JP6445416B2 - Oil-in-water organopolysiloxane emulsion and hair cosmetic - Google Patents

Description

  The present invention relates to an oil-in-water organopolysiloxane emulsion and a hair cosmetic.

In recent years, it has been known that hair is damaged by permanent, decolorization, hair dyeing, coloring, etc. In order to impart gloss, smoothness and flexibility to this damaged hair, organopolysiloxane is used as a hair repair agent and protective agent. Has been used. Examples of the organopolysiloxane include low viscosity to gum-like high polymer dimethylpolysiloxane, amino-modified organopolysiloxane, and the like. Amino-modified organopolysiloxane is known to have an amino group in the molecule, so that it is easily adsorbed on the hydrophilic part of the hair, and is excellent in surface protection and flexibility imparting effect by polysiloxane (Patent Document) 1, Patent Document 2). Since these organopolysiloxanes are difficult to handle and have poor workability when the viscosity is 1 million mm ² / s or more, hair cosmetics are prepared using a mixture diluted with a low-viscosity oil or an emulsion thereof. In the case of an emulsion, for the purpose of improving the adsorptivity of the organopolysiloxane to the hair, the emulsion particle size is controlled (Patent Document 3) and a cationic surfactant having a quaternary ammonium base is used (patent) Document 4) has been proposed. In Patent Document 4, an emulsion having a high activity and excellent stability can be obtained as the carbon number of the alkyl group or alkenyl group contained in the cationic surfactant is small. However, it is highly irritating and difficult to use in cosmetics. If the carbon number is increased, the stability of the emulsion is lowered. Therefore, there is a demand for emulsions that can further improve the adsorptivity, maintain the conditioning effect, and have excellent stability.

  On the other hand, organopolysiloxane having a quaternary ammonium base improves the adsorptivity to hair and improves the sustainability of the conditioning effect (Patent Document 5 to Patent Document 9), and a quaternary ammonium base and a polyoxyalkylene group. It is known that not only gloss, smoothness and flexibility can be imparted but also ease of brushing and antistatic properties can be imparted (Patent Document 10). Many block copolymers containing an organopolysiloxane, a quaternary ammonium base, and a polyoxyalkylene group and bonded with various linking groups are also known (Patent Documents 11 to 17).

JP-A-9-110653 Japanese Patent Laid-Open No. 1-190619 Japanese Unexamined Patent Publication No. 7-188557 Japanese Patent No. 3698853 Japanese Examined Patent Publication No. 3-22844 Japanese Patent No. 2722221 Japanese Patent No. 2722222 Japanese Patent No. 3062283 Japanese Patent No. 3081049 Japanese Patent Publication No. 6-96498 JP-T-2004-521967 Japanese Patent No. 4936631 Japanese Patent No. 4936632 Japanese Patent No. 4726234 Japanese Patent No. 4801322 JP-T-2006-505644 JP-T-2006-505643

  The present invention has been made in view of the above problems, protects the hair with excellent adsorption power, can impart conditioning effects such as smoothness, combing and flexibility when wet, and even when dry An object of the present invention is to provide an oil-in-water-type organopolysiloxane emulsion excellent in stability that can provide a hair cosmetic capable of imparting conditioning effects such as smoothness, combing, flexibility, gloss, and cohesiveness. . Moreover, it aims at providing the hair cosmetics containing such an oil-in-water type organopolysiloxane emulsion.

（式中、Ｒ^２、Ｒ^３は上記の通りであり、Ｒ^４、Ｒ^５、Ｒ^６はそれぞれ独立に水素原子、炭素数１〜１０の１価炭化水素基、下記一般式（２）で表される４級アンモニウム塩基、及び下記平均組成式（３）で表されるポリオキシアルキレン基のうちいずれかである。但し、（Ｂ）成分のオルガノポリシロキサン１分子中に、下記一般式（２）で表される４級アンモニウム塩基及び下記平均組成式（３）で表されるポリオキシアルキレン基をそれぞれ１個以上含む。ｎは上記の通りである。）

（式（３）中、Ｒ^７は水素原子又は炭素数１〜３０の１価炭化水素基であり、ｂ、ｃ、ｄは０〜１００である。）
（Ｃ）水：１０〜３００質量部
を含有する水中油型オルガノポリシロキサン乳化物であり、該乳化物中の乳化粒子の平均粒径が０．１〜２０μｍであることを特徴とする水中油型オルガノポリシロキサン乳化物を提供する。 In order to achieve the above object, in the present invention, (A) (i) a general formula R ¹ _a SiO _{(4-a) / 2} [wherein R ¹ is a hydroxy group, an alkyl group having 1 to 20 carbon atoms, An aryl group having 6 to 30 carbon atoms and —R ² — (NH—R ³ —) _n NH ₂ (where R ² is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ³ has 2 to 10 carbon atoms) Wherein n is 0 to 3.), a group selected from 1.8 ≦ a ≦ 2.2. The viscosity is 1000 Pa. At 25 ° C. s or more of organopolysiloxane 10 to 100% by mass and (ii) general formula R ¹¹ _a SiO _{(4-a) / 2} (where R ¹¹ is an alkyl group having 1 to 20 carbon atoms and 6 to 30 carbon atoms) Organo consisting of 0 to 90% by mass of an organopolysiloxane having a viscosity of 1 to 500 mm ² / s represented by a group selected from an aryl group, 1.8 ≦ a ≦ 2.2. Polysiloxane: 100 parts by mass,
(However, the total amount of components (i) and (ii) is 100 parts by mass.)
(B) Organopolysiloxane having a substituent represented by the following general formula (1): 1 to 20 parts by mass,

(In the formula, R ² and R ³ are as described above, and R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, and the following general formula (2): Or a polyoxyalkylene group represented by the following average composition formula (3), provided that in one molecule of the organopolysiloxane (B), the following general formula ( 2) Each of the quaternary ammonium bases represented by 2) and one or more polyoxyalkylene groups represented by the following average composition formula (3) are contained, where n is as described above.

(In Formula (3), R ⁷ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, and b, c and d are 0 to 100.)
(C) Water: an oil-in-water type organopolysiloxane emulsion containing 10 to 300 parts by mass, wherein the average particle size of the emulsified particles in the emulsion is 0.1 to 20 μm An organopolysiloxane emulsion is provided.

  Such an oil-in-water organopolysiloxane emulsion has good stability, and since component (B) is a surfactant (emulsifier), adsorption of organopolysiloxane of component (A) (i) to the hair It can further improve the properties, protects the hair, provides conditioning effects such as smoothness, combing, and flexibility when wet, and smoothing, combing, flexibility, gloss, cohesiveness, etc. even when dry A hair cosmetic capable of imparting an effect can be provided. Moreover, since the average particle diameter of the emulsified particles in the emulsion is 0.1 to 20 μm, the emulsifiability, emulsification stability, and adsorptivity to hair can be improved.

