JP4606866B2 - Hair cosmetic composition - Google Patents

Description

  The present invention relates to a hair cosmetic composition, and more particularly, to a hair cosmetic composition excellent in slipperiness upon washing and rinsing damaged hair.

  Conventionally, a hair treatment agent such as a hair rinsing agent that is used as a conditioning shampoo by blending a powder of silicone oil and silicone (polyorganosiloxane) cured product with hair cosmetics or used after washing. The use feeling is improved. For example, a hair treatment composition containing polymethylsilsesquioxane and polyorganosiloxane has been proposed. (For example, see Patent Document 1, Patent Document 2, and Patent Document 3)

However, although the compositions described in these Patent Documents 1 to 3 are all effective in improving the combing property at the time of drying, the effect on damaged hair caused by coloring or the like is sufficient. I could not say. In particular, it is required to provide such a damaged hair with a smooth and moist touch, but the present situation is that the request cannot be sufficiently satisfied.
JP-A-5-310533 JP-A-6-080559 JP-A-9-291215

  The present invention has been made to solve such problems, and in particular, a hair-hair cosmetic composition that is excellent in slipping feeling during washing and rinsing for damaged hair, and that is excellent in comb-through property and cohesiveness after drying. The purpose is to provide goods.

The hair cosmetic composition according to the first aspect of the present invention comprises (A) a spherical polyorgano surface-treated with an organosilicon compound containing an amino group represented by the following formula and / or a hydrolysis / condensation product thereof : Silsesquioxane fine particles 0.05 to 10% by weight, (B) 0.1 to 30% by weight of polyorganosiloxane having a viscosity at 25 ° C. of 1 to 100,000 Pa · s, and (C) melting point of 25 ° C. or more 0.1 to 15% by weight of a high melting point aliphatic compound, (D1) 0.1 to 10% by weight of a cation conditioning agent, and (E) water, and (A) the spherical polyorganosilsesquioxane The weight ratio of the fine particles to the (B) polyorganosiloxane is 1/9 to 1/4 .
H ₂ NCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ ,
H ₂ NCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ NHC ₃ H ₆ Si (OCH ₃ ) ₃ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH (CH ₃ ) CH ₂ Si (OCH ₃ ) ₃ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH (CH ₃ ) CH ₂ Si (OCH ₂ CH ₃ ) ₃ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH (CH ₃ ) CH ₂ SiCH ₃ (OCH ₃ ) ₂ ,
H ₂ NC ₆ H ₄ Si (OCH ₃ ) ₃ ,
C ₆ H ₅ NHCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃

The hair cosmetic composition of the second invention of the present invention is (A) a spherical polyorgano surface-treated with an organosilicon compound containing an amino group represented by the following formula and / or a hydrolysis / condensation product thereof : Silsesquioxane fine particles 0.05 to 10% by weight, (B) 0.1 to 30% by weight of polyorganosiloxane having a viscosity at 25 ° C. of 1 to 100,000 Pa · s, and (F) a detersive surfactant. 5 to 50% by weight, (D2) 0.1 to 20% by weight of a conditioning agent, and (E) water, and (B) polyorganosiloxane of (A) spherical polyorganosilsesquioxane fine particles. The weight ratio with respect to is 1/9 to 1/4 .
H ₂ NCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ ,
H ₂ NCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ NHC ₃ H ₆ Si (OCH ₃ ) ₃ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH (CH ₃ ) CH ₂ Si (OCH ₃ ) ₃ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH (CH ₃ ) CH ₂ Si (OCH ₂ CH ₃ ) ₃ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH (CH ₃ ) CH ₂ SiCH ₃ (OCH ₃ ) ₂ ,
H ₂ NC ₆ H ₄ Si (OCH ₃ ) ₃ ,
C ₆ H ₅ NHCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃

  According to the hair cosmetic composition of the present invention, it is possible to impart a smooth and moist feel to the hair, and in particular, it is excellent in slipping feeling against damaged hair during washing and rinsing. In addition, good combing property, cohesiveness and moist feeling can be imparted after drying.

  Embodiments of the present invention will be described below.

  The hair cosmetic composition according to the first embodiment of the present invention comprises (A) spherical silicone fine particles 0.05 to 10 which are surface-treated with an amino group-containing organosilicon compound and / or a hydrolyzate / condensate thereof. % By weight, (B) 0.1 to 30% by weight of a polyorganosiloxane having a viscosity of 1 to 100,000 Pa · s at 25 ° C., and (C) 0.1 to 0.1% of a high melting point aliphatic compound having a melting point of 25 ° C. or higher. 15% by weight, (D1) 0.1-10% by weight of a cation conditioning agent, and (E) water.

  The hair cosmetic composition according to the second embodiment of the present invention comprises (A) spherical silicone fine particles 0.05 to 10 which are surface-treated with an amino group-containing organosilicon compound and / or a hydrolyzate / condensate thereof. (B) 0.1 to 30% by weight of a polyorganosiloxane having a viscosity of 1 to 100,000 Pa · s at 25 ° C., (F) 5 to 50% by weight of a detersive surfactant, and (D2). Contains 0.1 to 20% by weight of conditioning agent and (E) water, respectively.

