hydroxylated aliphatic sulfonic acid. As an emulsifier in the form of an acid salt, an acid may be added after emulsification to generate the component (B) in the reaction system to contribute as an emulsion polymerization catalyst. The latter method is preferred because it is easy to obtain and handle.

The unsaturated aliphatic sulfonic acid salt and / or the hydroxylated aliphatic sulfonic acid salt are represented by the above formula (II) and / or
Or a salt of an acid represented by the formula (III). As the kind of the salt, sodium salt, potassium salt, ammonium salt, triethanolamine salt and the like are preferable from the emulsifying effect,
Specifically, sodium dodecenesulfonate, sodium tetradecenesulfonate, sodium hexadecenesulfonate, and the corresponding potassium and ammonium salts,
Unsaturated aliphatic sulfonates such as triethanolamine salts; and sodium hydroxide dodecanesulfonate, sodium hydroxytetradecanesulfonate, sodium hydroxyhexadecanesulfonate and the corresponding potassium salts, ammonium salts, triethanolamine salts and the like. Hydroxyaliphatic sulfonates are exemplified.

The acid added after the emulsification has a function of converting at least a part of the sulfonic acid salt into an acid form to act as the component (B). Examples of such an acid include sulfuric acid, hydrochloric acid, phosphoric acid, and formic acid. Itself (A)
Sulfuric acid is preferred because it functions as a catalyst for the dehydration polycondensation reaction of the silanol group of the component and a large polymerization rate can be obtained even at a low temperature, but one of the objects of the present invention is to form a cyclic siloxane oligomer present in an emulsion. From the viewpoint of suppressing the amount, phosphoric acid, formic acid, and the like, which do not produce a cyclic siloxane oligomer by the siloxane equilibration reaction during the polycondensation reaction even if they remain in the system, are preferable.

The above sulfonic acid type or sulfonic acid salt type anionic surfactants may be used alone or in combination. The amount of (A) component 100
1 to 100 parts by weight, preferably 1 to 50 parts by weight,
Parts by weight are more preferred. If the amount is less than 1 part by weight, the emulsion may have poor stability and may be separated. If the amount is more than 100 parts by weight, the emulsion may be thickened and the fluidity may be deteriorated. When the above-mentioned acid is used in combination, its use amount is not particularly limited, but is preferably 0.05 to 10 parts by weight based on 100 parts by weight of the component (A).

Water as the component (C) is a medium for dispersing and emulsifying the component (A). The amount of the component (C) used is usually 30 to 1,000 parts by weight based on 100 parts by weight of the component (A), and the concentration of the component (A) in the emulsion is 10 to 10 parts by weight.
An amount such that it becomes 70% by weight is preferred.

The polyorganosiloxane emulsion of the present invention can be produced as follows. That is, (A)
A polydiorganosiloxane having a molecular chain terminal blocked with a silanol group as a component, water as a component (C), and an unsaturated aliphatic sulfonic acid and / or a hydroxylated aliphatic sulfonic acid as (B), or Pre-mix the salt. The order of mixing is arbitrary, for example, in a stirring tank (C)
The component (B) and / or its salt are mixed and dissolved in the component, and the component (A) is added thereto with stirring. Then, homogenizer, colloid mill, line mixer,
Pass through an emulsifier such as a Sonorator. 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. Next, when a salt of the component (B) is used for emulsification, an acid is added and dispersed to produce the component (B). When the stirring is continued, the polycondensation reaction of the silanol group of the component (A) causes
A high molecular weight polyorganosiloxane is formed and an emulsion containing it is obtained. In order to obtain a polyorganosiloxane having a higher degree of polymerization and to prevent a cyclic siloxane oligomer from being produced by a side reaction,
The lower the temperature of the polycondensation reaction, the better. On the other hand, if the cooling is excessive, the stability of the emulsion is impaired. Therefore, in consideration of these, the preferable condensation conditions are 0 to 40 ° C., more preferably 0 to 15 ° C. for 2 to 24 hours. You can take longer.