（式（４）中、Ｒ^８は前記一般式（１）で表される置換基であり、Ｒ^９は互いに独立にヒドロキシ基、炭素数１〜２０のアルキル基、炭素数６〜３０のアリール基及び−Ｒ^２−（ＮＨ−Ｒ^３―）_ｎＮＨ_２（式中、Ｒ^２、Ｒ^３及びｎは上記の通りである。）から選択される基であり、Ｒ^１０はＲ^８又はＲ^９であり、Ａは下記平均組成式（５）

（上記平均組成式（５）において、Ｒ^８、Ｒ^９、Ｒ^１０は上記の通りであり、Ｑは酸素原子、又は炭素数１〜３の２価の炭化水素基である。）
で表されるオルガノポリシロキサンセグメントであり、上記平均組成式（４）及び上記平均組成式（５）において、ｅ、ｊ及びｍは互いに独立に０〜３であり、ｆは０〜５０００であり、ｇは０〜５００であり、ｈは０〜１００であり、ｉは０〜１００であり、ｋは０〜５０００であり、ｌは０〜５００である。但し、ｇが０の場合、ｅ＋ｈ＋ｊ＋ｌ＋ｍは１以上である。上記平均組成式（４）で表される化合物中に、Ｒ^８を少なくとも一個含み、かつ、上記一般式（２）で表される４級アンモニウム塩基及び上記平均組成式（３）で表されるポリオキシアルキレン基をそれぞれ１個以上含む。） Moreover, it is preferable that the organopolysiloxane of the said (B) component is a compound represented by the following average compositional formula (4).

(In the formula (4), R ⁸ is a substituent represented by the general formula (1), and R ⁹ are each independently a hydroxy group, an alkyl group having 1 to 20 carbon atoms, and an aryl having 6 to 30 carbon atoms. A group selected from a group and —R ² — (NH—R ³ —) _n NH ₂ , wherein R ² , R ³ and n are as defined above, and R ¹⁰ is R ⁸ or R ⁹ and A is the following average composition formula (5)

(In the average composition formula (5), R ⁸ , R ⁹ and R ¹⁰ are as described above, and Q is an oxygen atom or a divalent hydrocarbon group having 1 to 3 carbon atoms.)
In the average composition formula (4) and the average composition formula (5), e, j and m are independently 0 to 3 and f is 0 to 5000. , G is 0 to 500, h is 0 to 100, i is 0 to 100, k is 0 to 5000, and l is 0 to 500. However, when g is 0, e + h + j + l + m is 1 or more. The compound represented by the above average composition formula (4) contains at least one R ⁸ and is represented by the quaternary ammonium base represented by the above general formula (2) and the above average composition formula (3). Each contains at least one polyoxyalkylene group. )

  Thus, the organopolysiloxane having a substituent represented by the general formula (1) includes a compound represented by the average composition formula (4).

  Furthermore, it is preferable to contain a surfactant selected from (D) a cationic surfactant other than the component (B), an anionic surfactant, a nonionic surfactant and an amphoteric surfactant.

  Such an emulsified product can further improve emulsifying properties, emulsifying stability, and adsorptivity to hair.

  Furthermore, the present invention provides a hair cosmetic characterized by containing the oil-in-water organopolysiloxane emulsion of the present invention.

  With such hair cosmetics, hair can be protected by excellent adsorptive power, can provide conditioning effects such as smoothness, combing and flexibility when wet, and smooth, combing and flexible even when dry. Conditioning effects such as properties, gloss and cohesiveness can be imparted.

  Since the oil-in-water organopolysiloxane emulsion of the present invention has good stability and the component (B) is a surfactant, the (A) (i) component organopolysiloxane can be further adsorbed to the hair. Can improve hair, protects hair, provides conditioning effects such as smoothness, combing, and flexibility when wet, and provides conditioning effects such as smoothness, combing, flexibility, gloss, and cohesion even when dry Possible hair cosmetics can be provided.

  Hereinafter, the present invention will be described in more detail.

  As described above, an oil-in-water organopolysiloxane that protects the hair with an excellent adsorptive power and can provide a hair cosmetic capable of imparting conditioning effects such as smoothness, combing, flexibility, gloss, and coherence. There is a need for emulsions.

  The inventor has intensively studied to achieve the above object. As a result, it is an oil-in-water organopolysiloxane emulsion containing the following components (A), (B), and (C), and the average particle size of the emulsified particles in the emulsion is from 0.1 to 20 μm. The oil-type organopolysiloxane emulsion has excellent adsorptive power to hair, particularly damaged hair, and is effective in protecting hair. Specifically, smoothness, good combability, softness, gloss and cohesiveness. And the stability over time was also found, and the present invention was completed.

  Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited thereto.

（式中、Ｒ^２、Ｒ^３は上記の通りであり、Ｒ^４、Ｒ^５、Ｒ^６はそれぞれ独立に水素原子、炭素数１〜１０の１価炭化水素基、下記一般式（２）で表される４級アンモニウム塩基、及び下記平均組成式（３）で表されるポリオキシアルキレン基のうちいずれかである。但し、（Ｂ）成分のオルガノポリシロキサン１分子中に、下記一般式（２）で表される４級アンモニウム塩基及び下記平均組成式（３）で表されるポリオキシアルキレン基をそれぞれ１個以上含む。ｎは上記の通りである。）

（式（３）中、Ｒ^７は水素原子又は炭素数１〜３０の１価炭化水素基であり、ｂ、ｃ、ｄは０〜１００である。）
（Ｃ）水：１０〜３００質量部。 The oil-in-water organopolysiloxane emulsion of the present invention is an emulsion containing the following components (A), (B), and (C), and the average particle diameter (average particle diameter) of the emulsion particles in the emulsion: Is 0.1 to 20 μm.
(A) (i) General formula R ¹ _a SiO _{(4-a) / 2} [where R ¹ is a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and —R ^2. — (NH—R ³ —) _n NH ₂ (wherein R ² is a divalent hydrocarbon group having 1 to 10 carbon atoms, R ³ is a divalent hydrocarbon group having 2 to 10 carbon atoms, and n is 0 Is a group selected from: 1.8 ≦ a ≦ 2.2. The viscosity is 1000 Pa. At 25 ° C. s or more of organopolysiloxane 10 to 100% by mass and (ii) general formula R ¹¹ _a SiO _{(4-a) / 2} (where R ¹¹ is an alkyl group having 1 to 20 carbon atoms and 6 to 30 carbon atoms) Organo consisting of 0 to 90% by mass of an organopolysiloxane having a viscosity of 1 to 500 mm ² / s represented by a group selected from an aryl group, 1.8 ≦ a ≦ 2.2. Polysiloxane: 100 parts by mass,
(However, the total amount of components (i) and (ii) is 100 parts by mass.)
(B) Organopolysiloxane having a substituent represented by the following general formula (1): 1 to 20 parts by mass,

(In the formula, R ² and R ³ are as described above, and R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, and the following general formula (2): Or a polyoxyalkylene group represented by the following average composition formula (3), provided that in one molecule of the organopolysiloxane (B), the following general formula ( 2) Each of the quaternary ammonium bases represented by 2) and one or more polyoxyalkylene groups represented by the following average composition formula (3) are contained, where n is as described above.

(In Formula (3), R ⁷ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, and b, c and d are 0 to 100.)
(C) Water: 10 to 300 parts by mass.

  Such an oil-in-water organopolysiloxane emulsion has good stability and the component (B) is a surfactant, so that the (A) (i) component organopolysiloxane can be further adsorbed to the hair. Can improve hair, protects hair, provides conditioning effects such as smoothness, combing, and flexibility when wet, and provides conditioning effects such as smoothness, combing, flexibility, gloss, and cohesion even when dry Possible hair cosmetics can be provided.