  In these embodiments, the spherical silicone fine particles as the component (A) are components that characterize the present invention, and can impart good slipping feeling, moist feeling, etc. at the time of washing and after drying to the hair. it can.

In the first and second embodiments of the present invention, fine particles made of, for example, polyorganosilsesquioxane can be used as the spherical silicone fine particles. The polyorganosilsesquioxane fine particles are finely cross-linked silicone resin fine particles having a three-dimensional network structure due to siloxane bonds, and are excellent in solvent resistance that does not swell or dissolve in an organic solvent. The polyorganosilsesquioxane that makes up the fine particles
General formula: R ¹ Si (OR ² ) ₃ (1)
(Wherein R ¹ represents a monovalent group selected from a substituted or unsubstituted alkyl group, an alkenyl group and a phenyl group, and R ² represents a substituted or unsubstituted alkyl group which is the same or different from each other). Spherical silicone fine particles produced using one or more of organotrialkoxysilanes as a raw material and / or general formula: SiY ₄ (2)
(Wherein Y represents the same or different hydrolyzable groups) and one or more of organotrialkoxysilanes represented by the above general formula (1) are produced as raw materials. Spherical silicone fine particles.

Among these polyorganosilsesquioxanes, the organic group R ¹ bonded to the silicon atom is preferably a methyl group from the viewpoint of ease of production and availability. In addition, various modified polyorganosilsesquioxane fine particles can be used as long as the effects of the present invention are not impaired.

  The polyorganosilsesquioxane fine particles used in the first and second embodiments preferably have an average particle size of 1 to 30 μm, more preferably 2 to 25 μm. When the average particle size is less than 1 μm, a squeaky sensation appears after washing and after drying, and when the average particle size is 30 μm or more, the foaming property is lowered, and the particles are formed when the final preparation, for example, shampoo or conditioner is used. It becomes easy to settle. In addition, the shape of the polyorganosilsesquioxane fine particles is preferably a spherical shape independent from a practical aspect, and more preferably a true spherical shape.

  Such polyorganosilsesquioxane fine particles are described in, for example, JP-A 63-101857, JP-A 63-77940, JP-A 2000-186148, JP-A 2001-192452. It can be manufactured by a method.

  For example, in the method described in 2000-186148, an organotrialkoxysilane such as methyltrialkoxysilane is hydrolyzed in acidic water adjusted to an electric conductivity of 2 to 600 μS / cm to obtain organosilanetriol or Spherical polymethylsilsesquioxane fine particles can be obtained by preparing a water / alcohol solution of the partial condensate, adding an alkaline aqueous solution to this solution, mixing, and allowing a polycondensation reaction in a stationary state.

In the first and second embodiments of the present invention, the amino group-containing organosilicon compound for treating the surface of such polyorganosilsesquioxane fine particles includes:
A silane represented by the general formula: R ³ ₃ -nSiX (OR ² ) n can be given.

In the formula, R ² is a substituted or unsubstituted alkyl group that is the same as or different from each other, similarly to R ² in the general formula (1). Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. Is done. R ³ is a hydrogen atom or an alkyl group, and examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. Further, X is an organic group containing an amino group, the formula: _-Q- is represented by ^{_{(NHCH 2 CH 2) aNHR 4}} . In the formula, Q is a divalent hydrocarbon group, specifically, an alkylene group such as a methylene group, an ethylene group, a propylene group, or a butylene group; an arylene group represented by the formula: —C ₆ H ₄ — An alkylenearylene group represented by the formula: — (CH ₂ ) ₂ C ₆ H ₄ — is exemplified. Of these, propylene groups are the most common. R ⁴ is a hydrogen atom or a monovalent hydrocarbon group, and examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, a phenyl group, and a cyclohexyl group. a is an integer of 0-5, and 0 or 1 is common. n is an integer of 1 to 3, and is usually 2 or 3.

As such an amino group-containing organosilicon compound,
H ₂ NCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ ,
H ₂ NCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ NHC ₃ H ₆ Si (OCH ₃ ) ₃ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH (CH ₃ ) CH ₂ Si (OCH ₃ ) ₃ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH (CH ₃ ) CH ₂ Si (OCH ₂ CH ₃ ) ₃ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH (CH ₃ ) CH ₂ SiCH ₃ (OCH ₃ ) ₂ ,
H ₂ NC ₆ H ₄ Si (OCH ₃ ) ₃ ,
And _{C 6 H 5 NHCH 2 CH 2} CH 2 Si (OCH 3) 3
And alkoxysilanes. Moreover, what hydrolyzed and condensed these amino group containing organosilicon compounds can also be used.

