JPH11222554A - High molecular weight polyorganosiloxane emulsion and cosmetic containing same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a stable emulsion which contains a high-mol.-wt. polyorganosiloxane in a high concn. and hardly pollutes the environment when used and to provide a cosmetic contg. the same. SOLUTION: This polyorganosiloxane emulsion is prepd. by the emulsion polymn. of a silanol-terminated polydiorganosiloxane having a viscosity of 10-3,000 cSt in the presence of an alkylbenzenesulfonic acid and an alkylsulfuric acid. The objective cosmetic contains the emulsion.

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 a stable emulsion containing a high molecular weight polyorganosiloxane obtained by emulsion polymerization of The present invention also relates to a cosmetic 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 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 an alkylbenzenesulfonic acid is used, a stable emulsion can be obtained when emulsifying a low-viscosity substance such as octamethylcyclotetrasiloxane, but a polyorganosiloxane having a viscosity of 10 to 3,000 cSt is emulsified. In this case, it was difficult to obtain a sufficiently stable emulsion by using alkylbenzenesulfonic acid alone as an anionic surfactant.

[0007] Further, from the viewpoint of transportation or production efficiency, an emulsion having a higher siloxane concentration is required. However, when emulsifying a polyorganosiloxane at a high concentration, an alkylbenzenesulfonic acid is used as an anionic surfactant. When used alone, a stable high-concentration emulsion could not be obtained.

[0008] Japanese Patent Application Laid-Open No. 2-147632 discloses that the use amount of an aliphatic hydrocarbon group-substituted benzenesulfonic acid is reduced as much as possible by using an aliphatic hydrocarbon group-substituted benzenesulfonic acid and a trihalogenated acetic acid in combination. A method for producing a polyorganosiloxane emulsion, which suppresses the yellowing property of a substrate treated with an emulsion and improves the conversion of low-molecular-weight siloxane to avoid a decrease in the degree of polymerization of the resulting polyorganosiloxane, It has been disclosed. However, there are some problems such as complicated handling due to the use of solid hexamethylcyclotrisiloxane as the low-molecular-weight siloxane as a raw material, and a slight deterioration in emulsion stability.

On the other hand, a cyclic siloxane oligomer such as octamethylcyclotetrasiloxane is used as a low-molecular-weight siloxane to be subjected to such emulsion polymerization because it is easily available and is easily emulsified and ring-opened. I have. However, the ring-opening polymerization of the cyclic siloxane oligomer is an equilibrium reaction, and the emulsion after emulsion polymerization generally contains 5 to 10% by weight of the cyclic siloxane oligomer represented by octamethylcyclotetrasiloxane in polysiloxane. Typically it is present at about 7% by weight.

[0010] Therefore, in the case of an application that requires the use of a very homogeneous emulsion, the oligomer may volatilize from the emulsion during storage or use, thereby impairing the physical stability of the emulsified system. Further, such an emulsion is used in a large amount as a hair cosmetic for hair treatment, for example, in a beauty salon and the like, and particularly when accompanied by a heat blow treatment, the volatilized oligomer contaminates the surrounding environment, and It may contaminate the surrounding ventilation fan system and cause contact failure of various electric devices such as fan heaters. 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 such applications, it has been required to suppress the amount of the cyclic siloxane oligomer in the emulsion.
In particular, among cyclic siloxanes, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane are easily produced by an equilibration reaction, are stable compounds, and are volatile, so that their content must be suppressed. became. However, it has been difficult to remove the cyclic siloxane oligomers present in the emulsion without breaking the emulsion after emulsion polymerization.

JP-A-63-265924 and JP-A-4-178429 disclose that polydiorganosiloxanes whose molecular chain ends are blocked with silanol groups are used as starting materials, and that high molecular weight polyorganosiloxanes are obtained by emulsion polymerization. It is disclosed to make emulsions containing the same. However, the anionic surfactant used in these is an alkyl benzene sulfonic acid, an alkyl naphthalene sulfonic acid or a polyoxyethylene alkyl ether sulfuric acid alone, even if this is used in combination with a nonionic surfactant, It was difficult to obtain a sufficiently stable emulsion.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems involved in the prior art, and more specifically, the stability of an emulsion in a system using an anionic surfactant as a catalyst. And suppressed the amount of cyclic siloxane oligomer present in the emulsion,
An object of the present invention is to provide a stable emulsion containing a high concentration of a high molecular weight polyorganosiloxane. Another object of the present invention is to provide a cosmetic containing such an emulsion.