[(A) component]
(A) In the general formula R ¹ _a SiO _{(4-a) / 2} of component (i), R ^{1 s} are independently of each other a hydroxy group, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms. And —R ² — (NH—R ³ —) _n NH ₂ . Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and other alkyl groups, cyclopentyl group, and cyclohexyl group. And the like, and the like. Examples of the aryl group having 6 to 30 carbon atoms include a phenyl group and a tolyl group. —R ² — (NH—R ³ —) _{n In} NH ₂ , R ² is a divalent hydrocarbon group having 1 to 10 carbon atoms, specifically methylene group, ethylene group, propylene group, butylene group, isobutylene. Group, hexamethylene group and the like, preferably propylene, and R ³ is a divalent hydrocarbon group having 2 to 10 carbon atoms, specifically, ethylene group, propylene group, butylene group, isobutylene group, hexa A methylene group etc. are mentioned, Preferably it is an ethylene group. n is 0 to 3, preferably 0 or 1. Specific examples of —R ² — (NH—R ³ —) _n NH ₂ include —C ₃ H ₆ —NH ₂ , —C ₃ H ₆ —NH—C ₂ H ₄ —NH ₂ . a is in the range of 1.8 ≦ a ≦ 2.2.

  The highly polymerized organopolysiloxane of component (A) (i) in the present invention has a viscosity at 25 ° C. of 1000 Pa. From the viewpoint of adhesion to hair, feel and conditioning. s or more, preferably 3000 Pa.s. s or more. Even such high-viscosity organopolysiloxanes are easy to handle and have good workability by using an emulsion as in the present invention. In addition, the upper limit of the viscosity at 25 ° C. of the component (A) (i) is not particularly limited. s. The molecular weight of the organopolysiloxane (A) (i) can be, for example, in the range of a polystyrene-reduced number average molecular weight of 100,000 to 500,000 in gel permeation chromatography (GPC) analysis using toluene as a developing solvent. The structure of component (A) (i) is preferably linear.

Here, in the present invention, the component (A) (i) can be used alone as the component (A), but the components (A) (i) and (A) (ii) are used in combination as the component (A). You can also In the general formula R ¹¹ _a SiO _{(4-a) / 2} of the component (A) (ii), R ¹¹ is independently selected from an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 30 carbon atoms. It is a group. Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and other alkyl groups, cyclopentyl group, and cyclohexyl group. And the like, and the like. Examples of the aryl group having 6 to 30 carbon atoms include a phenyl group and a tolyl group. R ¹¹ is preferably a methyl group or a phenyl group. a is the same as above.

When a mixture of the components (A) (i) and (A) (ii) is used as the component (A), the viscosity of the component (A) (ii) at 25 ° C. is in the range of 1 to 500 mm ² / s. , Preferably it is the range of 1-300 mm < ² > / s, More preferably, it is the range of 1-100 mm < ² > / s. In this case, the ratio of the component (A) (ii) in the component (A) is 90% by mass or less. If it exceeds 90% by mass, the ratio of the organopolysiloxane of component (A) (i) will be low, and sufficient performance will not be obtained. The structure of component (A) (ii) is preferably linear or cyclic.

The component (A) of the oil-in-water organopolysiloxane emulsion of the present invention has a viscosity at 25 ° C. of 1000 Pa.s. s or more (i), or a mixture of the component (i) and the component (ii) having a viscosity at 25 ° C. of 1 to 500 mm ² / s. The viscosity of the mixture at 25 ° C. is preferably 1 a 000 to 1,000,000 ^mm 2 / s, more preferably 1,000~500,000mm ² / s. When the viscosity is 1,000 or more, the ratio of the organopolysiloxanes (A) and (i) is sufficient, and sufficient performance is obtained. When the viscosity is 1,000,000 mm ² / s or less, it is easy to handle and charged into the emulsification equipment. Work does not take time, and the load at the time of emulsification stirring becomes small.

[Component (B)]
The organopolysiloxane used as the component (B) of the oil-in-water organopolysiloxane emulsion of the present invention has a substituent represented by the above general formula (1), and includes the following in one molecule: One or more quaternary ammonium bases represented by the general formula (2) are contained, and one or more polyoxyalkylene groups represented by the following average composition formula (3) are contained in one molecule.

In the general formula (1), R ² , R ³ , and n are the same as above, R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, It is either a quaternary ammonium base represented by the general formula (2) or a polyoxyalkylene group represented by the following average composition formula (3).

In the general formula (1), the monovalent hydrocarbon group having 1 to 10 carbon atoms in R ⁴ , R ⁵ and R ⁶ includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and heptyl. C1-C10 alkyl groups, such as a group, an octyl group, a nonyl group, are mentioned.

In the general formula (1), R ⁴ , R ⁵ and R ⁶ are preferably a hydrogen atom, a quaternary ammonium base represented by the general formula (2), and a polyoxy represented by the average composition formula (3). An alkylene group;

In the average composition formula (3), R ⁷ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms. Examples of the monovalent hydrocarbon group having 1 to 30 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a decyl group. R ⁷ is preferably a hydrogen atom, a methyl group, or a butyl group.

  In the said average composition formula (3), b, c, and d are 0-100, respectively, Preferably, b is 0-50, c is 0-50, d is 0-20. The polyoxyalkylene group represented by the average composition formula (3) may be either a random type or a block type.

（式（４）中、Ｒ^８は前記一般式（１）で表される置換基であり、Ｒ^９は互いに独立にヒドロキシ基、炭素数１〜２０のアルキル基、炭素数６〜３０のアリール基及び−Ｒ^２−（ＮＨ−Ｒ^３―）_ｎＮＨ_２（式中、Ｒ^２、Ｒ^３及びｎは上記の通りである。）から選択される基であり、Ｒ^１０はＲ^８又はＲ^９であり、Ａは下記平均組成式（５）

（上記平均組成式（５）において、Ｒ^８、Ｒ^９、Ｒ^１０は上記の通りであり、Ｑは酸素原子、又は炭素数１〜３の２価の炭化水素基である。）
で表されるオルガノポリシロキサンセグメントであり、上記平均組成式（４）及び上記平均組成式（５）において、ｅ、ｊ及びｍは互いに独立に０〜３であり、ｆは０〜５０００であり、ｇは０〜５００であり、ｈは０〜１００であり、ｉは０〜１００であり、ｋは０〜５０００であり、ｌは０〜５００である。但し、ｇが０の場合、ｅ＋ｈ＋ｊ＋ｌ＋ｍは１以上である。上記平均組成式（４）で表される化合物中に、Ｒ^８を少なくとも一個含み、かつ、上記一般式（２）で表される４級アンモニウム塩基及び上記平均組成式（３）で表されるポリオキシアルキレン基をそれぞれ１個以上含む。） The (B) component organopolysiloxane only needs to have the substituent represented by the above general formula (1), and its specific structure is not particularly limited, but is represented by the following average composition formula (4). It is preferable that it is a compound.

