JPH09278626A - Silicone emulsion, cosmetic and production of silicone emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a silicone emulsion containing a terminal hydroxyl groups- blocked polyorganosiloxane having high viscosity and useful for a cosmetic having excellent effect in hair or skin by subjecting a specific low-molecular weight organosiloxane to an emulsion polymerization by a specific method. SOLUTION: A low molecular weight organosiloxane having a structural unit of the formula (R is a monofunctional hydrocarbon; (n) is 0-3) is subjected to an emulsion polymerization on the presence of a surfactant (especially a cationic surfactant is preferable), a catalyst component and water to make an emulsion, and the resultant emulsion is held at 70-90 deg.C for 1-15hrs, especially 5-15hrs, then held at 0-40 deg.C, especially 20-40 deg.C 1-500hrs, thus the reaction is finished. A hair cosmetic or a skin cosmetic is obtained by using the emulsion as a principal agent, This cosmetic forms a film excellent in water resistance, oil resistance and weatherability and can give wetness or smoothness to the skin for a long period of time.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicone emulsion obtained by emulsion-polymerizing a low molecular weight organosiloxane, a cosmetic composition containing the silicone emulsion as a main component, and a method for producing a silicone emulsion. Viscosity is 500,000 to 50,0
A silicone emulsion containing a polyorganosiloxane having a terminal hydroxyl group of 0,000 cP and a main component of this silicone emulsion forms a film excellent in water resistance, oil resistance, and weather resistance, and has good moistness and smoothness. Cosmetics having excellent makeup functionality, long-lasting makeup functionality and stability over time, 25 ° C.
Viscosity at 500,000 to 50,000,000 cP
For producing a silicone emulsion containing a polyorganosiloxane having a terminal hydroxyl group and a method for producing a cationic silicone emulsion containing a polyorganosiloxane having a terminal hydroxyl group having a viscosity at 25 ° C. of 50,000 cP or more Regarding

[0002]

2. Description of the Related Art Conventionally, polyorganosiloxane has been
Various cosmetics such as skin care cosmetics, hair care cosmetics and makeup cosmetics are important components that form a uniform film on the surface of skin or hair to impart moisture and smoothness, and to impart water repellency. Has been used for a fee. In particular, in the field of cosmetics, since it has excellent film forming ability, film functionality, cosmetic functionality and durability of these functions,
The demand for high molecular weight polyorganosiloxanes is expanding rapidly.

When a high molecular weight polyorganosiloxane is blended with various emulsified cosmetics, the emulsification technique is an important factor for exerting the above-mentioned excellent functions. Generally, the polyorganosiloxane emulsification method is It is a mechanical emulsification method.

The mechanical emulsification method is polyorganosiloxane,
In this method, mechanical energy is applied to a mixture of a surfactant and water to uniformly emulsify and disperse these components to obtain a desired stable emulsion. A colloid mill, a homomixer, a homogenizer, a combimix, a sand grinder, etc. are generally used for imparting mechanical energy.

For example, in the method described in US Pat. No. 2,755,194, polydimethylsiloxane of 350 cSt and a surfactant are mixed at 25 ° C., a small amount of water is added to this mixture, and the mixture is emulsified and dispersed in a colloid mill. After that, the desired emulsion is obtained by further continuously adding water. However, in the mechanical emulsification method, only polyorganosiloxane within the range of the mechanical energy applied from the equipment used can be used, and at most 5
Only polyorganosiloxanes with viscosities up to about 0,000 cP could be emulsified (JP-A 63-125530).
No. 56-109227). Therefore, when the emulsion containing the polyorganosiloxane emulsified by the mechanical emulsification method is used as a cosmetic,
There was a problem that it was not sticky and was not satisfactory as a cosmetic. In addition, in the emulsion thus obtained, generally the suspension microparticles made of polyorganosiloxane have a large particle size, so that the emulsion itself or the cosmetic containing the emulsion has a problem in stability over time.

Further, in the mechanical emulsification method, a method of emulsifying / dispersing a highly viscous fluid or resin, which is difficult to mechanically emulsify, by dissolving it in an organic solvent such as benzene, toluene or xylene, is also proposed. (JP-B-63-45748, JP-A-60-125)
No. 8 and No. 60-1259). However,
This method has a problem that it is difficult to use it as a cosmetic, since it uses an organic solvent and thus has a problem of danger due to solvent odor and flammability of the solvent.

Furthermore, in a mechanically emulsified emulsion, a method of improving stability with time by finely suspending fine particles by using a polyorganosiloxane in combination with a polyoxyalkylene group-containing polyorganosiloxane has been proposed. (JP-A-60-126209, 60)
-197610 gazette). However, since the polyoxyalkylene group-containing polyorganosiloxane used in this method is water-soluble, depending on the type of cosmetic,
There is a problem in that the durability of the excellent functionality of the polyorganosiloxane as a cosmetic may be reduced, and the upper limit of the viscosity of the polyorganosiloxane applicable to this method is at most about 1000 cP.

In such a mechanical emulsification method, when a quaternary ammonium salt-based surfactant having a rinsing effect itself is used as the surfactant, the surfactant is required to obtain an appropriate emulsion. There is a problem that it is necessary to use a large amount of the agent or to use a nonionic surfactant in combination.

Further, there is proposed a cosmetic composition containing a microemulsion having an average particle size of 0.15 μm or less obtained by emulsion polymerization of dimethylpolysiloxane (see JP-A-63-130512). However, this publication adopts a method of emulsion polymerization while dropping a crude siloxane emulsion into an aqueous solution to which a catalyst is added, and this method has a problem that it is generally difficult to obtain a high degree of polymerization. there were. In fact, only dimethylpolysiloxane having a degree of polymerization of up to 1200 is specifically shown, and at such a degree of polymerization, there is a problem that the viscosity of dimethylpolysiloxane is less than 100,000 cP.

Generally, in the emulsion polymerization method, a mixture of a low molecular weight siloxane or a reactive siloxane oligomer as a siloxane monomer, a surfactant, a water-soluble polymerization catalyst and water is emulsified / dispersed, and heated / cooled until the desired molecular weight is polymerized. This is a method of obtaining an emulsion by stirring, and it is possible to obtain a polyorganosiloxane having a viscosity over a wide range from a low molecular weight oil to a high molecular weight raw rubber region.

Examples of such emulsion polymerization method include:
A method of emulsifying and dispersing a low molecular weight siloxane and then adding an acid or alkali catalyst to carry out emulsion polymerization (Japanese Patent Publication No.
No. 2041), a method of simultaneously emulsifying and dispersing and polymerizing a low molecular weight siloxane using a surfactant having a catalytic activity (see Japanese Patent Publication No. 43-18800).

However, when a quaternary ammonium salt type surfactant is used in these emulsion polymerization methods, the polymerization rate is extremely low, and even if the polymerization is carried out over an industrially acceptable production time, for example, 48 hours. However, there is a problem that only a linear polyorganosiloxane having a viscosity of about 10,000 cp can be obtained.

Therefore, in the above-mentioned conventional methods, a silicone emulsion containing a polyorganosiloxane having a high viscosity, a cosmetic by the application thereof and a method for producing a silicone emulsion containing a polyorganosiloxane having a high viscosity have been suggested. There wasn't.

[0014]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned conventional examples. By using a silicone emulsion containing a polyorganosiloxane having a high viscosity end-capped hydroxyl group and a main component of this silicone emulsion, Forming a film with excellent water resistance, oil resistance, and weather resistance, having excellent cosmetic functionality such as moisture and smoothness, and having the durability of cosmetic functionality and stability over time -Free cosmetics, method for producing silicone emulsion containing high-viscosity end-capped polyorganosiloxane and silicone emulsion containing high-viscosity end-capped polyorganosiloxane emulsified with cationic surfactant It is intended to provide a manufacturing method.

[0015]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object, and as a result, in the presence of an anionic surfactant or a cationic surfactant and a catalyst component, Emulsion polymerization of an organosiloxane in water to give 500,000-5 at 25 ° C.
It is possible to obtain a silicone emulsion containing a polyorganosiloxane with a terminal hydroxyl group having a viscosity of 0,000,000 cP, and further, a cosmetic containing the silicone emulsion as a main component is excellent in water resistance, oil resistance and weather resistance. It forms a film and has excellent makeup functionality such as moisturizing and smoothness, and also has durability of makeup functionality and stability over time, and further, it has a cationic surfactant and a catalyst component. By emulsion polymerizing a low molecular weight organosiloxane in water in the presence of
It was found that a silicone emulsion containing a polyorganosiloxane having a terminal hydroxyl group and a viscosity of 50,000 to 50,000,000 cP was obtained, and the present invention was completed.

[0016] That is, the silicone emulsions of the present invention is represented by the general formula _{R n SiO (4-n)} / 2 (R is a substituted or unsubstituted monovalent hydrocarbon radical, n is an integer of from 0 to 3) It is obtained by emulsion polymerization of a low molecular weight organosiloxane having a structural unit in the presence of a surfactant, a catalyst component and water, and a viscosity at 25 ° C. of 500,000 to
It is characterized by containing a polyorganosiloxane having a terminal hydroxyl group blocking of 50,000,000 cP.