[0013]

Means for Solving the Problems As a result of repeated studies to achieve the above object, the present inventors have found that a polydiorganosiloxane having a molecular chain terminal capped with a silanol group is used and a specific surfactant is used. It has been found that the object can be achieved by performing a polycondensation reaction using a system, and the present invention has been completed.

That is, the present invention provides (A) a compound represented by the general formula:

Embedded image (Wherein R ¹ may be the same or different,
Represents a substituted or unsubstituted monovalent hydrocarbon group, m is a value that makes the viscosity of (A) at 25 ° C. 10 to 3,000 cSt), and the content of the cyclic siloxane oligomer is 1.5 (B) (1) alkylbenzenesulfonic acid and (2) alkylsulfuric acid; and (C) a high molecular weight polyorganosiloxane obtained by emulsion polymerization in the presence of water. It relates to emulsions and to cosmetics containing such emulsions.

[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 from 15 to 1,000 cSt, particularly preferably from 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-
Examples are substituted hydrocarbon groups such as trifluoropropyl, and the high molecular weight polyorganosiloxane obtained by emulsion polymerization has low surface tension, good spreadability, excellent elongation, water repellency, excellent gloss, etc., and lacks physiological activity. Preferably, 85% or more of R ^{1 in} the molecule is a methyl group, and it is particularly preferable that substantially all of R ¹ is a methyl group. 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-terminated polydiorganosiloxane is synthesized, for example, by hydrolyzing dimethyldichlorosilane and subjecting it to polycondensation. For example, using water as a terminal stopper, an acidic catalyst such as sulfuric acid, or It is synthesized by ring-opening polymerization of the corresponding cyclic siloxane oligomer in the presence of an alkaline catalyst such as potassium hydroxide or potassium silanolate. In the product, unreacted cyclic siloxane oligomer, for example, when the target substance is α, ω-dihydroxypoly (dimethylsiloxane), hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexene In order to avoid the above-mentioned problem caused by the cyclic siloxane oligomer remaining after the emulsion polymerization obtained by the present invention, a cyclic siloxane oligomer such as octamethylcyclotetrasiloxane in the component (A) is present. Is 3.5% by weight or less, preferably 2.5% by weight or less. The content of octamethylcyclotetrasiloxane in the cyclic siloxane oligomer is particularly preferably 1.5% by weight or less.
More preferably, the content is 8% 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 component (B) used in the present invention is a component that functions as an emulsifier and a polymerization catalyst. The component (B) includes (1) alkylbenzene sulfonic acid and (2)
Alkyl sulfate is used in combination. As described above, by using (1) and (2) in combination, a good emulsified state can be obtained, and the component (A) can be favorably emulsion-polymerized. (1) Examples of the alkylbenzenesulfonic acid include hexylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, tetradecylbenzenesulfonic acid, hexadecylbenzenesulfonic acid, and octadecylbenzenesulfonic acid. (2) Examples of the alkyl sulfate include octyl sulfate, dodecyl sulfate, tetradecyl sulfate, hexadecyl sulfate, and octadecyl sulfate.

Such a component (B) is a component (A) in the form of an acid.
It may be blended with the component and the component (C) and subjected to emulsification, but is used as an emulsifier in the form of an alkylbenzene sulfonate and an alkyl sulfate, and an acid is added after emulsification,
The component (B) may be generated in the reaction system to function as an emulsion polymerization catalyst. When the emulsification is carried out at a high temperature or when the temperature rises during the emulsification, it is easy to control the emulsion polymerization conditions, the emulsification state is good, and floating of the high molecular weight polyorganosiloxane occurs during storage. The latter method is preferable because an emulsion having excellent stability can be obtained, and the content of the cyclic siloxane oligomer in the obtained emulsion can be further reduced.