(In the formula (4), R ⁸ is a substituent represented by the general formula (1), and R ⁹ are each independently a hydroxy group, an alkyl group having 1 to 20 carbon atoms, and an aryl having 6 to 30 carbon atoms. A group selected from a group and —R ² — (NH—R ³ —) _n NH ₂ , wherein R ² , R ³ and n are as defined above, and R ¹⁰ is R ⁸ or R ⁹ and A is the following average composition formula (5)

(In the average composition formula (5), R ⁸ , R ⁹ and R ¹⁰ are as described above, and Q is an oxygen atom or a divalent hydrocarbon group having 1 to 3 carbon atoms.)
In the average composition formula (4) and the average composition formula (5), e, j and m are independently 0 to 3 and f is 0 to 5000. , G is 0 to 500, h is 0 to 100, i is 0 to 100, k is 0 to 5000, and l is 0 to 500. However, when g is 0, e + h + j + l + m is 1 or more. The compound represented by the above average composition formula (4) contains at least one R ⁸ and is represented by the quaternary ammonium base represented by the above general formula (2) and the above average composition formula (3). Each contains at least one polyoxyalkylene group. )

In the above average composition formula (4), R ⁹ is independently of each other a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms and —R ² — (NH—R ³ —) _n NH _2. (Wherein R ² , R ³ and n are as described above). Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and other alkyl groups, cyclopentyl group, and cyclohexyl group. And the like, and the like. Examples of the aryl group having 6 to 30 carbon atoms include a phenyl group and a tolyl group. Examples of —R ² — (NH—R ³ —) _n NH ₂ include —C ₃ H ₆ —NH ₂ and —C ₃ H ₆ —NH—C ₂ H ₄ —NH ₂ . R ⁹ is preferably a hydroxy group, a methyl group, a phenyl group, —C ₃ H ₆ —NH ₂ , or —C ₃ H ₆ —NH—C ₂ H ₄ —NH ₂ .

  In the average composition formula (5), Q is an oxygen atom or a divalent hydrocarbon group having 1 to 3 carbon atoms. Examples of the divalent hydrocarbon group having 1 to 3 carbon atoms include a methylene group, an ethylene group, and a propylene group. Q is preferably an ethylene group or a propylene group.

In the average composition formula (4) and the average composition formula (5), e, j and m are each independently an integer of 0 to 3, preferably 0 or 1, and f is 0 to 5000, preferably 10 to 4000, g is 0 to 500, preferably 0 to 100, h is 0 to 100, preferably 0 to 50, and i is 0 to 100, preferably 0 to 50. , K is 0 to 5000, preferably 10 to 4000, and l is 0 to 500, preferably 0 to 100. However, when g is 0, e + h + j + l + m is 1 or more. The compound represented by the above average composition formula (4) contains at least one R ⁸ and is represented by the quaternary ammonium base represented by the above general formula (2) and the above average composition formula (3). Each containing one or more polyoxyalkylene groups.

In the case where the compound represented by the above average composition formula (4) has a plurality of (substituent represented by the general formula (1)) ^{R 8} is, for each type of ^R 8 ^(R 2 ^{~R 6} and n values) may be the same or different.

  The organopolysiloxane of component (B) used in the present invention can be synthesized by the following method.

（式（７）中、Ｒ^７、ｂ、ｃ、ｄは上記の通りである。） The organopolysiloxane of component (B) is represented by an organopolysiloxane having an amino group, an epoxy group-containing cationizing agent (glycidyltrimethylammonium chloride) represented by the following general formula (6), and the following average composition formula (7). It can be obtained by a ring-opening reaction with an epoxy group-containing polyoxyalkylene compound.

(In formula (7), R ⁷ , b, c and d are as described above.)

  When reacting the organopolysiloxane having an amino group with the epoxy group-containing cationizing agent represented by the general formula (6) and the epoxy group-containing polyoxyalkylene compound represented by the average composition formula (7) It may be carried out without a solvent, and a solvent may be used if necessary. Solvents that can be used for the above reaction are not particularly limited, but hydrocarbon solvents such as hexane and toluene, ketone solvents such as acetone and methyl ethyl ketone, N, N-dimethylacetamide, and N, N-dimethylformamide. And amide solvents such as N-methyl-2-pyrrolidone, ether solvents such as tetrahydrofuran and 1,4-dioxane, alcohol solvents such as methanol, ethanol and isopropyl alcohol, and ester solvents such as butyl acetate. Of these, ethanol and isopropyl alcohol are particularly preferable.

  Although reaction temperature is not specifically limited, 20-100 degreeC is preferable, More preferably, it is 30-60 degreeC. A reaction temperature of 100 ° C. or lower is preferable because side reactions such as a decomposition reaction of a cation group hardly occur. Although reaction time is not specifically limited, 1 to 20 hours are preferable, More preferably, it is 2 to 5 hours.

  The reaction equivalent of the organopolysiloxane having an amino group and the compound containing an epoxy group (the compound represented by the above general formula (6) and the above average composition formula (7)) is 0.1 to the total amino group. The amount can be 1.1 equivalent, preferably 0.5 to 1.0 equivalent. In the case of 0.1 equivalent or more, an organopolysiloxane having excellent adhesion to hair can be obtained. When the amount is 1.1 equivalent or less, an unreacted epoxy compound does not remain, and the purity of the resulting organopolysiloxane is improved. The equivalent ratio ((6) / (7)) of the epoxy group-containing cationizing agent represented by the general formula (6) and the epoxy group-containing polyoxyalkylene compound represented by the average composition formula (7) is There is no particular limitation. The equivalent ratio ((6) / (7)) can be appropriately selected according to the purpose, but the equivalent ratio is preferably in the range of 0.1 to 10.

  The content of the component (B) that is an emulsifier is 1 to 20 parts by mass, preferably 3 to 15 parts by mass with respect to 100 parts by mass of the component (A). When the amount is less than 1 part by mass, the emulsion is unstable, and when the amount is more than 20 parts by mass, it is not preferable because it becomes a sticky feel when used as a hair cosmetic. Since the component (B) is usually a water-soluble or water-dispersible solid, it can be used by dissolving in advance in a mixture with water or a polyhydric alcohol.

[Component (C)]
The component (C) is water, and specific examples thereof include purified water. (A) With respect to 100 mass parts of component, content of the water of (C) component is 10-300 mass parts, Preferably it is 20-100 mass parts. If the amount is less than 10 parts by mass, the viscosity of the emulsion is high and difficult to handle. If the amount is more than 300 parts by mass, the viscosity of the emulsion is low and the emulsion is unstable, and the ratio of the organopolysiloxane as component (A) (i) Becomes low and sufficient performance cannot be obtained.

[(D) component]
The oil-in-water type organopolysiloxane emulsion of the present invention further comprises a cationic surfactant, an anionic surfactant, a nonionic surfactant and an amphoteric surfactant which are different from the component (B) as component (D). A surfactant selected from can also be contained. Such an emulsified product can further improve emulsifying properties, emulsifying stability, and adsorptivity to hair.