The cosmetic of the present invention has the general formula R _n Si
A low molecular weight organosiloxane having a structural unit represented by O _{(4-n) / 2} (R is a substituted or unsubstituted monovalent hydrocarbon group, n is an integer of 0 to 3), a surfactant, and a catalyst. And emulsion polymerization in the presence of water
Viscosity at 5 ° C is 500,000 to 50,000,000
It is characterized in that the main component is a silicone emulsion containing a polyorganosiloxane having a terminal hydroxyl group-capping property of cP.

Further, the method for producing the silicone emulsion of the present invention comprises (a) the general formula R _n SiO 2.
Low molecular weight organosiloxane having a basic unit represented by _{(4-n) / 2} (R is a substituted or unsubstituted monovalent hydrocarbon group, n is an integer of 0 to 3), a surfactant, and a catalyst. Mixing the ingredients with water in the presence of water to form an emulsion; and (b) adding the emulsion at 70 to 90 ° C. for 1 to 1
A first reaction step of maintaining for 5 hours, and (c) the first reaction step.
After the reaction step of, the second reaction step of maintaining the temperature at 0 to 40 ° C. for 1 to 500 hours and the step of (d) stopping the second reaction are sequentially performed.

In the first reaction step of the method for producing a silicone emulsion of the present invention, when the reaction temperature is less than 70 ° C. or the reaction time is less than 1 hour, sufficient heat energy is imparted to the low molecular weight organosiloxane. Therefore, it is impossible to produce a satisfactory emulsion because the reaction conversion rate of the low molecular weight organosiloxane as a raw material is low, or the polymerization rate of the polyorganosiloxane produced is slow. On the other hand, when the reaction temperature is higher than 90 ° C, water is evaporated and the emulsion becomes unstable and breaks. Therefore, the reaction temperature is preferably 70 to 90 ° C.
Is set in the range. Further, even if the reaction time exceeds 15 hours, there is no further improvement effect on the polymerization rate, which is disadvantageous in terms of production efficiency. Therefore, the reaction time is preferably 2 to 10 hours when an anionic surfactant is used as the surfactant, and 5 to 15 hours when a cationic surfactant is used as the surfactant. Is set.

In the second reaction step, when the reaction temperature is out of the range of 0 to 40 ° C., the polymerization rate of the polyorganosiloxane produced is slow, which is disadvantageous in terms of production efficiency. Since the tendency of the reaction is different between the case where the surfactant is an anionic surfactant and the case where it is a cationic surfactant, a preferable reaction temperature is when the surfactant is an anionic surfactant. 5 to 35 ° C., 20 to 40 when the surfactant is a cationic surfactant
It is in the range of ° C. Further, since the viscosity of the polyorganosiloxane in the emulsion becomes higher and a cosmetic having good properties can be obtained, the reaction time is 1 to 50.
It is set to 0 hours, preferably 2 to 300 hours.

The method for producing a cationic silicone emulsion according to the present invention includes (a) the general formula R _n SiO 2.
_{(4-n) / 2} (R is a substituted or unsubstituted monovalent hydrocarbon group, n is an integer of 0 to 3), a low molecular weight organosiloxane having a basic unit, and a cationic surfactant. A step of mixing the catalyst component with water in the presence of water to form an emulsion;
A first reaction step maintained at 0 ° C. for 5 to 15 hours;
(C) 1 to 5 at 20 to 40 ° C. after the first reaction step
The method is characterized in that the second reaction step of maintaining for 00 hours and (d) the step of stopping the second reaction are sequentially performed.

In the first reaction step of the method for producing a cationic silicone emulsion of the present invention, when the reaction temperature is less than 70 ° C. or the reaction time is less than 5 hours, sufficient heat is applied to the low molecular weight organosiloxane. Since energy cannot be imparted, the reaction conversion of the low molecular weight organosiloxane as a raw material is low, and the polyorganosiloxane produced has a slow polymerization rate, so that a satisfactory emulsion cannot be produced. On the other hand, when the reaction temperature is higher than 90 ° C, water is evaporated and the emulsion becomes unstable and breaks. Therefore, the reaction temperature is preferably set in the range of 70 to 90 ° C. Also, the reaction time is 1
Even if it exceeds 5 hours, there is no further improvement effect on the polymerization rate, which is disadvantageous in terms of production efficiency. Therefore, the reaction time is preferably 5 to 15 hours, more preferably 5 to 15 hours.
It is set to 10 hours.

In the second reaction step, when the reaction temperature is out of the range of 20 to 40 ° C., the polymerization rate of the polyorganosiloxane produced is slow, which is disadvantageous in terms of production efficiency. Therefore, the reaction temperature is preferably 2
It is set in the range of 0 to 40 ° C. Further, when the reaction time is within 1 hour, the viscosity of the polyorganosiloxane in the emulsion does not reach 50,000 cp or more, and when it exceeds 500 hours, the polymerization reaction has already reached an equilibrium state, which is wasteful. Therefore, the reaction time is 24 to 500 hours in the case of a linear polyorganosiloxane,
In the case of a branched polyorganosiloxane in which units or Q units are introduced, it is preferably about 1 to 250 hours, though it depends on the degree of branching.

In the method for producing a silicone emulsion of the present invention, when an anionic surfactant is used as the surfactant, the viscosity is 500,000 to 50,000.
An anionic emulsion of polyorganosiloxane having a high viscosity of about 10,000 cP can be obtained, and when a cationic surfactant, particularly a quaternary ammonium salt surfactant, is used as a surfactant, it can be obtained conventionally. A cationic emulsion of polyorganosiloxane having a viscosity of about 50,000 to 50,000,000 cP, which could not be obtained, can be obtained.

Here, the structural unit is a monofunctional type, which is a terminal unit of a molecule, M unit, a bifunctional type, which is a linear structural unit, a D unit, a trifunctional type, or a tetrafunctional type, which is a network structural factor. It is a concept that includes a certain T unit or Q unit.

The catalyst component is a substance added to polymerize a low molecular weight organosiloxane in the presence of water, and the surfactant itself may have this function like trimethylsulfonic acid. Therefore, it is not necessary to add it.

The silicone emulsion of the present invention has a viscosity of 500,000 to 50 at 25 ° C. in suspended fine particles.
It contains a polyorganosiloxane with a terminal hydroxyl group capping of, 000,000 cP and at the same time contains a low-molecular weight organosiloxane by-produced, and has a viscosity in suspension fine particles at 25 ° C. of 500,000 to 50,000.
The content of the end-hydroxyl-blocked polyorganosiloxane, which is 10,000 cP, is usually 5 to 60%. The particle size of suspended fine particles in silicone emulsion is usually 1
~ 1000 nm. The suspended fine particles are fine particles dispersed in a dispersion medium of an emulsion, and in the present invention, fine particles made of polyorganosiloxane or the like obtained by emulsion polymerization.

In the cosmetic of the present invention, the viscosity of the silicone emulsion as the main ingredient is 500,000 to
50,000,000 cP, preferably 600,000
~ 20,000,000 cP, particularly preferably 100
A silicone emulsion containing about 5 to 60% of polyorganosiloxane of 10,000 to 10,000,000 cP in suspended fine particles is used. Furthermore, the weight average molecular weight of the polyorganosiloxane is 100,0.
00 to 1,000,000, especially 200,000 to 50
000 is preferred. If the viscosity of the polyorganosiloxane is less than 500,000 cP, stickiness occurs and combability becomes insufficient.

The cosmetic of the present invention comprises a silicone emulsion containing a polyorganosiloxane having a terminal hydroxyl group blocked as a main ingredient, and the silicone emulsion in the cosmetic is 0.1 to 9 as a silicone component.
It is obtained by blending 9.9% by weight, preferably 0.5 to 30.0% by weight. Then, the cosmetic may be used as it is, but if necessary, an arbitrary amount of any component may be added to the cosmetic to the extent that the object of the present invention is not impaired. When the optional ingredients are added, preferably 0.1 to 99.9% by weight of the optional ingredients are added to the cosmetic.

Hydrocarbons such as liquid paraffin, petrolatum, solid paraffin, squalane, and olefin oligomers; and optional esters such as isopropyl palmitate, stearyl stearate, octyldodecyl myristate, and triglyceride 2-ethylhexanoate; Higher alcohols such as lauryl alcohol, cetyl alcohol and stearyl alcohol; paramitic acid,
Higher fatty acids such as stearic acid; moisturizers such as ethylene glycol, propylene glycol, 1,3-butylene glycol, glycerin and sorbitol; titanium oxide,
Inorganic powder such as carbon black, iron oxide, sericite, talc, kaolin, mica; organic powder such as nylon, polytitarene, polyethylene, polyacrylate; solvent such as ethanol; water; various surfactants described later; Bactericidal agents; examples include fragrances. Further, silicone having an arbitrary viscosity whose molecular end is blocked with an alkyl group or a hydroxyl group can be added as an optional component. In this case, it is desirable to add the silicone of any viscosity in the form of an emulsion.

To add the above-mentioned optional components to the cosmetic of the present invention, the main component silicone emulsion containing a polyorganosiloxane having a terminal hydroxyl group and the other optional components are simply mixed uniformly. Alternatively, the components other than the silicone emulsion containing the polyorganosiloxane having a terminal hydroxyl group blocked may be previously emulsified with a homogenizer, colloid mill, line mixer or the like, or uniformly mixed with a stirrer. A silicone emulsion containing a polyorganosiloxane that blocks hydroxyl groups may be added.