The alkyl benzene sulfonate and the alkyl sulfate are salts of the above-mentioned component (B). As the kind of the salt, an amine salt such as a sodium salt, a potassium salt, an ammonium salt and triethanolamine is preferable from the emulsifying effect. Specifically, examples of the alkylbenzene sulfonate include sodium alkylbensulfonate such as sodium decylbenzenesulfonate, sodium dodecylbenzenesulfonate, and sodium tetradecylbenzenesulfonate; and corresponding potassium salts, ammonium salts, and triethanol. Amine salts and the like are exemplified. Examples of the alkyl sulfates include sodium alkyl sulfates such as sodium octyl sulfate, sodium dodecyl sulfate and sodium octadecyl sulfate, and corresponding potassium salts, ammonium salts, and triethanolamine salts. Among them, a sodium salt and a triethanolamine salt are preferably used.

The acid added after the emulsification has a function of converting at least a part of the alkylbenzenesulfonate and the alkylsulfate 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. Among these acids, sulfuric acid and hydrochloric acid are preferred because they themselves also function as catalysts for the dehydration polycondensation reaction of the silanol group of the component (A), and a high polymerization rate can be obtained even at a low temperature. One of the reasons is that the amount of cyclic siloxane oligomers such as octamethylcyclotetrasiloxane present in the emulsion is suppressed. Phosphoric acid, formic acid, and the like that do not produce an oligomer are preferable.

In the present invention, (1) alkylbenzenesulfonic acid and (2) alkylsulfuric acid are used in combination as described above. For each acid, one type may be used alone or several types may be used in combination. Is also good. For example,
(1) Dodecylbenzenesulfonic acid and tetradecylbenzenesulfonic acid may be used in combination as alkylbenzenesulfonic acid, and (2) octylsulfuric acid and dodecylsulfuric acid may be used in combination as alkylsulfuric acid. When used as 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. The amount of the alkylbenzenesulfonic acid or a salt thereof, and the amount of the alkylsulfuric acid or a salt thereof are preferably from 0.5 to 100 parts by weight in terms of acid with respect to 100 parts by weight of the component (A). 1-5
0 parts by weight is more preferable, and 2 to 10 parts by weight is particularly preferable. 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. (1)
The ratio of alkylbenzenesulfonic acid / (2) alkylsulfuric acid or a salt thereof is from 1/9 to as weight ratio in terms of acid.
9/1 is preferred, and 2/8 to 8/2 is particularly preferred. When an acid such as the above-mentioned sulfuric acid is used in combination, the amount of use is not particularly limited, but the emulsification state during the emulsion polymerization is good, and the polymerization with less by-product of the cyclic siloxane oligomer is performed. 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of 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. Since the emulsion of the present invention has good stability at a high concentration,
From the viewpoint of the characteristics, 40 to 70% by weight is particularly preferable.

The polyorganosiloxane emulsion of the present invention can be produced as follows. That is, (A)
The components are polydiorganosiloxanes whose molecular chain ends are blocked with silanol groups, water as component (C), and (B) as components (1) alkylbenzenesulfonic acid and (2) alkylsulfuric acid, or salts thereof. Is premixed. The order of mixing is arbitrary, but for example, the component (B) and / or its salt are mixed and dissolved in the component (C) 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. Then, when the salt of the component (B) was used for emulsification,
An acid is added to disperse to produce the component (B), alkylbenzenesulfonic acid and alkylsulfuric acid. When the stirring is continued, a high molecular weight polyorganosiloxane is synthesized by a polycondensation reaction of the silanol group at the molecular end of the component (A), and an emulsion containing the same is formed.
In order to obtain a polyorganosiloxane having a higher degree of polymerization and to prevent the formation of a cyclic siloxane oligomer by a side 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 emulsion is impaired. Therefore, in consideration of these, the preferable condensation conditions are 0 to 80 ° C., more preferably 0 to 50 ° C. for 2 to 24 hours. You can take longer.