  In the first and second embodiments of the present invention, the poly described above with such an organosilicon compound containing an amino group and / or a hydrolysis / condensation product thereof (hereinafter referred to as an amino group-containing organosilicon compound). As a method for treating the surface of the organosilsesquioxane fine particles, any method may be used as long as the surface of the fine particles can be coated with an amino group-containing organosilicon compound. For example, after putting polyorganosilsesquioxane fine particles in a suitable container, and then adding an amino group-containing organosilicon compound as a surface treatment agent, the mixture is stirred at a temperature of room temperature to 120 ° C. for 1 to 8 hours with stirring, The method of making it contact can be taken. At this time, a more uniform surface treatment can be performed by using, together with the surface treatment agent, an alcohol such as methanol, ethanol or isopropyl alcohol, or an organic solvent such as toluene or xylene as a dispersion medium. Further, in order to uniformly treat the particles, the surface treatment can be performed after the particles are uniformly dispersed with an appropriate stirrer such as an ultrasonic disperser or a high-speed stirrer.

  By contacting in this way, the amino group-containing organosilicon compound can be adsorbed on the surface of the polyorganosilsesquioxane fine particles. The amount of the amino group-containing organosilicon compound thus adsorbed can be adjusted by appropriately selecting the type of compound, the treatment time, the particle diameter of the polyorganosilsesquioxane fine particles, and the like. Preferably, the amount of the amino group-containing organosilicon compound is 0.05 to 100 parts by weight, more preferably 0.1 to 50 parts by weight, and most preferably 0.1 to 100 parts by weight of the polyorganosilsesquioxane fine particles. 2 to 30 parts by weight.

  When the amount of the amino group-containing organosilicon compound used is less than 0.05 parts by weight, the hair is not sufficiently moisturized. On the other hand, when the amount used exceeds 100 parts by weight, the polyorganosilsesquioxane fine particles Aggregation or agglomeration of each other is likely to occur. In order to more effectively perform the coating with the amino group-containing organosilicon compound, it is preferable to use the polyorganosessesquioxane fine particles in an undried state after production.

  In the first and second embodiments, the polyorganosiloxane used as the component (B) has a viscosity at 25 ° C. of 1 to 100,000 Pa.s. s, more preferably 10 to 50,000 Pa.s. of s. Such polyorganosiloxane is preferably linear, but may have a partially branched structure or network structure. The terminal functional group is not particularly limited, but is preferably a methyl group, a hydroxyl group, or a methoxy group.

  The organic group bonded to the silicon atom in the polydiorganosiloxane (B) is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, or a hexyl group; an alkenyl group such as a vinyl group or a propenyl group. Examples thereof include an aryl group such as a phenyl group; an aralkyl group such as a phenethyl group; and a group in which part of hydrogen atoms of these hydrocarbon groups is substituted with a halogen atom, a nitrile group, or the like. Of these, the use of dimethicone (polydimethylsiloxane), dimethiconol (polydimethylsiloxane having both terminal hydroxyl groups), and amodimethicone (amino-modified silicone oil) is particularly preferable.

  In the first and second embodiments of the present invention, when (A) spherical silicone fine particles surface-treated with an amino group-containing organosilicon compound and (B) polyorganosiloxane are blended in a hair treatment composition Each component may be blended as it is, or may be blended in either a dispersion or an emulsion. However, from the viewpoint of dispersibility and sedimentation of the spherical silicone fine particles as component (A), It is preferable to mix in the state. Furthermore, as disclosed in JP-A-9-291215, an oil-in-water silicone emulsion (O / W emulsion) composition containing the components (A) and (B) is prepared and used as the composition. It is particularly preferable to blend in

  In the first embodiment of the present invention, the high melting point aliphatic compound as component (C) has a melting point of 25 ° C. or higher, and consists of an aliphatic alcohol, a fatty acid, a derivative thereof, and a mixture thereof. Selected from the group.

  (B) Examples of high melting point aliphatic compounds are the International Cosmetic Ingredient Dictionary, 5th edition, 1993, and CTFA (The Cosmetic, Toiletry, and Fragrance Association, Inc.) Cosmetic Ingredient Handbook, Second Edition, 1992, but is not limited thereto.

  Useful fatty alcohols are those having 14 to 30, preferably 16 to 22 carbon atoms. These aliphatic alcohols are saturated and are preferably linear or branched alcohols. Examples of aliphatic alcohols include, but are not limited to, cetyl alcohol, stearyl alcohol, behenyl alcohol, and mixtures thereof.

  Fatty acids include those having 10 to 30, preferably 12 to 22, more preferably 16 to 22 carbon atoms. These fatty acids can be saturated and have a linear or branched carbon skeleton. Dibasic acids, tribasic acids and higher polybasic acids are included, and salts of these fatty acids are also included. Examples include, but are not limited to, lauric acid, palmitic acid, stearic acid, behenic acid, sebacic acid, and mixtures thereof.

  Examples of the aliphatic alcohol derivative and the fatty acid derivative include the alkyl ether of the aliphatic alcohol, the alkoxylated aliphatic alcohol, the alkyl ether of the alkoxylated aliphatic alcohol, the ester of the aliphatic alcohol, and the fatty acid of the compound having an esterifiable hydroxy group. Esters, hydroxy substituted fatty acids, and mixtures thereof.