  Specifically, examples of the anionic surfactant include those shown below. Alkyl benzene sulfonate, preferably a linear or branched alkyl benzene sulfonate having an alkyl group having an average carbon number of 10 to 16. Alkyl ether sulfate or alkenyl ether sulfate, preferably having a linear or branched alkyl group or alkenyl group having an average carbon number of 10 to 20, and an average of 0.5 to 8 moles of ethylene oxide or propylene in one molecule Oxide, butylene oxide, ethylene oxide and propylene oxide in a molar ratio of 0.1 / 9.9 to 9.9 / 0.1, or ethylene oxide and butylene oxide of 0.1 / 9.9 to 9.9 / Alkyl ether sulfate or alkenyl ether sulfate added at a molar ratio of 0.1. Alkyl sulfates or alkenyl sulfates, preferably alkyl sulfates or alkenyl sulfates having an average alkyl group or alkenyl group having 10 to 20 carbon atoms. Olefin sulfonates, preferably olefin sulfonates having an average of 10 to 20 carbon atoms in one molecule. Alkane sulfonates, preferably alkane sulfonates having an average of 10 to 20 carbon atoms in one molecule. Higher fatty acid salts, preferably saturated or unsaturated fatty acid salts having an average of 10 to 24 carbon atoms in one molecule. (Amide) ether carboxylic acid type surfactant. α-sulfo fatty acid salts or esters, preferably α-sulfo fatty acid salts or esters having an alkyl or alkenyl group consisting of an average of 10 to 20 carbon atoms. N-acyl amino acid type surfactants, preferably N-acyl amino acid type surfactants having an acyl group having 8 to 24 carbon atoms and a free carboxylic acid residue (for example, N-acyl sarcosinate, N-acyl-β -Alanine etc.). Phosphoric acid ester type surfactants, preferably phosphoric acid mono- or diester type surfactants having an alkyl group or alkenyl group having 8 to 24 carbon atoms or an alkylene oxide adduct thereof. A sulfosuccinic acid ester type surfactant, preferably a sulfosuccinic acid ester derived from a higher alcohol having 8 to 22 carbon atoms or an ethoxylate thereof or a higher fatty acid amide. Polyoxyalkylene fatty acid amide ether sulfates, preferably sulfates such as ethoxylates of linear or branched saturated or unsaturated fatty acid monoethanolamides or diethanolamides having 8 to 24 carbon atoms. A monoglyceride sulfate salt, preferably a monoglyceride sulfate salt having a linear or branched saturated or unsaturated fatty acid group having 8 to 24 carbon atoms. An acylated isethionate, preferably an acylated isethionate having a linear or branched saturated or unsaturated fatty acid group having 8 to 24 carbon atoms. Alkyl glyceryl ether sulfate or alkyl glyceryl ether sulfonate, preferably alkyl glyceryl ether sulfate or alkyl glyceryl ether having a linear or branched alkyl group or alkenyl group having 8 to 24 carbon atoms or an alkylene oxide adduct thereof Sulfonate. Alkyl or alkenyl amide sulfonate, preferably an alkyl or alkenyl amide sulfonate having a linear or branched alkyl or alkenyl group having 8 to 24 carbon atoms. Alkanolamide sulfosuccinate, preferably an alkanolamide sulfosuccinate having a linear or branched alkyl or alkenyl group having 8 to 24 carbon atoms. An alkyl sulfoacetate, preferably an alkyl sulfoacetate having a linear or branched alkyl or alkenyl group having 8 to 24 carbon atoms. An acylated taurate, preferably an acyl taurate having a straight or branched chain saturated or unsaturated fatty acid group having 8 to 24 carbon atoms. N-acyl-N-carboxyethylglycine salt, preferably N-acyl-N-carboxyethylglycine salt having an acyl group having 6 to 24 carbon atoms.

  As salts of these anionic surfactants, that is, counter ions of anionic residues, alkali metal ions such as sodium and potassium, alkaline earth metal ions such as calcium and magnesium, ammonium ions, carbon atoms of 2 or 3 Examples include alkanolamines having 1 to 3 alkanol groups (for example, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.).

  Of these anionic surfactants, alkyl ether sulfates, particularly polyoxyethylene alkyl ether sulfates are preferred.

  Nonionic surfactants include, for example, polyoxyalkylene alkyl ethers or polyalkylenes having a linear or branched alkyl group or alkenyl group having an average carbon number of 10 to 24 and added with ethylene oxide, propylene oxide or butylene oxide. Oxyalkylene alkenyl ether; glycerin ester of fatty acid having 8 to 20 carbon atoms; glycol ester of fatty acid having 8 to 20 carbon atoms; alkylene oxide adduct of monoglyceride of fatty acid having 8 to 20 carbon atoms; fatty acid having 8 to 20 carbon atoms; Sucrose ester; sorbitan ester of fatty acid having 8 to 20 carbon atoms; polyglycerin fatty acid ester having an acyl group having 8 to 20 carbon atoms; monoethanolamide or diethanolamide of fatty acid having 8 to 20 carbon atoms or ethoxylate thereof; Polio Ethylene hydrogenated castor oil; polyoxyalkylene sorbitan fatty acid ester having an acyl group having 8 to 20 carbon atoms; polyoxyethylene sorbite fatty acid ester having an acyl group having 8 to 20 carbon atoms; linear or branched chain having 8 to 18 carbon atoms An alkyl saccharide surfactant having an alkyl group, an alkenyl group or an alkylphenyl group; a linear or branched alkyl group having 8 to 20 carbon atoms, an alkylamine oxide or an alkylamidoamine oxide having an alkenyl group; Polyether compound or ester compound of polyhydric alcohol having 20 linear or branched alkyl or alkenyl groups; polyoxyalkylene modified organopolysiloxane, polyoxyalkylene / alkyl co-modified organopolysiloxane, polyglycerin modified o Ganopolysiloxane, polyglycerin / alkyl co-modified organopolysiloxane, polyoxyalkylene / fluoroalkyl co-modified organopolysiloxane, cross-linked polyoxyalkylene / organopolysiloxane, sugar-modified silicone, oxazoline-modified silicone, polyoxyalkylene alkylaryl ether , Polyoxyalkylene lanolin alcohols, polyoxyalkylene fatty acid esters, pluronic block polymers, tetronic block polymers, polyoxyalkylene fatty acid amides, polyoxyalkylene alkyl amides, polyethyleneimine derivatives and the like.

  The amphoteric surfactant is not particularly limited as long as it is used in normal hair cosmetics. For example, amide amino acid type, carbobetaine type, amide betaine type, sulfobetaine type, amide sulfobetaine type, imidazolinium Examples include betaine type, amino acid type, phosphobetaine type, and phosphate ester type.

  Examples of the cationic surfactant include tertiary amines, quaternary ammonium salts, amidoamines and ester amines. For example, behenyltrimethylammonium chloride, distearyldimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, N-stearyl-N, N, N-tri (polyoxyethylene) ammonium chloride (total ethylene oxide) 3 mol addition), cetylbenzyldimethylammonium chloride, cetyltriethylammonium bromide, distearyldimethylammonium chloride, 2-decyltetradecyltrimethylammonium chloride, 2-dodecylhexadecyltrimethylammonium chloride, di-2-hexyldecyldimethyl Ammonium chloride, di-2-octyldodecyl di Chill chloride, behenyl tertiary amine, stearyl tertiary amines, can be cited stearamidopropyl dimethyl amine and the like.

  The content of the component (D) surfactant is preferably 0.5 to 20 parts by mass, more preferably 0 to 100 parts by mass of the component (A) in the oil-in-water organopolysiloxane emulsion. 5 to 15 parts by mass, more preferably 0.5 to 1 part by mass.

  Although the manufacturing method of the oil-in-water organopolysiloxane emulsion of this invention is not specifically limited, As for this emulsion, mass ratio (A) / (B) / (C) of each component is 100/1-20/3, for example. It is obtained by phase-inverting and emulsifying the mixture of ˜20 from a water-in-oil type to an oil-in-water type under high shear, and further diluting with water and / or an aqueous solution of the component (B). When the mass ratio of the component (C) is 3 or more, the phase can be easily inverted from the water-in-oil type to the oil-in-water type, and if it is 20 or less, the average particle size of the emulsified particles in the emulsion does not exceed 20 μm. .