When the desired degree of polymerization has been reached, the alkaline substances are added to neutralize the catalysts (1) alkylbenzenesulfonic acid and (2) alkylsulfuric acid, as well as the added acids. Examples of the alkaline substance include sodium hydroxide, potassium hydroxide,
Inorganic substances such as ammonia, sodium carbonate, potassium carbonate, ammonium carbonate and potassium acetate; and 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 such that the cyclic siloxane oligomer is produced during the emulsion polymerization.
If it is avoided by controlling the emulsion polymerization temperature or selecting a catalyst as described above, it is governed by the content of the cyclic siloxane oligomer in the component (A) used. The content of the cyclic siloxane oligomer in the polyorganosiloxane after the emulsion polymerization is controlled to 3.5% by weight or less, more preferably 2.5% by weight by controlling the content in the component (A) as described above. % 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. As the nonionic surfactant, one having an HLB of 6 to 19, preferably 8 to 18, or two or more additive HLBs of 6 to 19, preferably 8
~ 18 are preferred, 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, polyoxyethylene sorbite fatty acid ester, polyoxyethylene fatty acid amine, glycerin fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester and the like are exemplified. However, the present invention is not limited to these.

The amount of the anionic and / or nonionic surfactant arbitrarily added as described above is determined when the salt of the component (B) is added before the emulsion polymerization using the salt in combination with an acid as a catalyst. 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) or a salt thereof initially blended. .

In order to block the silanol group at the molecular end of the high molecular weight polyorganosiloxane obtained by emulsion polymerization with a stable triorganosilyl group, or to control the average degree of polymerization of the polyorganosiloxane to a desired value. At the time of emulsification, a small amount of the siloxane oligomer having a triorganosilyl group can be added as a terminal stopper. When the triorganosilyl group is a trimethylsilyl group, the added siloxane oligomer includes:
Examples include hexamethyldisiloxane, octamethyltrisiloxane, and decamethyltetrasiloxane. 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. hand,
It can also be an emulsion of a crosslinkable high molecular weight base polymer.

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 can be used as a cosmetic such as a hand cream or an anti-branch agent. 0.1% by weight or more of the emulsion is blended,
Various cosmetics can be prepared by blending other optional components within a range that does not impair the purpose of the present invention. 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, Hair cosmetics such as anti-splits;
Hand cream, hand lotion, skin cream,
Examples include foundations, eye shadows, eye liners, mascaras, facial cleansers, and skin cosmetics such as antiperspirants. Examples of the form of the cosmetic include solid, gel, liquid, and paste forms.

Other components used for preparing cosmetics by being blended with the polyorganosiloxane emulsion of the present invention include hydrocarbons such as liquid paraffin, petrolatum, solid paraffin, squalane and olefin oligomers; palmitine Esters such as isopropyl acrylate, stearyl stearate, octyldodecyl myristate, octyldodecyl oleate, lanolin acetate, and triglyceride 2-ethylhexanoate; higher alcohols such as lauryl alcohol, cetyl alcohol, stearyl alcohol, 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;
Humectants such as 1,3-butylene glycol, glycerin and sorbitol; inorganic powders such as titanium oxide, carbon black, iron oxide, sericite, talc, kaolin and mica; nylon, polyethylene, poly (meth) acrylic acid Organic polymer powders such as esters; solvents such as water and ethanol; anionic and nonionic surfactants exemplified as surfactants optionally incorporated in the above-mentioned emulsion polymerization of polyorganosiloxane And an amphoteric surfactant such as betaine; a bactericide; a coloring agent; a fragrance, and the like, but are not limited thereto.

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.

[0036]

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. 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, the environment is not polluted, and the feel to the skin is good.

Therefore, the polyorganosiloxane emulsion of the present invention can be used for cosmetics and the like to give a silicone-specific spread, touch and gloss. In addition, protective materials for furniture, miscellaneous goods, car interior and exterior, etc .;
It is also useful as a polishing agent for improving these appearances; and as a fiber treatment agent for fabrics, upholstery, hanging cloths and the like.

[0038]

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, cyclic siloxane oligomer content and storage stability test 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 end of the polyorganosiloxane The polyorganosiloxane taken out above is placed in a container, a small amount of tetraethoxysilane and dibutyltin dilaurate are added, and the mixture is sealed for 24 hours. The condition was observed. If there was no change, the molecular chain end was blocked with a trimethylsilyl group, and if the viscosity increased or the rubbery state was exhibited, it was determined that the molecular chain end was blocked with a silanol group.

Cyclic siloxane oligomer content 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 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 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.

Storage stability The storage stability of the emulsion was evaluated as follows 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. X: An oil layer is seen.