  Specific examples of fatty alcohol derivatives and fatty acid derivatives include methyl stearyl ether and the like; ceteth series such as ceteth-1 to ceteth-45, and ethylene glycol ether of cetyl alcohol in which the numerical designation represents the number of ethylene glycol moieties; Steerless series such as -1 to 10 where the numerical designation represents the number of ethylene glycol moieties; ethylene glycol ethers of steareth alcohol; ceteares 1 to 10, ethylene glycol ethers of cetealess alcohol, ie cetyl alcohol and stearyl alcohol A mixture of aliphatic alcohols mainly containing the number of ethylene glycol moieties; the ceteth, steareth, and ceteares compounds having 1 to 30 carbon atoms. Polyoxyethylene ether of behenyl alcohol; ethyl stearate, cetyl stearate, cetyl palmitate, stearyl stearate, myristyl myristate, polyoxyethylene cetyl ether stearate, polyoxyethylene stearyl ether stearate, polyoxyethylene lauryl ether Stearate, ethylene glycol monostearate, polyoxyethylene monostearate, polyoxyethylene distearate, propylene glycol monostearate, propylene glycol distearate, trimethylolpropane distearate, sorbitan stearate, polyglyceryl stearate, Glyceryl monostearate, glyceryl distearate, glyceryl tristearate and it Mixtures of the like.

  High melting point fatty compounds which are single compounds of high purity are preferred, and single compounds of pure fatty alcohols selected from the group consisting of pure cetyl alcohol, stearyl alcohol and behenyl alcohol are particularly preferred.

  In the present specification, the term “pure” means that the compound has a purity of at least 90%, preferably at least 95%. A single compound of high purity exhibits a good rinsing effect during rinsing.

  Commercially available products of such high melting point aliphatic compounds include KONOL series manufactured by Shin Nippon Rika Co., Ltd., NAA series cetyl alcohol, stearyl alcohol, and behenyl alcohol manufactured by Nippon Oil & Fats Co., Ltd., 1- Pure behenyl alcohol of 1-DOCOSANOL, NEO-FAT from Akzo, USA, HYSTRENE from Witco Corp., USA, and Italian baby (Vevy) DERMA (DERMA).

  The above-mentioned (C) high melting point aliphatic compound having a melting point of 25 ° C. or higher is 0.1 to 15% by weight, preferably 0.5 to 10% by weight, more preferably 0.75, in the hair cosmetic composition. It is contained at a ratio of ˜5% by weight. And it provides gel and network structure together with the cationic conditioning agent described later, and various conditioning effects such as smooth and smooth feel on wet hair, softness and moisture on dry hair, and suppression of hair splashing. To demonstrate.

  In the first embodiment, the cationic conditioning agent that is component (D) is selected from the group consisting of cationic surfactants, cationic polymers, and mixtures thereof. These (D) cationic conditioning agents are contained in the hair cosmetic composition in a proportion of 0.1 to 10% by weight, preferably 0.25 to 8% by weight, more preferably 0.5 to 3% by weight. The

As the cationic surfactant, those represented by the following general formula are preferably used.

In the formula, at least one of R ⁵ , R ⁶ , R ⁷ and R ⁸ is an aliphatic group having 8 to 30 carbon atoms or an aromatic group having 22 or less carbon atoms, an alkoxy group, Selected from a polyoxyalkylene group, an alkylamide group, a hydroxyalkyl group, an aryl group or an alkylaryl group, the rest being independently an aliphatic group having 1 to 22 carbon atoms, or 22 or fewer carbon atoms Selected from an aromatic group, an alkoxy group, a polyoxyalkylene group, an alkylamide group, a hydroxyalkyl group, an aryl group or an alkylaryl group having X is a salt selected from halogen (eg, chloride, bromide), acetate, citric acid, lactate, glycolate, phosphate, nitrate, sulfonate, sulfate, alkylsulfate and alkylsulfonate radicals, etc. Forming anions.

Aliphatic groups can contain other groups such as ether linkages and amino groups in addition to carbon and hydrogen atoms. Furthermore, long-chain aliphatic groups such as those having 12 or more carbon atoms may be saturated or unsaturated. R ⁵ , R ⁶ , R ⁷ and R ⁸ are preferably independently selected from alkyl groups having 1 to 22 carbon atoms.

  Specific examples of useful cationic surfactants include materials having the following CTFA names: quaternium-8, quaternium-14, quaternium-18, quaternium-18 mesosulfate, quaternium-24, and mixtures thereof, It is not limited to these.

  Among the cationic surfactants represented by the formula (Chemical Formula 1), those containing at least one alkyl chain having at least 16 carbon atoms in the molecule are preferable. Examples of such cationic surfactants are: for example, trade name INCROQUAT TMC-80 manufactured by Croda, or behenyltrimethylammonium chloride available as ECONOL TM22 from Sanyo Kasei. Cetyltrimethylammonium chloride available under the trade name CA-2350 from Nikko Chemicals; hydrogenated tallow alkyltrimethylammonium chloride, dialkyl (14-18) dimethylammonium chloride, ditallowalkyldimethylammonium chloride, two Hydrogenated tallow alkyldimethylammonium chloride, distearyldimethylammonium chloride, dicetyldimethylammonium chloride, di (behenyl / arachidyl) dimethylammonium Lorido, dibehenyldimethylammonium chloride, stearyldimethylbenzylammonium chloride, stearylpropylene glycol phosphate dimethylammonium chloride, stearoylamidopropyldimethylbenzylammonium chloride, stearoylamidopropyldimethyl (myristyl acetate) ammonium chloride, and N- (stearoylcholaminoformylmethyl) ) Pyridinium chloride and the like, but not limited thereto.