When the desired degree of polymerization has been reached, an alkaline substance is added to neutralize the catalyst component (B) and the acid added. Examples of the alkaline substance include sodium hydroxide, potassium hydroxide,
Inorganic substances such as ammonia, sodium carbonate, potassium carbonate, ammonium carbonate, and potassium acetate; amines such as triethanolamine;

Thus, a stable emulsion containing a high molecular weight polyorganosiloxane can be produced.
Polyorganosiloxane obtained by emulsion polymerization,
It has a silanol group at the end of the molecular chain and has a viscosity at 25 ° C. of preferably 10,000 cSt or more, more preferably 500,000 to 30,000,000 cSt. Alternatively, depending on the purpose, a triorganosilyl group,
For example, a polyorganosiloxane having a trimethylsilyl group and having a viscosity at 25 ° C of 10,000 to 1,000,000 cSt 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)
Examples of other anionic surfactants used in combination with the component and / or its salt include polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl ether carboxylate, 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, such as 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 ester,
Examples thereof include, but are not limited to, polyoxyethylene sorbite fatty acid ester, polyoxyethylene fatty acid amine, glycerin fatty acid ester, sorbitan fatty acid ester, and sucrose fatty acid ester.

The amount of the anionic and / or nonionic surfactant arbitrarily added as described above may be adjusted according to the amount of the component (B) when it is added before the emulsion polymerization using the component (B) as a catalyst. It is necessary that the amount does not impair the catalytic ability, and specifically, the amount is not more than 5 times the weight of the component (B) or its initially incorporated salt.

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:
Examples include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, and the like.
In the temperature range of 40 ° C, the reaction rate by the acidic catalyst is excellent,
Hexamethyldisiloxane is preferable because the residual component can be easily removed by volatilization even when it is excessively added. 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, it is necessary to use methyldimethoxysilane, methyltrimethoxysilane, dimethyldiethoxysilane, A small amount of a reactive silane, such as methacryloxypropyltrimethoxysilane, can be added during or after the emulsion polymerization.

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 thus obtained is used as a cosmetic such as a hand cream or an anti-branch agent or contains 0.1% by weight or more of the present invention. The composition can be used as a cosmetic by blending any components within a range that does not impair the object of the invention.

As cosmetics, hair oil, hair dye, skim oil,
Set lotions, tics, bottled oils, hair creams,
Hair tonic, hair liquid, hair spray, pomade, shampoo, hair rinse, hair conditioner,
Hair cosmetics such as a hair lotion and an anti-branch agent; and skin cosmetics such as a hand cream, a skin cream, a foundation, an eye shadow, an eyeliner, a mascara, a face wash, and an antiperspirant. Examples of the form of the cosmetic include solid, gel, liquid, and paste forms.

The components used to prepare the cosmetic of the present invention by being blended with the polyorganosiloxane emulsion of the present invention include hydrocarbons such as liquid paraffin, petrolatum, solid paraffin, squalane and olefin oligomers; Esters such as isopropyl acrylate, stearyl stearate, octyldodecyl myristate, octyldodecyl oleate, lanolin acetate, triglyceride 2-ethylhexanoate; lauryl alcohol, cetyl alcohol, stearyl alcohol;
Higher alcohols such as lanolin alcohol and beeswax; higher fatty acids such as palmitic acid and stearic acid and amines such as diethanolamine for neutralizing the same; ethylene glycol, propylene glycol,
Moisturizers such as 3-butylene glycol, glycerin, sorbitol; inorganic powders such as titanium oxide, carbon black, iron oxide, sericite, talc, kaolin, mica; nylon, polyethylene, poly (meth) acrylate; Organic polymer powders; solvents such as water and ethanol; anionic and nonionic surfactants exemplified as surfactants optionally incorporated during the emulsion polymerization of the polyorganosiloxane described above; and Examples include, but are not limited to, amphoteric surfactants such as betaine; fungicides; coloring agents;

To incorporate 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.

[0038]

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.
The state of the emulsion and its stability are very good. Moreover, the surfactant present in the emulsion is
Does not adversely affect the environment and does not reduce the feeling of use when used as a cosmetic. 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 pollution of the environment and a decrease in the feeling of use of the cosmetic.