The cosmetics of the present invention include hair oils, hair dyes, ski oils, set lotions, tics, bottled oils, hair creams, hair tonics, hair liquids, hair sprays, pomades, shampoos, hair lins, hair oils. Hair conditioners such as conditioners and hair lotions, hand creams,
Used for all products that are applied externally to the skin, including skin creams, foundations, eye shadows, facial cleansers, skin cleansing agents such as skin cleansing and cleaning agents, as well as external medicines whose tactile feel is a problem during use. be able to. In addition, examples of the form of the product include solid, gel, liquid, and paste forms.

The silicone emulsion of the present invention and the silicone emulsion produced by the present invention can be widely applied to cosmetics and applications other than cosmetics, such as release agents for rubber, plastics and shell molds, and electric wires. Lubricants for pulling out cores and ironing, polishing agents for rubber, plastic products or furniture, defoaming agents for latex or pulp waste, fiber treatment agents for imparting water repellency or flexibility to fibers Alternatively, it can be appropriately used for applications such as paint components.

As a method for producing a silicone emulsion containing a high molecular weight end-capped polyorganosiloxane according to the present invention, for example, first, a surfactant such as an anionic surfactant or a cationic surfactant is required. a catalyst component such as potassium hydroxide dissolved in water in accordance with, then the general formula _{R n SiO (4-n)} / 2 (R
Is a substituted or unsubstituted monovalent hydrocarbon group, n is 0 to 3
Of low molecular weight organosiloxane represented by This is roughly emulsified by using an emulsifying machine such as a homomixer, a colloid mill or a line mixer, and further emulsified through an emulsifying machine such as a pressure homogenizer or an ultrasonic homogenizer to obtain an emulsion. Then, as a first reaction step, the emulsion is maintained at 70-90 ° C. for 1-15 hours, then in the second reaction step.
In the reaction step of 1, the emulsion polymerization is promoted by maintaining the temperature at 0 to 40 ° C. for 1 to 500 hours, and the polymerization is stopped when the desired polymer viscosity is reached.

As a method for producing a silicone emulsion containing a polyorganosiloxane having a high molecular weight and a terminal hydroxyl group blocked according to the present invention, for example, first, a cationic surfactant and the like, if necessary, potassium hydroxide and the like are used. The catalyst component is dissolved in water, then the general formula R _n SiO 2
A low molecular weight organosiloxane represented by _{(4-n) / 2} (R is a substituted or unsubstituted monovalent hydrocarbon group, n is an integer of 0 to 3) is added with stirring. This is roughly emulsified by using an emulsifying machine such as a homomixer, a colloid mill or a line mixer, and further emulsified through an emulsifying machine such as a pressure homogenizer or an ultrasonic homogenizer to obtain an emulsion. Then, as a first reaction step, this emulsion is maintained at 70 to 90 ° C. for 5 to 15 hours, and then as a second reaction step, at 20 to 40 ° C. for 1 to 500 hours. The emulsion polymerization is advanced, and the polymerization is stopped when the desired polymer viscosity is reached.

Upon termination of the polymerization, when an anionic surfactant is used as a surfactant, an alkaline substance is added to neutralize it, and when a cationic surfactant is used, an acidic substance is added. By suspending the polymerization by the addition, it is possible to obtain a silicone emulsion in which the main component of the suspended fine particles is a polyorganosiloxane having a high degree of polymerization and having a terminal hydroxyl group blocking, and a by-product, a low molecular weight organosiloxane. it can.

In the method for producing a silicone emulsion according to the present invention, the general formula R _n Si used as a raw material is used.
The low molecular weight organosiloxane represented by O _{(4-n) / 2} (R is a substituted or unsubstituted monovalent hydrocarbon group, n is an integer of 0 to 3) is not particularly limited, but a cyclic polyorganosiloxane, A linear or branched polyorganosiloxane having a molecular chain terminal blocked with a hydroxyl group or an alkoxyl group or a mixture thereof can be preferably used, and usually has a molecular weight of 100 to 5,000, preferably 200 to 1,000 is used.

As the cyclic polyorganosiloxane, the following general formula 1 (wherein R ¹ and R ² are a hydrogen atom, a methyl group, an ethyl group, a propyl group, a vinyl group,
It is preferably a monovalent hydrocarbon group having 1 to 8 carbon atoms such as an allyl group or a phenyl group, and m is an average number of 3 to 8), and specifically, hexamethylcyclotrisiloxane. , Octamethylcyclotetrasiloxane,
Decamethylcyclopentasiloxane, 1,1-diethylhexamethylcyclotetrasiloxane, phenylheptamethylcyclotetrasiloxane, 1,1-diphenylhexamethylcyclotetrasiloxane, 1,2,3,4-
Tetravinyl-1,2,3,4-tetramethylcyclotetrasiloxane, 1,2,3,4-tetramethylcyclotetrasiloxane, dodecamethylcyclohexasiloxane, 1,2,3,4-tetramethyl-1, 2,3,4-
Examples include tetraphenylcyclotetrasiloxane.

Embedded image Further, as the linear or branched polyorganosiloxane, the following general formulas 2 and 3 (in the formula, R ³ is a hydrogen atom, a methyl group, an ethyl group, a propyl group, a vinyl group,
An allyl group, a phenyl group, or another monovalent hydrocarbon group; R ⁴ is a hydrogen atom, a methyl group, an ethyl group, a propyl group, a vinyl group, an allyl group, a phenyl group, or another such carbon number, A monovalent hydrocarbon group, a hydroxyl group or an alkoxy group, and n and l are numbers 0 to 50). Specifically, α, ω-dihydroxypolydimethylsiloxane, α, ω -Dimethoxypolydimethylsiloxane, tetramethyl-1,3-dihydroxydisiloxane, octamethyl-1,7-dihydroxytetrasiloxane, hexamethyl-1,5-diethoxytrisiloxane, etc. are exemplified, and in addition, methyltrimethoxysilane. It is also possible to use a crosslinking agent such as tetraethoxysilane.

[0039]

Embedded image

Embedded image The amount of the low molecular weight organosiloxane used is not particularly limited, but the concentration of the low molecular weight organosiloxane in the reaction system during the emulsion polymerization is 5 to 60% by weight, particularly 10 to 50% by weight. It is preferable that the content be 5% by weight or less, and if it is less than 5% by weight, the efficiency of emulsification becomes poor, and if it exceeds 60% by weight, the viscosity of the emulsion increases and it is not preferable because it is inconvenient for work.

In the method for producing a silicone emulsion of the present invention, the organosiloxane having a low molecular weight of 10 mol% or less, particularly 0.1 to 5 mol% as a siloxane unit (structural unit) is added to the organosiloxane having a low molecular weight. Hydrolyzable organosilane having, or an organosiloxane oligomer having a siloxane unit having an organic functional group may be added and emulsified within a range that does not impair the object of the present invention, and by adding these,
An organic functional group can be introduced into the resulting polyorganosiloxane.

In this case, as the hydrolyzable organosilane, for example, 3-aminopropyldimethoxysilane,
3-aminopropyltrimethoxysilane, Ν- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxy Silane, 3-glycidoxypropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, trifluoropropyltrimethoxysilane, 3-carboxypropylmethyldimethoxysilane, (vinyloxypropyl) methyldimethoxysilane, (vinyloxyethoxypropyl) Methyldimethoxysilane, p-vinylphenylmethyldimethoxysilane, 1- (m-vinylphenyl) methyldimethylisopropoxysilane, 2- (p-vinylphenyl) ethylmethyldimethoxy Run, 3- (p-vinylphenoxy) propyl triethoxysilane, 3- (p-vinyl acetoxyphenyl) propyl methyl dimethoxy silane, 1-
(P-Vinylphenyl) ethylmethyldimethoxysilane, 1- (o-vinylphenyl) -1,1,2-trimethyl-2,2-dimethoxydisilane, 1- (p-vinylphenyl) -1,1-diphenyl- 3-ethyl-3,3
-Diethoxydisiloxane, m-vinylphenyl-
[(3-Triethoxysilyl) propyl] diphenylsilane, [3- (p-isopropenylbenzoylamino)
Propyl] phenyldipropoxysilane, N-methacryloyl-N-methyl-3-aminopropylmethyldimethoxysilane, N-acryloyl-N-methyl-3-aminopropylmethyldimethoxysilane, N, N-bis (methacryloyl) -3- Aminopropyltrimethoxysilane, N, N-bis (acryloyl) -3-aminopropylmethyldimethoxysilane, N-methacryloyl-N
-Methyl-3-aminopropylphenyldiethoxysilane, 1-methacryloxypropyl-1,1,3-trimethyl-3,3-dimethoxydisiloxane, vinylmethyldimethoxysilane, vinylethyldiisopropoxysilane, allylmethyldimethoxysilane , 5-hexenylmethyldiethoxysilane, 3-octenylethyldiethoxysilane and the like can be mentioned, and these are used alone or as a mixture of two or more kinds.