Preferred cationic surfactants contain one or more aromatic, ether, ester, amide, or amino moieties in which at least one of the substituents is present as a substituent or bond in the radical chain, and R ^At least one of ^{5 to} R ⁸ groups is an alkoxy group (preferably an alkoxy group having 1 to 3 carbon atoms), a polyoxyalkylene group (preferably a polyoxyalkylene group having 1 to 3 carbon atoms), an alkylamide group, or a hydroxyalkyl group. , Alkyl ester groups, and hydrophilically substituted cationic surfactants containing one or more hydrophilic moieties selected from combinations thereof. The hydrophilically substituted cationic surfactant preferably contains 2 to 10 non-ionic hydrophilic moieties located within the above range. Preferred cationic surfactants that are hydrophilically substituted include those represented by the following formulas (Chemical Formula 2) to (Chemical Formula 7).

式中、ｎは８〜２８、ｘ＋ｙは２〜４０の数を表し、Ｚ¹は短鎖アルキル基、好ましくは炭素数１〜３のアルキル基、より好ましくはメチル基、あるいは（ＣＨ_２ＣＨ_２Ｏ）_ｚＨである。ｘ＋ｙ＋ｚは６０以下、Ｘは前記塩形成アニオンである。

In the formula, n represents 8 to 28, x + y represents a number of 2 to 40, Z ¹ is a short-chain alkyl group, preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group, or (CH ₂ CH ₂ O) _zH . x + y + z is 60 or less, and X is the salt-forming anion.

式中、ｍは１〜５の数、Ｒ^９、Ｒ^１０およびＲ^１１のうち１つ以上は、それぞれ独立して炭素数１〜３０のアルキル基であり、その他はＣＨ_２ＣＨ_２ＯＨであり、Ｒ^１２、Ｒ^１３およびＲ^１４のうち１つまたは２つはそれぞれ炭素数１〜３０のアルキル基であり、その他はＣＨ_２ＣＨ_２ＯＨである。Ｘは前記塩形成アニオンである。

In the formula, m is a number of 1 to 5, and one or more of R ⁹ , R ¹⁰ and R ¹¹ are each independently an alkyl group having 1 to 30 carbon atoms, and the others are CH ₂ CH ₂ OH. , R ¹² , R ¹³ and R ¹⁴ are each an alkyl group having 1 to 30 carbon atoms, and the other is CH ₂ CH ₂ OH. X is the salt-forming anion.

これらの式のそれぞれにおいて、Ｚ^２はアルキル基、好ましくは炭素数１〜３のアルキル基より好ましくはメチル基であり、Ｚ^３は短鎖ヒドロキシアルキル基好ましくはヒドロキシメチル基またはヒドロキシエチル基であり、ｐおよびｑはそれぞれ２〜４の整数で、好ましくは２〜３、より好ましくは２である。Ｒ^１５およびＲ^１６は、それぞれ置換または非置換炭化水素、好ましくは炭素数１２〜２０のアルキル基またはアルケニル基、Ｘは前記の塩形成アニオンである。

In each of these formulas, Z ² represents an alkyl group, preferably preferably from alkyl groups having 1 to 3 carbon atoms are methyl group, Z ³ is preferably a short chain hydroxyalkyl group be a hydroxymethyl group or a hydroxyethyl group , P and q are each an integer of 2 to 4, preferably 2 to 3, more preferably 2. R ¹⁵ and R ¹⁶ are each a substituted or unsubstituted hydrocarbon, preferably an alkyl or alkenyl group having 12 to 20 carbon atoms, and X is the salt-forming anion.

式中、Ｒ^１６はヒドロカルビル基、好ましくは炭素数１〜３のアルキル基より好ましくはメチル基であり、Ｚ^４およびＺ^５はそれぞれ短鎖ヒドロカルビル基、好ましくは炭素数２〜４のアルキル基またはアルケニル基より好ましくはエチル基であり、ｒは２〜４０好ましくは７〜３０の数、Ｘは前記の塩形成アニオンである。

In the formula, R ¹⁶ is a hydrocarbyl group, preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group, and Z ⁴ and Z ⁵ are each a short-chain hydrocarbyl group, preferably an alkyl group having 2 to 4 carbon atoms, or An alkenyl group is more preferably an ethyl group, r is a number of 2 to 40, preferably 7 to 30, and X is a salt-forming anion as described above.