Therefore, the polyorganosiloxane emulsion of the present invention can be used in cosmetics and the like, has excellent stability, and can impart the spread, touch, and gloss peculiar to silicone. In addition, it is also 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 as a fiber treatment agent for textiles, interior decoration materials, hanging cloths and the like.

[0040]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples. Parts and% in Examples are parts by weight and% by weight, unless otherwise specified, and the viscosity is 2%.
The value at 5 ° C. The present invention is not limited by these examples.

The viscosity, molecular terminal and cyclic siloxane oligomer content of the high molecular weight polyorganosiloxane contained in the emulsion obtained by emulsion polymerization were measured as follows.

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,
For 45 minutes in an oven 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.

The molecular chain ends of the polyorganosiloxane The removed polyorganosiloxane is put in a container, a small amount of tetraethoxysilane and dibutyltin dilaurate are added, the container is sealed, and the container is left standing for 24 hours to change the state of the polyorganosiloxane. Observed. If there was no change, it was determined that the molecular chain end was blocked with a trimethylsilyl group, and if it was thickened or had a rubbery state, it was blocked with a silanol group.

Cyclic siloxane oligomer content 5 parts by volume of the emulsion were sampled,
Volume part, 100 parts by volume of n-hexane and 50 parts by volume of water were added and shaken vigorously, and allowed to stand for 24 hours to separate into two layers. The n-hexane layer was collected with a microsyringe and subjected to gas chromatography. The amount of cyclic siloxane oligomer in the sample was determined. From this value and the amount of polyorganosiloxane obtained by volatilizing n-hexane separately from the n-hexane layer, the content of cyclic siloxane oligomer in the polyorganosiloxane was calculated.

The stability of the emulsion obtained by emulsion polymerization was measured as follows.

Stability of Emulsion 100 parts by volume of the emulsion were placed in a transparent glass bottle of 500 parts by volume, sealed, placed near a window exposed to direct sunlight, allowed to stand for 3 months, and the separated state and the colored state were observed. ,
The evaluation was as follows.

Example 1 8 parts of an anionic surfactant, which is a mixture of 75% sodium tetradecenesulfonate and 25% sodium hydroxytetradecanesulfonate, were uniformly dispersed in 80 parts of deionized water. This dispersion has a viscosity of 83 cSt,
Α, ω- containing 1.8% of cyclic siloxane oligomer
After adding 100 parts of dihydroxypoly (dimethylsiloxane) and premixing by stirring, the mixture is passed twice through a pressure homogenizer at a pressure of 300 kgf / cm ² to obtain α, ω.
-An emulsion containing dihydroxypoly (dimethylsiloxane) was obtained.

To this emulsion, 0.3 part of sulfuric acid was added, and kept at 35 ° C. for 24 hours while stirring. Then
A 10% aqueous solution of sodium carbonate was added to the mixture at pH 7 while stirring was continued.
To stop the polycondensation reaction, thereby producing an emulsion E-1 containing high-molecular-weight polydimethylsiloxane.

Example 2 4 parts of an anionic surfactant, which is a mixture of 75% sodium tetradecenesulfonate and 25% sodium hydroxytetradecanesulfonate, were uniformly dispersed in 300 parts of deionized water. This dispersion has a viscosity of 250 cSt
Α, ω-dihydroxypoly (dimethylsiloxane) 10 containing 0.11% of cyclic siloxane oligomer
After adding 0 parts and 0.15 parts of hexamethyldisiloxane and premixing by stirring, the mixture was passed through a pressure homogenizer twice at a pressure of 400 kgf / cm ² to obtain α, ω-
An emulsion containing dihydroxypoly (dimethylsiloxane) was obtained.

To this emulsion, 0.5 part of sulfuric acid was added, and the mixture was kept at 25 ° C. for 10 hours with stirring. Then
A 10% aqueous solution of sodium carbonate was added to the mixture at pH 7 while stirring was continued.
To stop the polycondensation reaction, thereby producing an emulsion containing high-molecular-weight polydimethylsiloxane. To this, 3 parts of polyoxyethylene (7) secondary dodecyl ether was further added and mixed.
Emulsion E-2 was obtained.