Examples of the organosiloxane oligomer having a siloxane unit having an organic functional group include trimethyltriphenylcyclotrisiloxane, tris (3,3,3-trifluoropropyl) trimethylcyclotrisiloxane, 1,3,5. , 7-Tetra (3-aminopropyl) tetramethylcyclotetrasiloxane,
1,3,5,7-Tetra [N- (2-aminoethyl)-
3-Aminopropyl] tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (3-mercaptopropyl) tetramethylcyclotetrasiloxane, 1,3,3
5,7-Tetra (3-glycidoxypropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-Tetra (3-methacryloxypropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-Tetra (3-acryloxypropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (3-carboxypropyl) tetramethylcyclotetrasiloxane, 1,3,3
5,7-Tetra (vinyloxypropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-Tetra (vinyloxyethoxypropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-Tetra (p-vinyl) Phenyl) tetramethylcyclotetrasiloxane, 1,3
5,7-Tetra [1- (m-vinylphenyl) methyl]
Tetramethylcyclotetrasiloxane, 1,3,5,7
-Tetra [2- (p-vinylphenyl) ethyl] tetramethylcyclotetrasiloxane, 1,3,5,7-tetra [3- (p-vinylphenoxy) propyl] tetramethylcyclotetrasiloxane, 1,3,5 , 7-Tetra [3- (p-pinylbenzoyloxy) propyl] tetramethylcyclotetrasiloxane, 1,3,5,7-tetra- [3- (p-isopropenylbenzoylamino) propyl] tetramethylcyclotetra Siloxane, 1,
3,5,7-Tetra (N-methacryloyl-N-methyl-3-aminopropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (N-acryloyl-
N-methyl-3-aminopropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra [N, N-
Bis (methacryloyl) -3-aminopropyl] tetramethylcyclotetrasiloxane, 1,3,5,7-tetra [Ν, N-bis (acryloyl) -3-aminopropyl] tetramethylcyclotetrasiloxane, 1,3,3
5,7-tetravinyltetramethylcyclotetrasiloxane, octavinylcyclotetrasiloxane, 1,3,
5-trivinyltrimethylcyclotrisiloxane, 1,
3,5,7-Tetraallyltetramethylcyclotetrasiloxane, 1,3,5,7-tetra (5-hexenyl)
Tetramethylcyclotetrasiloxane, 1,3,5,7
Examples include cyclic compounds such as -tetra (7-octenyl) tetramethylcyclotetrasiloxane, and these can be used alone or as a mixture of two or more kinds. In addition to this, an organosiloxane oligomer having a linear or branched organic functional group may be used.

However, when an organosiloxane oligomer containing a linear or branched organic functional group is used,
The terminal of the molecular chain is not particularly limited, but from the viewpoint of easy handling and introduction of the organic functional group into the polyorganosiloxane to be formed, the terminal of the molecular chain is an organic group other than a hydroxyl group, for example, an alkoxy group. , Trimethylsilyl group, dimethylvinylsilyl group, methylphenylvinylsilyl group, methyldiphenylsilyl group, or 3,3,3-
It is preferably blocked with a trifluoropropyldimethylsilyl group or the like.

Next, as anionic surfactants that can be used as the surfactant, aliphatic substituted benzenesulfonic acids, aliphatic hydrogen sulfates, or unsaturated aliphatic sulfones represented by the following general formulas 4 to 7 are used. A mixture of acid and hydroxyaliphatic sulfonic acid is preferably used.

R ⁵ C ₆ H ₄ SO ₃ H ・ ・ ・ 4 R ⁵ OSO ₃ H ・ ・ ・ 5 R ⁶ CH = CΗ (CΗ ₂ ) _n SO ₃ H ・ ・ ・ 6 R ⁶ CHCΗ (OH) (CΗ ₂ ) _m SO ₃ H 7 (wherein R ⁵ is a monovalent aliphatic hydrocarbon group having ^{6 to} 30 carbon atoms, R ⁶ is a monovalent aliphatic hydrocarbon group having 1 to 30 carbon atoms) A hydrogen group, and n and m are integers such that the total number of carbon atoms in the surfactants of formulas 6 and 7 is 6 to 30).

Here, R ⁵ in the formulas 4 and 5 is a monovalent aliphatic hydrocarbon group having 6 to 30 carbon atoms, preferably 6 to 18 carbon atoms, for example, hexyl group, octyl group, decyl group, Examples thereof include dodecyl group, cetyl group, stearyl group, myricyl group, oleyl group, nonenyl group, octynyl group, phytyl group and pentadecadienyl group.

R ⁶ in the formulas 6 and 7 is a monovalent aliphatic hydrocarbon group having 1 to 30 carbon atoms, preferably 6 to 18 carbon atoms. For example, the same monovalent aliphatic hydrocarbon group as R ⁵ is used. A hydrogen group is mentioned.

Such 4 or 5 formula anionic surfactants include hexylbenzenesulfonic acid, octylbenzenesulfonic acid, dodecylbenzenesulfonic acid cetylbenzenesulfonic acid, octylsulfate, laurylsulfate, oleylsulfate, cetylsulfate. Are exemplified.

The anionic surfactant of formula 6 is exemplified by tetradecene sulfonic acid, and the anionic surfactant of formula 7 is exemplified by hydroxytetradecane sulfonic acid.

Furthermore, an anionic surfactant having a weak catalytic action can be used in combination with the polymerization catalyst. As such an anionic surfactant, the above-mentioned 4
Formula aliphatic substituted benzene sulfonic acid, formula 5 aliphatic hydrogen sulphates or formula 6 unsaturated aliphatic sulfonic acid sodium salts, potassium salts, ammonium salts and the like, and specifically dodecylbenzene sulfonic acid sodium salt , Sodium octylbenzenesulfonate, ammonium dodecylbenzenesulfonate, sodium lauryl sulfate, ammonium lauryl sulfate, triethanolamine lauryl sulfate and the like.

In addition to the above-mentioned anionic surfactants of formula 4 or 5, for example, polyoxyethylene (4) lauryl ether sulfate, polyoxyethylene (1
3) polyoxyethylene alkyl ether sulfate such as cetyl ether sulfuric acid, polyoxyethylene (6) stearyl ether sulfuric acid, polyoxyethylene (4) sodium lauryl sulfate, polyoxyethylene (4) octylphenyl ether ammonium sulfate Its salt, polyoxyethylene (3) lauryl ether carboxylic acid,
Polyoxyethylene (3) stearyl ether carboxylic acid, polyoxyethylene (6) sodium lauryl ether carboxylate, polyoxyethylene (6) sodium octyl ether carboxylate and other polyoxyethylene alkyl ether ether carboxylic acid esters or salts thereof, etc. One kind or two or more kinds can be used, but the present invention is not limited thereto.

The polymerization catalyst used in combination with the anionic surfactant is usually an aliphatic-substituted benzenesulfonic acid, an aliphatic hydrogensulfate, or an unsaturated aliphatic sulfone, which is used as a polymerization catalyst for low-molecular weight organosiloxanes. Acidic catalysts such as a mixture of acid and hydroxyaliphatic sulfonic acid, hydrochloric acid, sulfuric acid, phosphoric acid are preferably used, but not limited to these, and a low molecular weight organosiloxane is polymerized in the presence of water. Any catalyst can be used as long as it can be used.

The amount of the anionic surfactant used is 0.1% by weight based on 100 parts by weight of the above-mentioned low molecular weight organosiloxane.
The amount is more preferably 5 to 20 parts by weight, particularly preferably 0.5 to 10 parts by weight. If the amount is less than 0.5 parts by weight, the stability of the emulsion may be poor and separation may occur. The emulsion may thicken and the fluidity may deteriorate. When the polymerization catalyst is used in combination, the amount of the polymerization catalyst used is not particularly limited, but it is preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of the low molecular weight organosiloxane.

Further, as the cationic surfactant which can be used as the surfactant, the following general formula 8 (wherein R ⁷ is a monovalent aliphatic hydrocarbon group having 6 to 30 carbon atoms, R ⁴ , R ⁹ and R ¹⁰ are each a monovalent organic group, and Χ is a hydroxyl group, a chlorine atom or a bromine atom), and a quaternary ammonium salt-based surfactant is preferable.

[0055]

Embedded image In formula 8, R ⁷ is an aliphatic hydrocarbon group having 6 to 30 carbon atoms, preferably 8 to 18 carbon atoms, for example, a hexyl group, an octyl group, a decyl group, a dodecyl group, a cetyl group, a stearyl group, a mylyl group, Examples thereof include an oleyl group, a hexadecyl group, a nonenyl group, an octynyl group, a phytyl group, and a pentadecadienyl group. In addition, R ⁸ , R ⁹ and R ¹⁰
Are monovalent organic groups of the same type or different types, for example, alkyl groups such as methyl group, ethyl group, propyl group, alkenyl groups such as vinyl group and allyl group, aryl groups such as phenyl group, xenyl group, naphthyl group, etc. And cycloalkyl groups such as cyclohexyl group.

Examples of such a quaternary ammonium salt type surfactant of formula 8 include lauryl trimethyl ammonium hydroxide, stearyl trimethyl ammonium hydroxide, dioctyl dimethyl ammonium hydroxide, distearyl dimethyl ammonium hydroxide and lauryl trimethyl chloride. Ammonium, stearyl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, dicocoyl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, benzalkonium chloride, stearyl dimethyl benzyl ammonium chloride, etc. are mentioned, These 1 type, or 2 or more types are used. be able to.

Since the above-mentioned cationic surfactant has a weak catalytic action, it is preferably used in combination with a polymerization catalyst. As the polymerization catalyst used in combination, a hydroxylation usually used as a polymerization catalyst for low molecular weight organosiloxanes is used. Examples thereof include alkali metal hydroxides such as lithium, sodium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide.