式中、Ｒ^１８およびＲ^１９は、それぞれ炭素数１〜３のアルキル基より好ましくはメチル基、Ｚ^６は炭素数１２〜２２のヒドロカルビル基、アルキルカルボキシ基またはアルキルアミド基である。Ａはたんぱく質、好ましくはコラーゲン、ケラチン、乳たんぱく質、シルク、大豆たんぱく質、小麦たんぱく質、またはそれらの加水分解型であり、Ｘは前記塩形成アニオンである。

In the formula, R ¹⁸ and R ¹⁹ are each preferably a methyl group, more preferably an alkyl group having 1 to 3 carbon atoms, and Z ⁶ is a hydrocarbyl group, alkylcarboxy group or alkylamide group having 12 to 22 carbon atoms. A is a protein, preferably collagen, keratin, milk protein, silk, soy protein, wheat protein, or a hydrolyzed form thereof, and X is the salt-forming anion.

式中、ｓは２または３、Ｒ^２０およびＲ^２１は、それぞれ炭素数１〜３のヒドロカルビル基好ましくはメチル基であり、Ｘは前記塩形成アニオンである。

In the formula, s is 2 or 3, R ²⁰ and R ²¹ are each a hydrocarbyl group having 1 to 3 carbon atoms, preferably a methyl group, and X is the salt-forming anion.

  Examples of useful hydrophilically substituted cationic surfactants include the following CTFA names: quaternium-16, quaternium-26, quaternium-27, quaternium-30, quaternium-33, quaternium-43, quaternium- 52, quaternium-53, quaternium-56, quaternium-60, quaternium-61, quaternium-62, quaternium-70, quaternium-71, quaternium-72, quaternium-75, quaternium-76 hydrolyzed collagen, quaternium-77, quaternium -78, quaternium-79 hydrolyzed collagen, quaternium-79 hydrolyzed keratin, quaternium-79 hydrolyzed milk protein, quaternium-79 hydrolyzed silk, quaternium-79 hydrolyzed soy protein And Quaternium -79 hydrolyzed wheat protein, quaternium -80, Quaternium -81, Quaternium -82, Quaternium -83, and materials and mixtures thereof having a quaternium -84 include, but are not limited to.

  Particularly preferred hydrophilically substituted cationic surfactants include dialkylamidoethylhydroxyethylmonium salts, dialkylamidoethyldimonium salts, dialkyloethylethylhydroxyethylmonium salts, dialkyloylethyldimonium salts, and These mixtures are mentioned.

  These are commercially available under the following trade names: Witco Chemical's VARISOFT 110, VariQuat K1215 and 638, McIntyre's MacPro KLP, MacPro WLW, MacPro MLP, MacPro NSP, MacPro NLW, MacPro WWP, MacPro NLP, MacPro SLP, Akzo's Etquad 18/25, Etquad 0 / 12PG, Etquad C / 25, Etquad S / 25, Etduqua, Such as Henkel's DEHYQUA SP and ICI America's ATLAS G265.

  Next, a cationic polymer useful in the embodiment will be described. The term “polymer” is intended to include a substance produced by polymerization of one kind of monomer and a substance produced by two or more kinds of monomers.

  The cationic polymer is preferably a water-soluble cationic polymer. A “water-soluble” cationic polymer is sufficiently soluble in water to form a substantially transparent solution in water at 25 ° C. (distilled or equivalent water) at a concentration of 0.1%. Means polymer. Preferred cationic polymers are sufficiently soluble to form a substantially clear solution at a concentration of 0.5%, more preferably at a concentration of 1.0%.

  Also, the cationic polymer of embodiments has an average molecular weight of at least 5,000, typically at least 10,000 and less than 10,000.000. A preferred average molecular weight is 100,000 to 2,000,000. It has a cationic nitrogen-containing moiety such as a quaternary ammonium moiety and / or a cationic amino moiety.

  The cationic charge density is preferably 0.1 meq / g or more, more preferably 0.5 meq / g or more, still more preferably 1.1 meq / g, and even more preferably 1.2 meq / g or more. The cationic charge density of the cationic polymer can be measured by the Kjeldahl method. Since the charge density of the amino-containing polymer varies depending on the pH and the isoelectric point of the amino group, the charge density is set within the above range at the pH of the desired application.

  Any anion counterion can be utilized for the cationic polymer as long as the water solubility criteria is met. Suitable counterions include halides (eg, Cl, Br, I or F compounds, preferably Cl, Br or I compounds), sulfates and methyl sulfates, although others can be used.

  The cationic nitrogen-containing moiety is present as a substituent on all monomer units of the cationic polymer. This cationic polymer thus includes copolymers or polymers of quaternary ammonium or cationic amine substituted monomer units, and other non-cationic units referred to as spacer monomer units. Such polymers are already known in the art and are described, for example, in the International Cosmetic Ingredient Dictionary, 3rd edition, 1982. Suitable cationic polymers include acrylamide, methacrylamide, alkyl acrylamide and dialkyl acrylamide, alkyl methacrylamide and dialkyl methacrylamide, alkyl acrylate, alkyl methacrylate, vinyl caprolactone, and water-soluble spacer monomers such as vinyl pyrrolidone, cationic amines or Mention may be made of copolymers with vinyl monomers having secondary ammonium functional groups.