Example 3 30 parts of an anionic surfactant, which is a mixture of 75% sodium tetradecenesulfonate and 25% sodium hydroxytetradecanesulfonate, and 1 part of sodium polyoxyethylene (4) lauryl sulfate were added to 2 parts of deionized water.
It was uniformly dispersed in 00 parts. The dispersion has a viscosity of 1
Α, ω-dihydroxypoly (dimethylsiloxane) containing 5% cSt and 2.2% cyclic siloxane oligomer
Then, the mixture was premixed by stirring, and then passed through a pressure homogenizer three times at a pressure of 400 kgf / cm ² to obtain α, ω-dihydroxypoly (dimethylsiloxane).
Was obtained.

To this emulsion, 1.0 part of sulfuric acid was added, and the mixture was kept at 10 ° C. for 5 hours with stirring. Then, the polycondensation reaction was stopped by dropping a 10% aqueous solution of sodium carbonate until the pH became 7 while continuing stirring, thereby producing an emulsion E-3 containing high-molecular-weight polydimethylsiloxane.

Example 4 15 parts of an anionic surfactant, which is a mixture of 75% of tetradecenesulfonic acid and 25% of hydroxytetradecanesulfonic acid, and 3 parts of polyoxyethylene (6) lauryl ether were added to 100 parts of deionized water. Dispersed uniformly. To this dispersion, 100 parts of α, ω-dihydroxypoly (dimethylsiloxane) having a viscosity of 700 cSt and containing 0.25% of a cyclic siloxane oligomer is added and premixed by stirring.
By passing once at 0 kgf / cm ² , an emulsion containing α, ω-dihydroxypoly (dimethylsiloxane) was obtained.

This emulsion was kept at 15 ° C. for 3 hours while stirring. Then, the polycondensation reaction was stopped by dropping an aqueous ammonia solution until the pH reached 7 while continuing stirring, thereby producing an emulsion E-4 containing high-molecular-weight polydimethylsiloxane.

Example 5 An emulsion containing α, ω-dihydroxypoly (dimethylsiloxane) was obtained in the same manner as in Example 1. To this was added 0.5 part of phosphoric acid, and the mixture was maintained at 15 ° C. for 10 hours with stirring. Then, a 10% aqueous solution of sodium carbonate was added dropwise until the pH reached 7 while continuing stirring.
The polycondensation reaction was stopped to produce Emulsion E-5 containing high molecular weight polydimethylsiloxane.

Example 6 An emulsion containing α, ω-dihydroxypoly (dimethylsiloxane) was obtained in the same manner as in Example 1. To this was added 0.5 part of formic acid, and the mixture was kept at 15 ° C. for 10 hours while stirring. Then, the polycondensation reaction was stopped by dropping a 10% aqueous sodium carbonate solution until the pH reached 7 while continuing stirring, thereby producing an emulsion E-6 containing high-molecular-weight polydimethylsiloxane.

Example 7 An emulsion containing α, ω-dihydroxypoly (dimethylsiloxane) was obtained in the same manner as in Example 1. 0.3 parts of sulfuric acid was added thereto, and the mixture was maintained at 8 ° C. for 30 hours with stirring. Then, the polycondensation reaction was stopped by dropping a 10% aqueous sodium carbonate solution until the pH reached 7 while continuing stirring, thereby producing an emulsion E-7 containing high-molecular-weight polydimethylsiloxane.

COMPARATIVE EXAMPLE 1 2 parts of an anionic surfactant, which is a mixture of 75% sodium tetradecenesulfonate and 25% sodium hydroxytetradecanesulfonate, was added to a mixture of 150 parts of deionized water and 0.4 part of sulfuric acid. Dispersed uniformly. After 100 parts of octamethylcyclotetrasiloxane was added to the dispersion and premixed by stirring, the mixture was passed through a pressure homogenizer twice at a pressure of 300 kgf / cm ² to obtain an emulsion containing octamethylcyclotetrasiloxane. .

While stirring this emulsion, 85 ° C.
For 5 hours. After gradually cooling to 15 ° C. over 3 hours, stirring was further continued at 15 ° C. for 5 hours. The ring-opening polymerization reaction was stopped by dropping a 10% aqueous solution of sodium carbonate until the pH reached 7 while continuing stirring, and the emulsion E-C containing high molecular weight polydimethylsiloxane was added.
1 was produced.