Example 1 3 parts of sodium dodecylbenzenesulfonate and 5 parts of sodium dodecyl sulfate were uniformly dispersed in 100 parts of deionized water. This dispersion has a viscosity of 83 cSt and contains a total of 0.70% of cyclic siloxane oligomers.
After adding 100 parts of ω-dihydroxypoly (dimethylsiloxane) and premixing by stirring, the mixture was passed through a pressure homogenizer once at a pressure of 1,000 kgf / cm ² to obtain α, ω-dihydroxypoly (dimethylsiloxane).
Was obtained.

To this emulsion was added 0.2 part of sulfuric acid, and the mixture was stirred at 50 ° C. for 1 hour and then at 10 ° C. for 15 hours.
Hold for hours. Next, 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-1 containing high-molecular-weight polydimethylsiloxane.

Example 2 Emulsion containing α, ω-dihydroxypoly (dimethylsiloxane) using the same surfactant and α, ω-dihydroxy (polymethylsiloxane) as in Example 1 and under the same blending ratio and conditions. I got 0.2 parts of sulfuric acid was added to this emulsion, and the mixture was kept at 5 ° C. for 24 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-2 containing high molecular weight polydimethylsiloxane.

Example 3 Triethanolamine dodecylbenzenesulfonate 10
Parts and 10 parts of sodium octadecyl sulfate were uniformly dispersed in 60 parts of deionized water. This dispersion has a viscosity of 2
At 50 cSt, a total of 1.01
%, Containing 100 parts of α, ω-dihydroxypoly (dimethylsiloxane), and premixed by stirring.
An emulsion containing α, ω-dihydroxypoly (dimethylsiloxane) was obtained by passing twice through a pressure homogenizer at a pressure of 400 kgf / cm ² .

To this emulsion, 1.0 part of phosphoric acid was added, and the mixture was stirred at 50 ° C. for 1 hour and then at 25 ° C. for 5 hours.
Hold for hours. Subsequently, 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 containing high-molecular-weight polydimethylsiloxane. To this, 5 parts of polyoxyethylene (7) secondary dodecyl ether was further added and mixed to obtain emulsion E-3.

Example 4 3 parts of sodium dodecylbenzenesulfonate and 5 parts of triethanolamine dodecyl sulfate were uniformly dispersed in 200 parts of deionized water. This dispersion has a viscosity of 15 cSt
Α, ω-dihydroxypoly (dimethylsiloxane) 1 containing a total of 2.73% of cyclic siloxane oligomers
After adding 00 parts and 0.2 parts of hexamethyldisiloxane and premixing by stirring, the mixture was passed through a pressure homogenizer three times at a pressure of 1,000 kgf / cm ² to obtain α,
An emulsion containing ω-dihydroxypoly (dimethylsiloxane) and hexamethyldisiloxane was obtained.

To this emulsion was added 0.2 part of sulfuric acid, and the mixture was kept at 10 ° C. for 5 hours while stirring. Next, the polycondensation reaction was stopped by dropping triethanolamine until the pH reached 7 while continuing stirring, and the emulsion E-containing high molecular weight polydimethylsiloxane was added.
4 was produced.

Example 5 2 parts of sodium dodecylbenzenesulfonate and 2 parts of sodium octadecyl sulfate were uniformly dispersed in 150 parts of deionized water. This dispersion has a viscosity of 700 cSt,
Α, ω-dihydroxypoly (dimethylsiloxane) 10 containing a total of 1.80% of cyclic siloxane oligomers
After adding 0 parts 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-dihydroxypoly (dimethylsiloxane).
Was obtained.

To this emulsion, 0.05 parts of hydrochloric acid was added, and the mixture was stirred at 35 ° C. for 1 hour and then at 15 ° C. for 3 hours.
Hold for hours. Subsequently, the polycondensation reaction was stopped by dropping an aqueous ammonia solution until the pH reached 7 while continuing stirring, thereby producing an emulsion E-5 containing high-molecular-weight polydimethylsiloxane.

Comparative Example 1 3 parts of sodium dodecylbenzenesulfonate and 2 parts of sodium dodecyl sulfate were uniformly dispersed in 100 parts of deionized water. To this dispersion, 100 parts of octamethylcyclotetrasiloxane was added, and the mixture was premixed by stirring. Then, the mixture was added to a pressure homogenizer at a pressure of 1,000 kgf / cm ² .
By passing through the emulsion, an emulsion containing α, ω-dihydroxypoly (dimethylsiloxane) was obtained.