The amount of the cationic surfactant used is 0. 100 parts by weight based on 100 parts by weight of the above low molecular weight organosiloxane.
5 to 50 parts by weight, especially 1 to 20 parts by weight is preferable, and if it is less than 0.5 parts by weight, the emulsion itself may have insufficient cationic property and the emulsion may be poor in stability and may be separated. If it exceeds 50 parts by weight, the emulsion may thicken and lose its fluidity. When the polymerization catalyst is used in combination, the amount of the polymerization catalyst used is not particularly limited, but the low molecular weight organosiloxane 100 is used.
It is preferably 0.05 to 10 parts by weight with respect to parts by weight.

Further, in order to improve the stability of the silicone emulsion obtained by emulsion polymerization, a nonionic surfactant is added to the above-mentioned surfactant before or after the emulsion polymerization so long as the object of the present invention is not impaired. You may use it together. As such nonionic surfactants, those having an HLB value of 6 to 20 are preferable, and examples thereof include polyoxyethylene (6) lauryl ether, polyoxyethylene (7) cetyl ether, and polyoxyethylene (7) cetyl ether. Oxyethylene (20) stearyl ether, polyoxyethylene (3) octylphenyl ether, polyoxyethylene (18) nonylphenyl ether, polyethylene glycol monostearate (EO14), polyethylene glycol distearate (EE 80), polyoxyethylene (20 ) Hydrogenated castor oil, polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene monostearate (6)
Sorbitan polyoxyethylene trioleate (20)
Sorbitan, polyoxyethylene tetraoleate (4
0) sorbit, polyoxyethylene (15) glyceryl monooleate, polyoxyethylene (15) glyceryl monostearate, sorbitan monopalmitate, polyoxyethylene (10) behenyl ether, polyoxyethylene (10) phytosterol, polyoxy Ethylene (1) polyoxypropylene (4) cetyl ether, polyoxyethylene (5) stearylamine,
Examples thereof include polyoxyethylene (8) stearyl propylene diamine polyoxyethylene (5) cetyl ether sodium phosphate, but are not limited thereto.

When the nonionic surfactant is used in combination before emulsion polymerization, the amount of the nonionic surfactant is 10.
If the amount exceeds 500 parts by weight relative to 0 parts by weight, it may be a factor that inhibits the polymerization reaction of the low molecular weight organosiloxane.
It is preferable to use parts by weight.

Further, the amount of water added in the present invention is not particularly limited, but is 50 to 2000 parts by weight, particularly 1 part by weight based on 100 parts by weight of the low molecular weight organosiloxane.
It is preferably used in a proportion of 100 to 1000 parts by weight.
If the amount of water added is less than 50 parts by weight with respect to 100 parts by weight of the low molecular weight organosiloxane, the amount of the organosiloxane that is the hydrophobic oil is too large and the emulsion is W / O.
Organosiloxane 1 with a low molecular weight, in which water may not form a continuous layer without phase inversion from the mold to the O / W type.
If it exceeds 2000 parts by weight with respect to 00 parts by weight, the concentration of the organosiloxane may be too low and the emulsification efficiency may deteriorate.

Examples of the alkaline substance used for neutralization include inorganic substances such as sodium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate and potassium acetate, and amines such as ammonia and triethanolamine. Examples of the acidic substance used for this neutralization include organic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, stearic acid and glycolic acid, and inorganic acids.

[0063]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to Examples, in which parts and% are
Unless otherwise specified, they are parts by weight and% by weight.

The average particle size of the suspended fine particles in the obtained silicone emulsion is the laser particle size analysis system LPA-3 manufactured by Otsuka Electronics Co., Ltd., which adopts the dynamic light scattering method.
It was measured using 000S / 3100. The nonvolatile content of the obtained silicone emulsion was measured by heating the silicone emulsion at 105 ° C. for 3 hours to evaporate the nonvolatile content. Further, for measuring the swelling degree and gel content of the polyorganosiloxane having a cross-linking point introduced, a polyorganosiloxane obtained by dropping a silicone emulsion into isopropyl alcohol, coagulating and drying is used. Went by. That is, the degree of swelling was 2 for polyorganosiloxane.
It was determined as a value obtained by dividing the weight of toluene occluded by the polyorganosiloxane when immersed in toluene at 3 ° C. for 48 hours by the weight of the polyorganosiloxane before immersion. The gel content was determined by subjecting polyorganosiloxane to extraction treatment in toluene at 23 ° C. for 48 hours. Furthermore, the measurement of the organic functional group content of the polyorganosiloxane introduced with an organic functional group was carried out by the same method as in the measurement of the swelling degree, with respect to the polyorganosiloxane obtained by coagulation and drying, manufactured by Nippon Bruker Co., Ltd. Nuclear magnetic resonance spectrometer A
It was carried out by performing a 1Η-ΝMR analysis using M-300.

Example 1 100 parts of octamethylcyclotetrasiloxane was added to a mixed solution of 2 parts of n-dodecylbenzene sulfonic acid (manufactured by Nissan Chemical Industries, Ltd., Soft Oarai 5S) and 150 parts of distilled water. , After pre-stirring with a homomixer, 300 kgf / with a pressure homogenizer
The mixture was emulsified and dispersed by passing it twice at a pressure of cm ² . The emulsion was transferred to a separable flask equipped with a condenser, nitrogen inlet and stirrer and heated at 85 ° C. for 5 hours with stirring and mixing, then 2 hours over 3 hours.
After gradually cooling and stirring to 5 ° C., the polymerization reaction was allowed to proceed in the second reaction step by further cooling and stirring at 25 ° C. for 5 hours. Then, this emulsion was subsequently neutralized to pH 7 with a 10% aqueous sodium carbonate solution to stop the polymerization reaction, to obtain a polydimethylsiloxane emulsion. This is Emulsion A.

The nonvolatile content of the obtained emulsion A is 3
It was 6.5%, and the average particle size of the suspended fine particles was 275 nm.

Further, the emulsion A was destroyed with isopropyl alcohol, the silicone polymer was taken out, and IR
As a result of analysis, it was confirmed that this was a dimethyl silicone polymer having hydroxyl groups sealed at both ends, and the viscosity at 25 ° C. was measured and found to be 98,000 cP.

To evaluate the stability of centrifugation, 10 ml of Emulsion A was placed in a centrifuge tube, and 3000
After being subjected to a separator at rpm for 15 minutes, the nonvolatile content of the upper layer and the lower layer was measured to be 36.5% and 3%, respectively.
At 6.4%, there was almost no difference. Furthermore, in order to evaluate the dilution stability, a 50 times water-diluted solution of Emulsion A was allowed to stand at 40 ° C for 24 hours, and the appearance, especially the liquid surface condition, was visually observed.
It was a stable emulsion with no abnormalities.

Water was added to this emulsion A so that the silicone concentration was 0.4% to prepare a rinse agent a-1. Emulsion A was diluted with an aqueous 5% ethanol solution to a silicone concentration of 0.4%.
A rinse agent a-2 was prepared. Similarly 10 and 20%
Silicone concentration is 0.4 using ethanol aqueous solution
The rinsing agents a-3 and a-4 were prepared so as to be%.

Each of these rinse agents a-1 to a-4 is 2
100 cc each in a glass bottle, one at 25 ℃
Left for 60 days, and the other one every 5 hours at 5 ℃
It was left for 60 days in an environmental tester set to repeat a temperature cycle of 50 ° C., and the stability of each was visually observed. The results are shown in Table 1 (results of standing at 25 ° C. for 60 days) and Table 2 (results of repeating a temperature cycle of 5 ° C. to 50 ° C. every 24 hours for 60 days).

[0071]

[Table 1]

[Table 2] In addition, rinse agents a-1 and a-4 immediately after production, and 24
By repeating the temperature cycle of 5 ° C to 50 ° C every hour and using the rinse agents a-1 and a-4 after standing for 60 days, the improvement rate of combability of hair was evaluated (calculated) according to the following procedure. .

[Combability improvement rate] <Pretreatment of hair> 12 g of a hair bundle having a length of 20 cm is washed with a 1% by weight aqueous sodium lauryl sulfate solution, rinsed with warm water, and dried with a dryer. Dip this in water for 30 seconds, wrap it with a towel, and apply 5 kg under a pressure of 20 kg / 314 cm ^2.
Drain for seconds and brush until there is no catch.

<Rinse Agent-treated Hair> The pretreated hair is immersed in the rinse agent for 1 minute, then immersed in warm water for 30 seconds, wrapped with a towel, and drained for 5 seconds under a pressure of 20 kg / 314 cm ² to eliminate snagging. Brush up to.

<Measurement of Combability> Using a “tension universal tester” manufactured by Tester Sangyo Co., Ltd., a comb was set on a moving table, one end of the treated hair was fixed, and the hair bundle was fixed on the moving table. Read the maximum value of the pulling force when moving the moving table at 200 mm / min through the comb.

The combing passability measurement was performed on the hair pretreated only and the hair treated with the rinse agent, and the combing passability improvement rate was evaluated (calculated) by the following formula.

Tensile force of hair pretreated only = Α Rinse agent treatment Tensile force of hair = Β Combability improvement rate [%] = (Α-Β) / A × 100 Further, the hair was treated with a rinse agent immediately after production. The comb combability improvement rate was also evaluated for the hair washed five times in the same manner as in the above-mentioned “<Pretreatment of hair>”. Table 3 shows the results.