Comparative Example 2 8 parts of dodecylbenzene sulfonic acid were uniformly dispersed in 80 parts of deionized water. To this dispersion, 100 parts of α, ω-dihydroxypoly (dimethylsiloxane) similar to that used in Example 1 was added, and the mixture was preliminarily mixed by stirring, and then twice in a pressure homogenizer at a pressure of 300 kgf / cm ^2. By passing through, an emulsion containing α, ω-dihydroxypoly (dimethylsiloxane) was obtained.

The emulsion was kept at 15 ° C. for 15 hours with stirring. Then, the polycondensation reaction was stopped by dropping a 10% aqueous solution of sodium carbonate until the pH reached 7 while continuing stirring, thereby producing an emulsion E-C2 containing high-molecular-weight polydimethylsiloxane.

The average particle diameter of the oil phase of each of the polydimethylsiloxane emulsions E-1 to E-7, E-C1, and E-C2 obtained in Examples and Comparative Examples was measured. The viscosity, molecular chain terminal and cyclic siloxane oligomer content of the polydimethylsiloxane contained in these emulsions were measured. Furthermore, the stability of the emulsion was evaluated. Table 1 shows the results.

[0063]

[Table 1]

Examples 8 to 14 and Comparative Example 3 (Hand lotion) Hand lotions having the compositions shown in Table 2 were prepared using the polydimethylsiloxane emulsions E-1 to E-7 or E-C1, respectively.

[0065]

[Table 2]

The hand lotion thus obtained was subjected to a feeling test for checking the presence or absence of stickiness by 30 female panelists. The results were as shown in Table 3.

[0067]

[Table 3]

Example 15, Comparative Examples 4 and 5 (Foundations) Polyorganosiloxane Emulsions E-4 and E-C1
Alternatively, a foundation having a composition shown in Table 4 was prepared using each of E-C2. When a similar feel test was performed on these, the results shown in Table 4 were obtained. The evaluation results of the adhesion, water resistance and oil resistance were almost the same and excellent.

[0069]

[Table 4]

Example 16, Comparative Examples 6 and 7 (Eyeliner) Polyorganosiloxane emulsions E-4 and E-C1
Alternatively, an eyeliner having a composition shown in Table 5 was prepared using each of E-C2. When a similar feel test was performed on these, the results shown in Table 5 were obtained. The evaluation results of the friction resistance, water resistance, and oil resistance were almost the same and excellent.

[0071]

[Table 5]

Example 17, Comparative Examples 8 and 9 (Hair Set Lotion) Polyorganosiloxane Emulsions E-4 and E-C1
Alternatively, a hair setting lotion having the composition shown in Table 6 was prepared using each of E-C2. When a similar touch test was performed on these, the results shown in Table 6 were obtained.
The evaluation results of combability, flexibility, and set holding power were almost the same and excellent.

[0073]

[Table 6]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI B01J 13/00 B01J 13/00 A C08K 5/42 C08K 5/42

Claims (5)

[Claims] (A) A general formula: HO [(R ¹ ) ₂ SiO] _m H (I) (wherein R ¹ is a substituted or unsubstituted monovalent carbon atom which may be the same or different. M represents (A) a hydrogen group;
(A value that makes the viscosity at 25 ° C. of 10 to 3,000 cSt) (B) unsaturated aliphatic sulfonic acid and / or hydroxylated aliphatic sulfonic acid; A) a polyorganosiloxane emulsion obtained by emulsion polymerization in the presence of water. 2. The polyorganosiloxane emulsion according to claim 1, wherein (B) is formed in a reaction system by reacting the sulfonic acid salt with an acid. 3. The polyorganosiloxane emulsion according to claim 1, wherein the content of the cyclic siloxane oligomer in the polyorganosiloxane is 3.5% by weight or less. 4. The polyorganosiloxane emulsion according to claim 1, wherein the viscosity at 25 ° C. of the polyorganosiloxane is 10,000 cSt or more. 5. A cosmetic using the polyorganosiloxane emulsion according to any one of claims 1 to 4.