  Furthermore, when adding (D) component, for example, the mass ratio (A) / (B) / (C) of each component is 100/1 to 20/3 to 20 from a water-in-oil type under high shear. After phase inversion and emulsification into an oil-in-water type, component (D) or an aqueous solution thereof may be added and diluted in a step of diluting with water and / or an aqueous solution of (B), or (A) / (B) / The mixture of (C) / (D) is phase-inverted and emulsified from a water-in-oil type to an oil-in-water type under high shear, and water, an aqueous solution of (B) and an aqueous solution of (D) are added. It may be added and diluted.

  As an apparatus used for obtaining the oil-in-water organopolysiloxane emulsion of the present invention, a high shear force represented by a homomixer, an ultramixer, a planetary mixer and a combimixer (named above) is obtained. And an emulsifier. When phase inversion or emulsification from a water-in-oil type to an oil-in-water type is performed, if the stirring time after phase inversion is too short, the degree of dispersion of the particle size tends to be widened, resulting in insufficient stability. If the stirring time after phase inversion is too long, particle breakage of the phase inversion occurs, so that even if diluted with water, the oil is separated and a stable oil-in-water emulsion cannot be obtained. Therefore, the stirring time is preferably 20 minutes or more and 3 hours or less.

  The average particle diameter of the emulsified particles in the oil-in-water organopolysiloxane emulsion of the present invention is 0.1 to 20 μm, preferably 0.3 to 10 μm. It is technically difficult to make the average particle size less than 0.1 μm. When the average particle size exceeds 20 μm, the emulsion is separated over time and the storage stability becomes insufficient. The average particle size of the emulsified particles can be achieved by setting the stirring time after phase inversion from water-in-oil type to oil-in-water type to 20 minutes or more and 3 hours or less. It is not limited to. A method for evaluating the storage stability of the emulsion will be described later.

  In addition, as an emulsified particle, what consists of (A) component and (B) component is mentioned. Moreover, when the oil-in-water organopolysiloxane emulsion of this invention contains (D) component, what consists of (A) component, (B) component, and (D) component is mentioned.

  Furthermore, in this invention, the hair cosmetics containing the said oil-in-water type organopolysiloxane emulsion of this invention are provided. With such hair cosmetics, hair can be protected by excellent adsorptive power, can provide conditioning effects such as smoothness, combing and flexibility when wet, and smooth, combing and flexible even when dry. Conditioning effects such as properties, gloss and cohesiveness can be imparted.

  When the oil-in-water organopolysiloxane emulsion of the present invention is used in a hair cosmetic, the content is 0.001 to 20% by mass in the hair cosmetic from the viewpoint of obtaining a good conditioning effect and its sustainability ( Hereinafter, it is simply expressed as%), preferably 0.001 to 15%, more preferably 0.001 to 10%.

  In the hair cosmetic composition of the present invention, other components to be blended in the hair cosmetic composition can be used singly or in appropriate combination of two or more. Specific examples include the following.

  As an oil agent component, for example, an alcohol-based water-soluble oil agent, a saturated or unsaturated alcohol having 10 to 30 carbon atoms, an ester of the alcohol and a fatty acid having 1 to 30 carbon atoms, a saturated or unsaturated fatty acid having 12 to 30 carbon atoms, and the above Esters of fatty acids and mono- or polyhydric alcohols, amides of the above fatty acids and amines, sterols, squalene, phospholipids, glycolipids containing cationic sugars, animal fats and oils, vegetable fats and oils, (A) and (B) Examples include organopolysiloxanes other than the components. Examples of organopolysiloxanes other than the components (A) and (B) include, for example, cyclic, linear or branched dimethylpolysiloxane, methylpolysiloxane, amino-modified polysiloxane, alkyl-modified polysiloxane, methylphenylpolysiloxane, Examples include silicone oils such as polyether-modified silicone. In addition, an oil agent can be used individually by 1 type or in combination of 2 or more types. The content of these oils is preferably 0.01 to 30%, more preferably 1 to 25%, and still more preferably 3 to 20% in the hair cosmetic.

  In this case, a surfactant selected from a cationic surfactant other than the component (B), an anionic surfactant, a nonionic surfactant and an amphoteric surfactant can be further contained. . Thus, surfactants other than (B) component should just be used for normal hair cosmetics. By containing such a surfactant, the stability of the emulsion is further improved. Specific examples of this surfactant include the same examples as those described above for the component (D) surfactant.

  The content of the surfactant is preferably 0.1 to 50% in the hair cosmetic, more preferably 0.5 to 40%, and still more preferably 1 to 30% from the viewpoint of foamability.

  The hair cosmetic composition of the present invention includes a thickening agent such as hydroxyethyl cellulose, an anionic / amphoteric / cationic / nonionic polymer, a fragrance, a pearling agent, a hair set polymer, a dye, and an ultraviolet ray absorbing agent as necessary. You may mix | blend an agent, antioxidant, preservative, etc. further.

  With these hair cosmetics, hair can be protected by excellent adsorptive power, imparting conditioning effects such as smoothness, combing and flexibility when wet, and smooth, combing and flexibility even when dry. , Gloss and coherence can be added.

  Examples of the hair cosmetic of the present invention include hair shampoos, hair rinses, hair treatments, hair conditioners used in the bathroom, hair foams, hair sprays, hair creams, hair waxes, hair gels, and hair dyes used outside the bathroom. , Permanents, hair manicures, hair bleaches, and the like, which are used in home and beauty salon treatments, and the like. The oil-in-water organopolysiloxane emulsion of the present invention can be incorporated into any of these. Among them, since it has an excellent hair protecting effect, it is suitable for shampoos, hair treatments, hair conditioners, and the like, and particularly for hair damaged by bleaching, etc., it is suitable for damaged hair.

  EXAMPLES Hereinafter, although a preparation example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, the quantity of each component in the table | surface which has no special mention is the quantity converted into the pure part. The viscosity of component (A) (i) is the viscosity at 25 ° C. measured with a rheometer “AR 2000ex” (manufactured by TS Instruments Japan Co., Ltd.), and (A) (ii) component and The viscosities of the following mixtures 1 to 3 are viscosities at 25 ° C. measured with a capillary viscometer (Canon / Fenske).

[Preparation Example 1]
(A) (i) Viscosity of 5000 Pa. s highly polymerized dimethylpolysiloxane (in the general formula R ¹ _a SiO _{(4-a) / 2} , R ¹ is a methyl group and a is 2.00) 20 parts by mass, (A) (ii) Decamethylcyclopentasiloxane having a viscosity of 4 mm ² / s (in general formula R ¹¹ _a SiO _{(4-a) / 2} , where R ¹¹ is a methyl group and a is 2.00) uniformly 80 parts by mass By dissolution, an organopolysiloxane mixture having a viscosity of 3,000 mm ² / s was obtained (hereinafter referred to as mixture 1).

[Preparation Example 2]
(A) (i) Viscosity of 30000 Pa. s, a highly polymerized aminopropyldimethylpolysiloxane having an amine equivalent of 25,000 g / mol (in the general formula R ¹ _a SiO _{(4-a) / 2} , R ¹ is a methyl group or —C ₃ H ₆ —NH ₂ , A is 2.00) 20 parts by mass, (A) (ii) dimethylpolysiloxane having a viscosity of 20 mm ² / s (in the general formula R ¹¹ _a SiO _{(4-a) / 2} , R ¹¹ is a methyl group) 80 parts by mass were uniformly dissolved to obtain an organopolysiloxane mixture having a viscosity of 40,000 mm ² / s (hereinafter referred to as mixture 2).