[0077]

[Table 3] (Comparative Example 1) 100 parts of polydimethylsiloxane (viscosity 1,000,000 cP) with hydroxyl groups blocked at both ends, 10 parts of polyoxyethylene (9) lauryl ether (NIKKOL BL-9EX manufactured by Nikko Chemicals Co., Ltd.) and water. After 20 parts were uniformly mixed, the mixture was emulsified using a colloid mill, and this was uniformly dispersed in 160 parts of water to obtain a mechanically emulsified polydimethylsiloxane emulsion (referred to as emulsion B). The nonvolatile content of the obtained emulsion B was 37.5%, and the average particle size of suspended fine particles was 820 nm. In order to evaluate the stability of centrifugation, 10 ml of emulsion B was placed in a centrifuge tube and subjected to a separator at 3000 rpm for 15 minutes, and then the nonvolatile content of the upper layer and the lower layer was measured.
The difference was 2.3% and 32.1%, and there was a difference of about 10%. Furthermore, to evaluate the dilution stability, Emulsion B
When the appearance, especially the liquid surface state, was examined by leaving a 50-fold diluted water solution of 40 times at 40 ° C for 24 hours, a slight amount of an oily substance considered to be polydimethylsiloxane was deposited on the liquid surface, and stability was confirmed. It was an emulsion with problems.

Using this emulsion B, water and 5, 1 were added so that the silicone concentration became 0.4%.
Rinsing agent b-1 to b-with 0, 20% ethanol aqueous solution
4 was prepared and left in an environmental tester set to repeat a temperature cycle of 5 ° C to 50 ° C every 24 hours for 60 days at 25 ° C as in Example 1, and then to stabilize each of them. Was visually observed. The results are shown in Table 1 (results of leaving at 25 ° C. for 60 days) and Table 2 (24
The result of repeating the temperature cycle of 5 ° C. to 50 ° C. every hour for 60 days) is shown.

In addition, rinse agents b-1 and b immediately after production
-4, a rinse agent b after the temperature cycle of 5 ° C to 50 ° C was repeated every 24 hours and left for 60 days
-1 and b-4, and hair immediately after the preparation, which was treated with rinsing agents b-1 and b-4, washed 5 times by the same method as the above-mentioned "<Pretreatment of hair>". The combability improvement rate was tested in the same manner as in Example 1. Table 3 shows the results.

(Example 2) 30% cetyltrimethylammonium chloride aqueous solution (manufactured by Kao Corporation, Kotamine 6)
0 W, active ingredient 30%) 6.7 parts, polyoxyethylene (18) nonyl phenyl ether (manufactured by Nikko Chemicals, NIKKOL NP-18TX; Η LΒ1
9) 4 parts, 0.5 parts potassium hydroxide and 150 distilled water
100 parts of octamethylcyclotetrasiloxane was added to the mixed solution of 1 part and after preliminarily stirring with a homomixer,
The mixture was emulsified and dispersed by passing it twice through a pressure homogenizer at a pressure of 300 kgf / cm ² .

The emulsion was transferred to a separable flask equipped with a condenser, a nitrogen inlet and a stirrer,
Heat at 85 ° C. for 10 hours with stirring and mixing, then cool to 25 ° C. over 3 hours, then cool at 168 ° C. at 168
The polymerization reaction proceeded by holding for a time. And
Subsequently, this emulsion was neutralized to pH7 with acetic acid to terminate the polymerization reaction, to obtain a polydimethylsiloxane emulsion (this is referred to as emulsion C).

The nonvolatile content of the obtained emulsion C is 3
It was 6.2%, and the average particle size of the suspended fine particles was 203 nm. Furthermore, this emulsion C is destroyed with isopropyl alcohol, the silicone polymer is taken out, and
As a result of analysis, it was confirmed that this was a dimethyl silicone polymer with both end hydroxyl groups blocked, and the viscosity at 25 ° C. was measured and found to be 845,000 cP.

To evaluate the stability of centrifugation, 10 ml of Emulsion C was placed in a centrifuge tube, and 3000
After applying a separator for 15 minutes at rpm, the nonvolatile content of the upper and lower layers was measured to be 36.2% and 3%, respectively.
The difference was 6.1%, and there was almost no difference. Further, in order to evaluate the dilution stability, a 50 times water dilution of Emulsion C was allowed to stand at 40 ° C. for 24 hours, and the appearance, especially the liquid surface state was examined with the naked eye. It was

Then, using this emulsion C, water and 5,1 were added so that the silicone concentration became 0.4%.
Rinsing agent c-1 to c- with a 0,20% ethanol aqueous solution
2 was prepared and left for 60 days in the same manner as in Example 1 at 25 ° C. and for 60 days in an environmental tester set to repeat a temperature cycle of 5 ° C. to 50 ° C. every 24 hours, and each stability was evaluated. Was visually observed. The results are shown in Table 4 (results of standing at 25 ° C. for 60 days) and Table 5 (24
The result of repeating the temperature cycle of 5 ° C. to 50 ° C. every hour for 60 days) is shown.

[0085]

[Table 4]

[Table 5] In addition, the hair treated with the rinse agents c-1 and c-4 immediately after the production, the rinse agents c-1 and c after the temperature cycle of 5 ° C to 50 ° C was repeated every 24 hours and left for 60 days
-4 treated hair and a rinse agent c-1 immediately after production
The combability improvement rate was tested in the same manner as in Example 1 with respect to the hair treated with c-4 and c-4, which was washed 5 times by the same method as in the above-mentioned "<Pretreatment of hair>". The results are shown in Table 6.

[0086]

[Table 6] (Examples 3 to 6 and Comparative Examples 2 to 3) Silicone emulsions D to I were prepared in the same manner as in Example 1 except that the raw materials used and -part of the production conditions were changed.
The raw material composition of each emulsion, the production conditions and its characteristics are shown in Table 7 (in the table, (A), (D) to (I) represent each emulsion).

[0087]

[Table 7] Then, using each emulsion, a rinse agent was prepared with a 20% aqueous ethanol solution so that the silicone concentration was 0.4%, and the rinse agent was allowed to stand at 25 ° C. for 60 days in the same manner as in Example 1 and 5 ° C. every 24 hours. The sample was left for 60 days in an environmental tester set to repeat a temperature cycle of 50 ° C., and the stability of each was visually observed. Furthermore, hair treated with a rinse agent immediately after production, hair treated with a rinse agent after repeating a temperature cycle of 5 ° C. to 50 ° C. every 24 hours and left for 60 days, and hair treated with a rinse agent immediately after production In the same manner as in "<Pretreatment of hair>" described above.
With respect to the one that was washed twice, the combing improvement rate was tested in the same manner as in Example 1. The results are also shown in Table 7.

(Examples 7 to 11 and Comparative Examples 4 to 5) In order to confirm the effect of introducing a crosslinking point and an organic functional group, the same as Example 1 except that the part of the raw material used was changed. Silicone emulsions G to P were prepared in the same manner.
Then, the degree of swelling and gel content were measured for the emulsion having the cross-linked points introduced, and the content of the organic functional group was measured by ¹ H-NMR for the emulsion having the organic functional group introduced. Table 8 shows the raw material composition, production conditions and characteristics of each emulsion.

[0089]

[Table 8] Then, using each emulsion, a rinse agent was prepared with a 20% aqueous ethanol solution so that the silicone concentration was 0.4%, and the rinse agent was allowed to stand at 25 ° C. for 60 days in the same manner as in Example 1 and 5 ° C. every 24 hours. The sample was left for 60 days in an environmental tester set to repeat a temperature cycle of 50 ° C., and the stability of each was visually observed. Furthermore, hair treated with a rinse agent immediately after production, hair treated with a rinse agent after repeating a temperature cycle of 5 ° C. to 50 ° C. every 24 hours and left for 60 days, and hair treated with a rinse agent immediately after production In the same manner as in "<Pretreatment of hair>" described above.
With respect to the one that was washed twice, the combing improvement rate was tested in the same manner as in Example 1. The results are also shown in Table 8.

(Example 12, Comparative Example 6; Shampoo Composition) Using the emulsions A to C prepared in Examples 1 and 2 and Comparative Example 1, shampoo composition No. 1 having the composition shown in Table 9 was used. 1-3 were prepared. Then, using these compositions, the stability under a temperature cycle of 60 days was tested in the same manner as in Example 1, and the state was visually observed.

The shampoo composition after repeating the temperature cycle for 60 days was diluted 100 times with water, 10 ml of this solution was placed in a 100 ml measuring cylinder, and vigorously shaken 10 times, and after 1 minute. The volume of the foam portion was measured to confirm the foamability (foamability test). The results are shown in Table 9.

[0092]

[Table 9] (Example 13, Comparative Example 7; Hair Conditioner Composition) Using the emulsions A to C prepared in Examples 1 and 2 and Comparative Example 1, hair conditioner composition No. 1 having the composition shown in Table 10 was obtained. 1-3 were prepared. Then, using these compositions, the stability under a temperature cycle of 60 days was tested in the same manner as in Example 1, and the state was visually observed.

Further, the hair conditioner composition after repeating the temperature cycle and left for 60 days was diluted two-fold with water, and the same combability improving rate test as in Example 1 was carried out. The results are shown in Table 10.

[0094]

[Table 10] (Example 14, Comparative Example 8; Hair Treatment Composition)
Emulsion A prepared in Examples 1 and 2 and Comparative Example 1
To C, the hair treatment composition No. 1 having the composition shown in Table 11 was used. 1-3 were prepared. Then, using these compositions, the stability under a temperature cycle of 60 days was tested in the same manner as in Example 1, and the state was visually observed.