To this emulsion, 0.2 part of sulfuric acid was added, and the mixture was stirred at 80 ° C. for 3 hours and then at 10 ° C. for 24 hours.
Hold for hours. Next, the ring-opening 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-C1 containing high-molecular-weight polydimethylsiloxane.

Comparative Example 2 5 parts of sodium dodecylbenzenesulfonate were uniformly dispersed in 150 parts of deionized water. To this dispersion, 100 parts of α, ω-dihydroxypoly (dimethylsiloxane) having a viscosity of 700 cSt and a total of 1.80% of a cyclic siloxane oligomer is added, and the mixture is preliminarily mixed by stirring. 2,000kgf / cm ²
3 times, but a uniform emulsion was not obtained.

Comparative Example 3 8 parts of sodium dodecylbenzenesulfonate were uniformly dispersed in 100 parts of deionized water. The dispersion had a viscosity of 83 cSt and a cyclic siloxane oligomer
After adding 100 parts of α, ω-dihydroxypoly (dimethylsiloxane) containing 1% and premixing by stirring, the mixture was added to a pressure homogenizer at a pressure of 1,000 kgf / cm ² .
By passing through the emulsion, an emulsion containing α, ω-dihydroxypoly (dimethylsiloxane) was obtained.

0.2 parts of sulfuric acid was added to this emulsion, and the mixture was stirred at 70 ° C. for 1 hour and then at 10 ° C. for 24 hours.
Hold for hours. 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.

Comparative Example 4 5 parts of sodium dodecyl sulfate were dispersed uniformly in 150 parts of deionized water. This dispersion has a viscosity of 83 cSt
Α, ω-dihydroxypoly (dimethylsiloxane) 1 containing a total of 0.70% of cyclic siloxane oligomers
After adding 00 parts and premixing by stirring, the mixture was passed through a pressure homogenizer three times at a pressure of 1,000 kgf / cm ² ,
A uniform emulsion could not be obtained.

Comparative Example 5 3 parts of sodium dodecylbenzenesulfonate and 5 parts of sodium polyoxyethylene (4) nonylphenyl ether sulfate were uniformly dispersed in 100 parts of deionized water. 100 parts of α, ω-dihydroxypoly (dimethylsiloxane) having a viscosity of 83 cSt and a total of 1.01% of a cyclic siloxane oligomer is added to the dispersion, and the mixture is preliminarily mixed by stirring.
By passing once at 000 kgf / cm ² , an emulsion containing α, ω-dihydroxypoly (dimethylsiloxane) was obtained.

To this emulsion was added 0.2 part of sulfuric acid, and the mixture was kept at 10 ° C. for 24 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 E-C3 containing high-molecular-weight polydimethylsiloxane.

Evaluation Examples Polydimethylsiloxane emulsions E-1 to E-5 and E-C1 to E-C3 obtained in Examples and Comparative Examples
Of the oil phase was measured. The viscosity, molecular chain terminal and cyclic siloxane oligomer content of the polydimethylsiloxane contained in these emulsions were measured. Further, the storage stability of each emulsion was evaluated. Table 1 shows the results.

[0062]

[Table 1]

Example 6 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 was 3 cm × 3 cm
, And a patch test was carried out by 30 women and fixed on the inside of the base of the arm with a tape, which was changed every day for 3 days. As a result, no abnormality such as itching was observed in any of the hand lotions using the polydimethylsiloxane emulsion.

Example 7 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.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Frank J. Traber New York, USA 12180, Troy, Downey Road 1

Claims (2)

[Claims] (A) A general formula: (Wherein R ¹ may be the same or different,
Represents a substituted or unsubstituted monovalent hydrocarbon group, m is a value that makes the viscosity of (A) at 25 ° C. 10 to 3,000 cSt), and the content of the cyclic siloxane oligomer is 3.5. (B) (1) an alkylbenzene sulfonic acid and (2)
A high molecular weight polyorganosiloxane emulsion obtained by emulsion polymerization in the presence of (C) water. 2. A cosmetic comprising the polyorganosiloxane emulsion according to claim 1.