[Preparation Example 3]
(A) (i) Viscosity is 5000 Pa. 40 parts by weight of dimethylpolysiloxane having hydroxy groups at both ends of s (in the general formula R ¹ _a SiO _{(4-a) / 2} , R ¹ is a methyl group or a hydroxy group, and a is 2.00) (A) (ii) Dimethylpolysiloxane having a viscosity of 100 mm ² / s (in the general formula R ¹¹ _a SiO _{(4-a) / 2} , R ¹¹ is a methyl group and a is 2.02) 60 mass The parts were uniformly dissolved to obtain an organopolysiloxane mixture having a viscosity of 124,000 mm ² / s (hereinafter referred to as mixture 3).

で表されるアミン当量が６５０ｇ／ｍｏｌのアミノ変性オルガノポリシロキサン６５質量部、イソプロピルアルコール５０質量部、下記一般式（６）で表されるエポキシ基含有カチオン化剤の８０ｗｔ％水溶液９．５質量部、下記一般式（９）で表されるエポキシ基含有ポリオキシアルキレン化合物６７．５質量部を窒素雰囲気下添加し、５０℃にて３時間撹拌した。

得られた反応混合物を減圧下、６０℃でストリップすることにより、溶剤を取り除き、黄色透明でガム状の下記平均組成式（１０）で表されるオルガノポリシロキサンを１３４．１ｇ（収率９５．６％）得た。

上記平均組成式（１０）におけるＲの平均モル比は、下記式（２）／下記式（１１）／Ｈ＝６／４／１４であった。

[(B) Component Synthesis Example 1]
The following average composition formula (8)

65 parts by weight of an amino-modified organopolysiloxane having an amine equivalent represented by 650 g / mol, 50 parts by weight of isopropyl alcohol, and 9.5 parts by weight of an 80 wt% aqueous solution of an epoxy group-containing cationizing agent represented by the following general formula (6) Part, 67.5 parts by mass of an epoxy group-containing polyoxyalkylene compound represented by the following general formula (9) was added in a nitrogen atmosphere and stirred at 50 ° C. for 3 hours.

The obtained reaction mixture was stripped at 60 ° C. under reduced pressure to remove the solvent, and 134.1 g of a yellow transparent, gum-like organopolysiloxane represented by the following average composition formula (10) (yield: 95.95%). 6%).

The average molar ratio of R in the average composition formula (10) was the following formula (2) / the following formula (11) / H = 6/4/14.

で表されるアミン当量が５６４０ｇ／ｍｏｌのアミノ変性オルガノポリシロキサン５６．４質量部、イソプロピルアルコール５０質量部、下記一般式（６）で表されるエポキシ基含有カチオン化剤の８０ｗｔ％水溶液１．９質量部、下記一般式（１３）で表されるエポキシ基含有ポリオキシアルキレン化合物７質量部を窒素雰囲気下添加し、５０℃にて３時間撹拌した。

得られた反応混合物を減圧下、６０℃でストリップすることにより、溶剤を取り除き、黄色透明でガム状の下記平均組成式（１４）で表されるオルガノポリシロキサンを６１．０ｇ（収率９３．３％）得た。

上記平均組成式（１４）におけるＲの平均モル比は、下記式（２）／下記式（１５）／Ｈ＝７／３／１０であった。

[(B) Component Synthesis Example 2]
The following average composition formula (12)

1. An amino-modified organopolysiloxane 56.4 parts by mass with an amine equivalent of 5640 g / mol, 50 parts by mass of isopropyl alcohol, and an 80 wt% aqueous solution of an epoxy group-containing cationizing agent represented by the following general formula (6) 9 parts by mass and 7 parts by mass of an epoxy group-containing polyoxyalkylene compound represented by the following general formula (13) were added in a nitrogen atmosphere and stirred at 50 ° C. for 3 hours.

The obtained reaction mixture was stripped at 60 ° C. under reduced pressure to remove the solvent, and 61.0 g of a yellow transparent, gum-like organopolysiloxane represented by the following average composition formula (14) (yield: 93.93). 3%).

The average molar ratio of R in the average composition formula (14) was the following formula (2) / the following formula (15) / H = 7/3/10.

[Examples 1-4, Comparative Examples 1-4]
[Emulsion production method]
In the TK combination M type (manufactured by Primix Co., Ltd.) equipped with an anchor mixer that can stir the entire container, a homomixer that is a high shear force loading device, and a dispermixer, each component is charged at the mixing ratio shown in Table 1, An anchor mixer was simultaneously stirred at 30 rpm and a dispermixer 2000 rpm to invert the phase to obtain an emulsion. Next, the remaining water or the remaining water and an aqueous surfactant solution were added, and the mixture was further stirred and homogenized at 2000 rpm to obtain the desired emulsion. Here, the organopolysiloxanes of Synthesis Examples 1 and 2 were added after dissolving in purified water in advance.

[Evaluation]
The average particle size of the emulsified particles was measured with a laser diffraction / scattering particle size distribution measuring apparatus LA-920 (Horiba, Ltd.).
Further, the storage stability of the emulsion was evaluated by the following criteria by observing the appearance after taking each emulsion in a glass bottle and storing it in a thermostat at 50 ° C. for 1 month.
○: Separation of oil phase and water phase is not observed Δ: Slight separation occurred ×: Completely separated into two layers

表１中の（Ａ）（ｉ）ジメチルポリシロキサンは一般式Ｒ^１ _ａＳｉＯ_{（４−ａ）／２}において、Ｒ^１がメチル基であり、ａが２．００であるものである。

(A) (i) Dimethylpolysiloxane in Table 1 is ^{one in} which R ¹ is a methyl group and a is 2.00 in the general formula R ¹ _a SiO _{(4-a) / 2} .

  As shown in Table 1, the oil-in-water organopolysiloxane emulsions of the present invention (Examples 1 to 4) are all stable, Comparative Example 1 having a large average particle size and Comparative Example 2 having a large amount of water addition are stable. The nature was bad. In Comparative Example 3 which does not contain the component (B) in the present invention and contains a polyoxyalkylene alkyl ether as an emulsifier, the stability was not bad. In Comparative Example 4 which did not contain the component (B) in the present invention and contained an alkyl quaternary ammonium base as an emulsifier, the emulsion was slightly separated.

[Examples 5 to 8, Comparative Examples 5 and 6]
A hair conditioner having the composition shown in Table 2 below was prepared by a conventional method. For Examples 5-8, the emulsions of Examples 1-4 were used. For Comparative Examples 5 and 6, the emulsions of Comparative Examples 3 and 4 that did not have poor emulsion stability among Comparative Examples 1 to 4 were used.
About the obtained hair conditioner, sensory evaluation was performed by the following method. The results are shown in Table 2 below.