Further, the same combability improving rate test as in Example 1 was carried out using the hair treatment composition after repeating the temperature cycle and leaving it for 60 days as it was. Further, after the combing improvement rate test, the treated hair was dried, and the glossiness of the hair was visually observed. Table 11 shows the results.

[0096]

[Table 11] (Example 15, Comparative Example 9; hair dye composition) Examples 1, 2
Using the emulsions A to C prepared in Comparative Example 1 and the hair dye composition No. 1 having the composition shown in Table 12. The first to third preparations were prepared. Further, using the first agents of these compositions, the stability under a temperature cycle of 60 days was tested in the same manner as in Example 1, and the state was visually observed.

Further, after repeating the temperature cycle and leaving for 60 days, the hair dye composition No. 1 to 3 of each
The second agent was added to the agent to prepare a hair dye solution, and the hair dyeability was evaluated as follows.

That is, first, a hair bundle having a length of 20 cm and a weight of 12 g was immersed in 500 ml of this hair dye solution for 20 minutes to dye hair. Then, this hair bundle was immersed in an aqueous solution of 1% by weight sodium lauryl sulfate for 10 minutes for washing, rinsed thoroughly with warm water at 40 ° C., and dried in a hot air circulation oven at 50 ° C. for 1 hour. In addition, a blank except that the emulsion A in the first part of the hair dye composition was removed was prepared, and hair treatment was performed in the same manner. Then, the effect of hair dyeing on the obtained hair dyeing was evaluated depending on how many out of 10 judges judged the hair to be darker than the blank. The results are shown in Table 12.

[0099]

[Table 12] (Example 16, Comparative Example 10; Cold Perm Composition)
Emulsion A prepared in Examples 1 and 2 and Comparative Example 1
To C, the cold perm composition No. 1 having the composition shown in Table 13 was used. The first to third preparations were prepared.

Further, cold perm composition No. 1 having the composition shown in Table 13 was used. The first agent of 4 is emulsion A to C
It was prepared as a blank for comparison containing neither of the above. Then, using the first agents of these compositions, the stability under a temperature cycle of 60 days was tested in the same manner as in Example 1, and the state was visually observed.

Further, after the temperature cycle was repeated and left standing for 60 days, the cold perm composition No. The second agent was added to each of the first to third agents to prepare a cold perm solution, and the perm agent treatment was performed as described below to evaluate glossiness and curl retention.

That is, first, the cold perm solution 500
A curler (diameter 25 mm, width 70 mm) in which a hair bundle of 20 cm in length and 12 g in weight is wound around 10 ml at 25 ° C.
Soak for minutes. Next, the hair bundle removed from the curler was washed in a 1% by weight aqueous sodium lauryl sulfate solution and rinsed with warm water. Then, this hair bundle was dried in the same manner as in Example 1 and the combability improvement rate was measured.

On the other hand, the hair was dried by leaving it at room temperature, and the glossiness was visually evaluated. Furthermore, the hair bundle whose glossiness was judged was wrapped with cellophane tape, and the temperature was 30 ° C and the relative humidity was 9
Suspend for 24 hours in an environmental tester under 0% conditions,
The curl retention was measured. The curl retention is 24
The wave length was evaluated before standing for 24 hours and after standing for 24 hours. The results are shown in Table 13.

[0104]

[Table 13] (Example 17, Comparative Example 11; Hairblow Composition) Using the emulsions A to C prepared in Examples 1 and 2 and Comparative Example 1, the hairblow composition No. 1 having the composition shown in Table 14 was used.
1-3 were prepared. And using these compositions,
The stability under a temperature cycle of 60 days was tested in the same manner as in Example 1, and the state was visually observed.

Further, the same combability improvement rate test as in Example 1 was carried out using the hair blow composition after repeating the temperature cycle and leaving it for 60 days as it was. In addition,
The treatment of the hair bundle with the hair-blowing composition was carried out by filling the hair-blowing composition in a dispenser container and spraying it uniformly in a mist state, and subjected to a combability improvement rate test without post-washing. Further, the glossiness of the hair after this test was visually observed. The results are shown in Table 14.

[0106]

[Table 14] (Example 18, Comparative Example 12; foamy hair setting agent composition)
Emulsion A prepared in Examples 1 and 2 and Comparative Example 1
To C, the foamy hair setting composition No. 1 having the composition shown in Table 15 was used. 1-3 were prepared. Then, using these compositions, the stability under a temperature cycle of 60 days was tested in the same manner as in Example 1, and the state was visually observed.

Further, the same combability improvement rate test as in Example 1 was conducted using the foamy hair setting agent composition after repeating the temperature cycle and leaving it for 60 days.

The treatment of the hair bundle with the foamy hair setting agent composition is carried out by filling the foamy hair setting agent composition in a dispenser container, directly putting out an appropriate amount on the hair bundle, and uniformly stretching with a comb. Was subjected to the combability improvement rate test without performing. Then, the treated hair after this test was sufficiently dried, and the glossiness of the hair was visually observed. The results are shown in Table 15.

[0109]

[Table 15] (Example 19, Comparative Example 13; skin cream composition)
Of the compositions shown in Table 16, the oil phase component and the water phase component were separately heated to 70 ° C. and uniformly mixed.
Next, the oil phase mixed solution was added to the aqueous phase mixed solution, and further mixed with a homomixer and cooled. When the temperature reached 45 ° C., the emulsions A to C prepared in Examples 1 and 2 and Comparative Example 1 were added, and the mixture was cooled to room temperature (25 ° C.) with uniform mixing to give a skin cream composition N.
o. 1-3 were prepared. Then, using these compositions, the stability under a temperature cycle of 60 days was tested in the same manner as in Example 1, and the state was visually observed.

Further, the skin cream composition after repeating the temperature cycle for 60 days, was actually used as a skin cream, the feeling of use, the adhesiveness when holding a cup after use, and 5 The water repellency after repeated washing was evaluated by conducting a monitor test by 10 people. These results are
It is also shown in Table 6.

[0111]

[Table 16] (Example 20, Comparative Example 14; Liquid foundation composition) Liquid foundation composition No. 10 shown in Table 17.
1-3 were prepared by the following procedure.

[Procedure 1] Preparation of pigment component: A predetermined pigment component is thoroughly mixed and ground in a ball mill.

[Procedure 2] Preparation of water phase component: water at 70 ° C
After heating, add bentonite and stir and mix thoroughly.
Next, propylene glycol and glycerin are dispersed in sodium carboxycellulose, and this is added and dissolved in an aqueous bentonite solution. To this, triethanolamine and methylparaben are added and dissolved.

[Procedure 3] Preparation of oil phase components: All of the oil phase components are heated and melted at 80 ° C.

[Procedure 4] The pigment component obtained in Procedure 1 is added to the aqueous phase component obtained in Procedure 2, uniformly dispersed by a homomixer, and kept at 70 ° C.

[Procedure 5] The oil phase component at 80 ° C. obtained in Step 3 was mixed with the solution at 70 ° C. in which the pigment component obtained in Step 4 was dispersed, and then cooled. Liquid emulsion compositions Nos. 1 and 2 and emulsions A to C prepared in Comparative Example 1 were added, and the mixture was cooled to room temperature (25 ° C.) with uniform mixing. 1-3 are obtained.

Then, using these compositions, the stability under a temperature cycle of 60 days was tested in the same manner as in Example 1, and the state was visually observed.

Further, the following transferability test was conducted using the liquid foundation composition after repeating the temperature cycle and leaving it for 60 days.

[Test Method] First, a filter paper impregnated with water or squalene is prepared. Then, the liquid foundation composition is applied to the filter paper and a dried nylon plate is pressure-bonded to the filter paper to move it up and down 10 times. After the vertical movement is completed, the transfer amount of the sample from the nylon plate onto the filter paper is judged by the naked eye based on the color density, and evaluated by the following scores. The evaluation is an average value of the scores of a total of 5 tests.

Score 1: No transfer is made.

Rating 2: Slight transfer.

Score 3: Marked transfer.

The results are also shown in Table 17.

[0124]

[Table 17] (Example 21, Comparative Example 15; Moisture lotion composition) Of the compositions shown in Table 18, the oil phase component and the aqueous phase component were separately heated to 70 ° C and uniformly mixed. Next, the oil phase mixed solution was added to the aqueous phase mixed solution, further mixed with a homomixer and cooled. When the temperature reached 45 ° C., the emulsions A to C prepared in Examples 1 and 2 and Comparative Example 1 were added, and the mixture was cooled to room temperature (25 ° C.) with uniform mixing to give Moisture Lotion Composition No. ． 1-3 were prepared. Then, using these compositions, the stability under a temperature cycle of 60 days was tested in the same manner as in Example 1, and the state was visually observed. The moisture lotion composition after repeating the temperature cycle for 60 days was actually used as a moisture lotion, and the feeling of use was evaluated by conducting a monitor test by 10 persons. The results are shown in Table 18 together.

[0125]

[Table 18] (Example 22, Comparative Example 16; Emulsion composition) Of the compositions shown in Table 19, the oil phase component and the aqueous phase component were separately heated to 70 ° C and uniformly mixed. Next, the oil phase mixed solution was added to the aqueous phase mixed solution, further mixed with a homomixer and cooled. When the temperature reached 45 ° C., Example 1,
Emulsions A to C prepared in Comparative Example 1 and Comparative Example 1 were added, and the mixture was cooled to room temperature (25 ° C.) with uniform mixing. 1-3 were prepared. Then, using these compositions, the stability under a temperature cycle of 60 days was tested in the same manner as in Example 1, and the state was visually observed. Moreover, the emulsion composition after repeating the temperature cycle and left for 60 days was actually used as an emulsion, and the feeling of use was evaluated by carrying out a monitor test by 10 persons. The results are shown in Table 19.