The alkyl-substituted monomer and dialkyl-substituted monomer preferably have an alkyl group having 1 to 7 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. Other suitable spacer monomers include vinyl esters, vinyl alcohol obtained by hydrolysis of polyvinyl acetate, maleic anhydride, propylene glycol and ethylene glycol. The cationic amine can be a primary, secondary or tertiary amine. Secondary and tertiary amines are preferred, and tertiary amines are particularly preferred. Amine-substituted vinyl monomers can be polymerized in the amine form and then optionally converted to ammonium by a quaternization reaction. The amine can be quaternized in the same way after the polymer is formed. For example, a tertiary amine functional group can be quaternized by reacting with a salt of formula R ⁰ X. Here, R ⁰ is a short-chain alkyl group, preferably an alkyl group having 1 to 7 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and X is an anion that forms a water-soluble salt with quaternized ammonium. is there.

  Suitable cationic amino monomers and quaternary ammonium monomers include, for example, dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, monoalkylaminoalkyl acrylate, monoalkylaminoalkyl methacrylate, trialkylmethacryloxyalkylammonium salt, trialkylacryloxyalkyl Ammonium salts, vinyl compounds substituted with diallyl quaternary ammonium salts, and vinyl quaternary ammonium monomers and quaternized pyrrolidones having cyclic cation nitrogen-containing rings such as pyridinium, imidazolium and quaternized pyrrolidones such as alkyl vinyl imidazolium, alkyl vinyl Examples include pyridinium and alkyl vinyl pyrrolidone salts.

  The alkyl part of these monomers is preferably a lower alkyl group such as an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms. Suitable amine substituted vinyl monomers include dialkylaminoalkyl acrylates, dialkylaminoalkyl methacrylates, dialkylaminoalkyl acrylamides, and dialkylaminoalkyl methacrylamides. Here, the alkyl group is preferably a hydrocarbyl group having 1 to 7 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. The cationic polymer can comprise a mixture of monomer units derived from amines and / or quaternary ammonium substituted monomers and / or compatible spacer monomers.

  Suitable cationic polymers include, for example, copolymers of 1-vinyl-2-pyrrolidone and 1-vinyl-3-methylimidazolium salt (eg, chloride) (referred to as polyquaterium-16 in “CTFA”), BASF Wyandotte (BASF Wyandotte Corp., Parsippany, NJ, USA) under the trade name LUVIQUAT (e.g. RUQUIQUAT FC 370); copolymer of 1-vinyl-2-pyrrolidone and dimethylaminoethyl methacrylate ("CTFA") In the trade name of GAFQUAT (for example, Gafquat 755N) commercially available from Gaf Corporation (Wayne, NJ, USA); dimethyldiallylammonium chloride; Homopolymers and cationic diallyl quaternary ammonium-containing polymers including acrylamide and dimethyldiallylammonium chloride copolymer (referred to in the “CTFA” industry as polyquaternium 6 and polyquaternium 7); described in US Pat. No. 4,009,256 Mention may be made of mineral acid salts of aminoalkyl esters of homopolymers and copolymers of unsaturated carboxylic acids having 3 to 5 carbon atoms.

式中、Ａはデンプン無水グルコース残基またはセルロース無水グルコース残基などの無水グルコース残基であり、Ｒは、アルキレンオキシアルキレン基、ポリオキシアルキレン基、またはヒドロキシアルキレン基またはこれらの組み合わせである。Ｒ^２２、Ｒ^２３およびＲ^２４は、それぞれ独立してアルキル基、アリール基、アルキルアリール基、アリールアルキル基、アルコキシアルキル基、またはアルコキシアリール基から選択され、それぞれの基は１８個以下の炭素を含有し、各カチオン部分の炭素総数（すなわちＲ^２２、Ｒ^２３およびＲ^２４の炭素数の合計）は好ましくは２０以下である。Ｘは前述のようなアニオン対イオンである。 Other cationic polymers that can be used include polysaccharide polymers such as cationic cellulose derivatives and cationic starch derivatives. Suitable cationic polysaccharide polymers include those having the following formula:

In the formula, A is an anhydroglucose residue such as a starch anhydroglucose residue or a cellulose anhydroglucose residue, and R is an alkyleneoxyalkylene group, a polyoxyalkylene group, a hydroxyalkylene group, or a combination thereof. R ²² , R ²³ and R ²⁴ are each independently selected from an alkyl group, an aryl group, an alkylaryl group, an arylalkyl group, an alkoxyalkyl group, or an alkoxyaryl group, each group having 18 or fewer carbons. The total number of carbons in each cation moiety (that is, the total number of carbon atoms of R ²² , R ²³ and R ²⁴ ) is preferably 20 or less. X is an anion counter ion as described above.

  Cationic cellulose is commercially available from Amerchol Corp. (Edison, NJ, USA) as a salt obtained by reacting hydroxyethyl cellulose with a trimethylammonium substituted epoxide under the trade name polymer JR and LR series. In this case, it is called polyquaternium 10. Other types of cationic cellulose include polymeric quaternary ammonium salts reacted with hydroxyethyl cellulose and lauryldimethylammonium substituted epoxide, what is called polyquaternium 24 in the “CTFA” industry. These substances are commercially available from Amercor as trade name polymer LM-200. Other cationic polymers include cationic guar rubber derivatives such as guar hydroxypropyltrimonium chloride (trade name Jaguar® series commercially available from Celanese Corp.). Also included are quaternary nitrogen-containing cellulose ethers (such as those described in US Pat. No. 3,962,418), and etherified celluloses and starches (such as those described in US Pat. No. 3,958,581). It is done.