[Sensory evaluation method]
The hair bundle (20 g, 20 cm) of a Japanese woman that was bleached with a commercially available bleaching agent was subjected to sensory evaluation while 5 panelists treated the hair bundle in the following manner. After applying 2 g of the hair conditioner shown in Table 2 to the hair bundle washed with 3 g of a standard shampoo having the following composition and fully acclimatizing the entire hair, the hair was wet for about 30 seconds under running water at about 40 ° C. Evaluation was performed. Next, towel drying was performed, and after drying with a dryer, evaluation after drying was performed. Sensory evaluation was performed on whether the hair smoothness, combing and softness when wet, and the smoothness, combing, softness, gloss and cohesiveness of the hair when dry were present. The results are shown in the following evaluation criteria, depending on the number of panelists who answered “effective”.

Standard shampoo formulation 25% polyoxyethylene (2.5) sodium lauryl ether sulfate 62.0%
Lauric acid diethanolamide 2.3%
Edetate disodium 0.15%
Sodium benzoate 0.5%
Sodium chloride 0.8%
75% phosphoric acid appropriate amount perfume appropriate amount methylparaben appropriate amount
Purified water remaining
Total 100.0%

[Evaluation criteria]
◎: Reply if 4 to 5 people are effective ○: Reply if 3 people are effective △: Reply if 2 people are effective ×: 1 or 0 responded that it was effective

表２中の「←」は実施例５と同じ配合量であることを意味する。

“←” in Table 2 means the same blending amount as in Example 5.

  As shown in Table 2, the hair conditioners (Examples 5 to 8) containing the oil-in-water organopolysiloxane emulsion of the present invention have good evaluation of smoothness, combing and flexibility when wet, In addition, the evaluation of smoothness, combing, flexibility, gloss and cohesiveness during drying was also good. The hair conditioner (Comparative Example 5) in which the emulsifier is a polyoxyalkylene alkyl ether was particularly poor in evaluation of smoothness during wet and dryness and combing and cohesiveness during dryness. Further, the hair conditioner (Comparative Example 6) in which the emulsifier is an alkyl quaternary ammonium base was particularly poor in evaluation of smoothness, gloss and cohesiveness when combed when wet and when dried.

[Example 9]
A hair treatment (pH 7.0) having the following composition was prepared by a conventional method.
Composition%
Octadecyloxy (2-hydroxypropyl) dimethylamine 0.5
Stearic acid dimethylaminopropylamide 2.0
Stearyl alcohol 5.0
Dipropylene glycol 1.0
Benzyl alcohol 0.5
Phenoxyethanol 0.1
Emulsion obtained in Example 1 5.0
Highly polymerized dimethylpolysiloxane ^{* 1} 0.5
Glycerin 5.0
Polypropylene glycol 2.5
Lanolin fatty acid 0.5
Sunflower oil 0.5
Lactic acid 1.5
Fragrance 0.4
Total amount of ion-exchanged water remaining 100.0
* 1: KF-96H 100000cs (Shin-Etsu Chemical Co., Ltd.)

  The obtained hair treatment had good smoothness at the time of rinsing, flexibility, smoothness, smoothness after drying, softness, and combing feeling.

[Example 10]
A hair treatment (pH 4.0) having the following composition was prepared by a conventional method.
Composition%
Dimethylbehenamine 2.0
Behenyltrimethylammonium chloride 0.3
Stearyl alcohol 4.5
Behenyl alcohol 1.5
Isononyl isononanoate 0.5
Emulsion obtained in Example 3 5.0
Amino-modified organopolysiloxane ^{* 2} 0.5
Glycolic acid 0.5
Malic acid 0.1
Dipropylene glycol 3.0
Benzyl alcohol 0.3
Arginine 0.2
Pantothenyl ethyl ether 0.1
Hydrolyzed conchiolin solution (dry matter 3%) 0.05
Panax ginseng extract (dry matter 3%) 0.05
Soybean extract (0.4% dry matter) 0.05
Eucalyptus extract (dry matter 0.2%) 0.05
Rice germ oil 0.05
Perfume Appropriate amount Methylparaben Appropriate amount
Purified water remaining
Total 100.0
* 2: KF-8004 (Shin-Etsu Chemical Co., Ltd.)

  The obtained hair treatment had good smoothness at the time of rinsing, flexibility, smoothness, smoothness after drying, softness, and combing feeling.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

Claims (4)

(A) (i) General formula R ¹ _a SiO _{(4-a) / 2} [where R ¹ is a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and —R ^2. — (NH—R ³ —) _n NH ₂ (wherein R ² is a divalent hydrocarbon group having 1 to 10 carbon atoms, R ³ is a divalent hydrocarbon group having 2 to 10 carbon atoms, and n is 0 Is a group selected from: 1.8 ≦ a ≦ 2.2. And 10 to 100% by mass of an organopolysiloxane having a viscosity of 1000 Pa · s or more at 25 ° C. and (ii) a general formula R ¹¹ _a SiO _{(4-a) / 2} (where R ¹¹ is the number of carbon atoms) A group selected from an alkyl group having 1 to 20 and an aryl group having 6 to 30 carbon atoms, wherein 1.8 ≦ a ≦ 2.2.) The viscosity at 25 ° C. is 1 to 500 mm ² / s. Organopolysiloxane consisting of 0 to 90% by mass of organopolysiloxane: 100 parts by mass,
(However, the total amount of components (i) and (ii) is 100 parts by mass.)
(B) Organopolysiloxane having a substituent represented by the following general formula (1): 1 to 20 parts by mass,

(In the formula, R ² and R ³ are as described above, and R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, and the following general formula (2): Or a polyoxyalkylene group represented by the following average composition formula (3), provided that in one molecule of the organopolysiloxane (B), the following general formula ( 2) Each of the quaternary ammonium bases represented by 2) and one or more polyoxyalkylene groups represented by the following average composition formula (3) are contained, where n is as described above.

(In Formula (3), R ⁷ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, and b, c and d are 0 to 100.)
(C) Water: an oil-in-water type organopolysiloxane emulsion containing 10 to 300 parts by mass, wherein the average particle size of the emulsified particles in the emulsion is 0.1 to 20 μm Type organopolysiloxane emulsion. The oil-in-water organopolysiloxane emulsion according to claim 1, wherein the organopolysiloxane of the component (B) is a compound represented by the following average composition formula (4).

(In the formula (4), R ⁸ is a substituent represented by the general formula (1), and R ⁹ are each independently a hydroxy group, an alkyl group having 1 to 20 carbon atoms, and an aryl having 6 to 30 carbon atoms. A group selected from a group and —R ² — (NH—R ³ —) _n NH ₂ , wherein R ² , R ³ and n are as defined above, and R ¹⁰ is R ⁸ or R ⁹ and A is the following average composition formula (5)

(In the average composition formula (5), R ⁸ , R ⁹ and R ¹⁰ are as described above, and Q is an oxygen atom or a divalent hydrocarbon group having 1 to 3 carbon atoms.)
In the average composition formula (4) and the average composition formula (5), e, j and m are independently 0 to 3 and f is 0 to 5000. , G is 0 to 500, h is 0 to 100, i is 0 to 100, k is 0 to 5000, and l is 0 to 500. However, when g is 0, e + h + j + l + m is 1 or more. The compound represented by the above average composition formula (4) contains at least one R ⁸ . )   And (D) a surfactant other than the component (B), a surfactant selected from a cationic surfactant, an anionic surfactant, a nonionic surfactant and an amphoteric surfactant. The oil-in-water organopolysiloxane emulsion according to claim 1 or 2, characterized in that   A hair cosmetic comprising the oil-in-water organopolysiloxane emulsion according to any one of claims 1 to 3.