[0126]

[Table 19] (Example 23, Comparative Example 17; skin cleansing and cleaning composition)
Of the compositions shown in Table 20, the oil phase component and the aqueous phase component were separately heated to 70 ° C. and uniformly mixed. Next, the oil phase mixed solution was added to the aqueous phase mixed solution, further mixed with a homomixer and cooled. When the temperature reached 45 ° C., the emulsions A to C prepared in Examples 1 and 2 and Comparative Example 1 were added, and the mixture was further uniformly mixed at room temperature (25
(C) and then the skin cleansing and cleaning composition No. 1 to
3 was prepared. Then, using these compositions, the stability under a temperature cycle of 60 days was tested in the same manner as in Example 1, and the state was visually observed. In addition, after the temperature cycle was repeated and left for 60 days, the tissue paper was impregnated with an appropriate amount of the skin cleansing / washing agent composition and used for cleaning / washing the skin.
It was conducted by conducting a monitor test by name.
The results are shown in Table 20.

[0127]

[Table 20] (Examples 24 to 30 and Comparative Examples 18 to 22) 30% cetyltrimethylammonium chloride aqueous solution (Kao Co., Ltd., Kotamin 60W, active ingredient 30%) 6.7
Part, polyoxyethylene (18) nonylphenyl ether (manufactured by Nikko Chemicals Co., Ltd., NIKKOL NP-1)
8 TX; Η L 19) 4 parts, 0.5 parts of potassium hydroxide and 150 parts of distilled water were added with 100 parts of octamethylcyclotetrasiloxane, and after preliminarily stirring with a homomixer, 300 kg with a pressure homogenizer.
The mixture was emulsified and dispersed by passing it twice at a pressure of f / cm ² .

The emulsion was transferred to a separable flask equipped with a condenser, a nitrogen inlet and a stirrer,
Heat at 85 ° C. for 10 hours with stirring and mixing, then 8
After cooling to 40 ° C over a period of 24 hours,
The polymerization reaction proceeded by holding for a time. continue,
This emulsion was neutralized to pΗ7 with acetic acid to terminate the polymerization reaction to obtain a polyorganosiloxane emulsion (Example 1).

The nonvolatile content of the obtained polyorganosiloxane emulsion was 36.2%, and the average particle size of suspended fine particles was 203 nm. Further, this polyorganosiloxane emulsion was destroyed with isopropyl alcohol, the silicone polymer was taken out and subjected to ΙR analysis. As a result, it was confirmed that this was a dimethylsilicone polymer, and the viscosity at 25 ° C was measured.
It was 4,800 cP.

In order to evaluate the stability of centrifugation, 10 ml of this polyorganosiloxane emulsion was put into a centrifuge tube and subjected to a separator at 3000 rpm for 15 minutes, and then the non-volatile content of the upper and lower layers was measured.
There was almost no difference between 36.2% and 36.1%, respectively. Furthermore, in order to evaluate the dilution stability, 4 times a 50 times water dilution of this polyorganosiloxane emulsion was used.
After standing for 24 hours at 0 ° C., the appearance, particularly the liquid surface state, was visually inspected, but there was no abnormality at all, and it was a stable emulsion.

Further, in order to confirm the influence of the heating conditions (first reaction step) on the viscosity of the polyorganosiloxane emulsion, the polyorganosiloxane emulsion was prepared in the same manner as in Example 1 except that the heating conditions were changed. Was adjusted. The temperature emulsion C was tested under the same conditions as in Example 1 and evaluated in the same manner (Examples 25 to 30 and Comparative Examples 18 to 22).

Table 21 shows the production conditions of each polyorganosiloxane emulsion and the obtained properties. Table 2
In 1, the heating temperature and the heating time indicate the reaction time and the reaction temperature in the first reaction step, and the aging temperature and the aging time indicate the reaction time and the reaction temperature in the second reaction step. The arrow indicates that the conditions are the same as those on the left.

[0133]

[Table 21] (Examples 31 to 36 and Comparative Examples 23 to 27) In order to confirm the effect of the aging conditions (second reaction step) on the viscosity of the polyorganosiloxane emulsion, the aging conditions were changed in Example 1 except that the aging conditions were changed. A polyorganosiloxane emulsion was prepared in the same manner as in 1.

Table 22 shows the production conditions of each polyorganosiloxane emulsion and the characteristics obtained. Table 2
In 2, the heating temperature and the heating time indicate the reaction time and the reaction temperature in the first reaction step, and the aging temperature and the aging time indicate the reaction time and the reaction temperature in the second reaction step. The arrow indicates that the conditions are the same as those on the left.

[0135]

[Table 22] (Examples 37 to 41) Polyorganosiloxane emulsions were prepared in the same manner as in Example 1 except that the starting materials used were changed in order to confirm the permissible range of the starting materials. Table 23 shows the raw material composition of each polyorganosiloxane emulsion and the characteristics obtained.

[0136]

[Table 23] (Examples 42 to 47) In order to confirm the cross-linking point and the introduction property of the organic functional group, some of the raw materials used in Example 1 were added,
A polyorganosiloxane emulsion was prepared in the same manner as in Example 1 except that the production conditions were changed. Table 24 shows the raw material composition of each polyorganosiloxane emulsion, the production conditions and the obtained properties.

[0137]

[Table 24]

[0138]

As described above, according to the present invention, since a low molecular weight organosiloxane is highly polymerized by emulsion polymerization, a silicone emulsion containing a polyorganosiloxane having a terminal hydroxyl group with high viscosity is obtained. Can be provided.

Further, according to the present invention, since the main component is the silicone emulsion containing the polyorganosiloxane having a high-viscosity terminal hydroxyl group-sealing, it is excellent in water resistance, oil resistance and weather resistance on hair and skin. A film can be easily formed to provide moisture and smoothness for a long period of time, and when used as a hair cosmetic, it has excellent effects of preventing and protecting hair from damage, and the effect does not easily deteriorate even after washing hair. When used as a skin cosmetic, it has a good feeling of use, is resistant to water and sweat, and has a high affinity for the skin. It is possible to provide a cosmetic composition which is excellent in stability by mixing and stability during storage.

Further, according to the present invention, it is possible to provide a method for producing a silicone emulsion containing a polyorganosiloxane having a high viscosity by polymerizing a low molecular weight organosiloxane by emulsion polymerization.

Further, according to the present invention, by emulsion-polymerizing a low molecular weight organosiloxane using a cationic surfactant, the stability is high and the viscosity is high under the production conditions that are easy to manage and are industrially advantageous. A method for producing a cationic silicone emulsion containing a high polyorganosiloxane can be provided.

Therefore, the present invention has an extremely great industrial significance.

[0143]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location A61K 7/08 A61K 7/08 7/09 7/09 7/11 7/11 7/13 7 / 13 7/48 7/48 7/50 7/50 B01J 13/00 B01J 13/00 A C08L 83/06 LRT C08L 83/06 LRT

Claims (4)

[Claims] 1. A low molecular weight compound having a structural unit represented by the general formula R _n SiO _{(4-n) / 2} (R is a substituted or unsubstituted monovalent hydrocarbon group, and n is an integer of 0 to 3). It is obtained by emulsion polymerization of an organosiloxane in the presence of a surfactant, a catalyst component and water, and further has a viscosity at 25 ° C. of 500,0.
A silicone emulsion comprising a polyorganosiloxane having a terminal hydroxyl group blocking of from 50 to 50,000,000 cP. 2. A low molecular weight compound having a structural unit represented by the general formula R _n SiO _{(4-n) / 2} (R is a substituted or unsubstituted monovalent hydrocarbon group, and n is an integer of 0 to 3). It is obtained by emulsion polymerization of an organosiloxane in the presence of a surfactant, a catalyst component and water, and further has a viscosity at 25 ° C. of 500,0.
A cosmetic, which comprises a silicone emulsion containing a polyorganosiloxane having a terminal hydroxyl group of 0 to 50,000,000 cP as a main ingredient. (A) General formula R _n SiO
Low molecular weight organosiloxane having a basic unit represented by _{(4-n) / 2} (R is a substituted or unsubstituted monovalent hydrocarbon group, n is an integer of 0 to 3), a surfactant, and a catalyst. Mixing the components in the presence of water to form an emulsion, and (b) the emulsion at 1
A first reaction step of maintaining for 15 hours, (c) a second reaction step of maintaining at 0 to 40 ° C. for 1 to 500 hours after the first reaction step, and (d) the first reaction step. A process for producing a silicone emulsion, which comprises sequentially performing the step of stopping the reaction of 2. (A) General formula R _n SiO
_{(4-n) / 2} (R is a substituted or unsubstituted monovalent hydrocarbon group, n is an integer of 0 to 3), a low molecular weight organosiloxane having a basic unit, and a cationic surfactant. A step of mixing the catalyst component with water in the presence of water to form an emulsion;
A first reaction step maintained at 0 ° C. for 5 to 15 hours;
(C) 1 to 5 at 20 to 40 ° C. after the first reaction step
A method for producing a silicone emulsion, which comprises sequentially performing a second reaction step of maintaining for 00 hours and (d) a step of stopping the second reaction.