  In the first embodiment of the present invention, the water as component (E) is (A) spherical silicone fine particles surface-treated with an amino group-containing organosilicon compound, and (B) has a viscosity at 25 ° C. of 1 to 100,000 Pa. Used as a dispersion medium for polyorganosiloxane of s, (C) high melting point aliphatic compound and (D1) cation conditioning agent. (E) A uniform hair cosmetic composition such as a conditioner composition can be obtained by blending water.

  In the second embodiment of the present invention, the detersive surfactant which is the component (F) is an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant for the purpose of imparting cleaning performance to the composition. A surfactant selected from zwitterionic surfactants and mixtures thereof. The term “detergent surfactant” is intended to distinguish these from surfactants that mainly emulsify the surfactant, ie, surfactants that provide emulsification benefits and have low detergency. ing. However, since many surfactants have both detergency and emulsifying properties, emulsifying surfactants are not excluded from the detersive surfactants of the present invention.

  Examples of the anionic surfactant include polyoxyethylene alkyl ether sulfuric acid, alkyl sulfuric acid, and salts thereof. Specifically, polyoxyethylene alkyl ether sulfuric acid includes polyoxyethylene (2) octyl ether sulfuric acid, polyoxyethylene (8) decyl ether sulfuric acid, polyoxyethylene (3) lauryl ether sulfuric acid, and the like. Examples thereof include sulfuric acid, myristyl sulfuric acid, cetyl sulfuric acid, and the like, and salts thereof, that is, salt-type anionic surfactants are also included. As the kind of salt, amine salts such as sodium salt, potassium salt, ammonium salt and triethanolamine are preferable, and from the viewpoint of feeling at the time of rinsing, among them, use of triethanolamine and ammonium salt is preferable. As the anionic surfactant, polyoxyethylene alkyl ether carboxylate, N-acyl amino acid salt, N-acyl taurate and the like can also be used.

  Nonionic surfactants include, for example, condensation of linear or branched aliphatic (C8 to C18) primary or secondary alcohols or phenols with alkylene oxides (usually ethylene oxide, propylene oxide, butylene oxide). And generally having 3 to 50 ethylene oxide groups. For example, Neugen ET-102 (polyoxyethylene lauryl ether (EO: 5), manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Neugen YX-400 (polyoxyethylene lauryl ether (EO: 40), Daiichi Kogyo Seiyaku Co., Ltd.) )) Is a commercially available product.

  As the amphoteric surfactant and / or the semipolar surfactant, all those usually used for cosmetic bases and the like are applied. In particular, the following general formulas: (Chemical Formula 9) to (Chemical Formula 13) are used. One or more selected from the group consisting of compounds are preferably used.

で表されるアミドベタイン型両性界面活性剤。

で表されるアミドスルホベタイン型両性界面活性剤。

で表されるベタイン型両性界面活性剤。

で表されるスルホベタイン型両性界面活性剤。

で表されるイミダゾリニウム型両性界面活性剤。 That is,

Amidobetaine-type amphoteric surfactant represented by

Amidosulfobetaine-type amphoteric surfactant represented by

Betaine amphoteric surfactant represented by

A sulfobetaine type amphoteric surfactant represented by the formula:

An imidazolinium type amphoteric surfactant represented by

In the general formula: (Chemical Formula 9) to (Chemical Formula 13), R ²⁶ represents an alkyl group or an alkenyl group having 9 to 21 carbon atoms, and the number of carbon atoms is more preferably 1 to 17, Most preferably, it is 11-13. If the number of carbon atoms is less than 9, it is difficult to form a complex because the hydrophilicity is too strong. On the other hand, if the number of carbon atoms exceeds 21, the solubility in water becomes poor and it is difficult to form a complex. R ²⁷ and R ²⁸ each independently represents an alkyl or alkenyl group having 10 to 18 carbon atoms, t represents an integer of 2 to 4, u represents an integer of 0 to 3, and v represents 1 or 2. Represents an integer.

  Here, examples of the amide betaine type amphoteric surfactant represented by the general formula: (Chemical Formula 9) include, for example, palm oil fatty acid amidopropyldimethylaminoacetic acid betaine and the like, “Levon 2000” (manufactured by Sanyo Chemical Industries, Ltd.). ), “Anon BDF” (manufactured by NOF Corporation) and the like are exemplified as commercial products. As the amidosulfobetaine type amphoteric surfactant represented by the general formula: (Chemical Formula 10), “Lonzain-CS” (manufactured by Lonza), “Miratine CBS” (manufactured by Milanol), etc. are commercially available products. As an example. Examples of the betaine-type amphoteric surfactant represented by the general formula: (Chemical Formula 11) include, for example, lauryldimethylaminoacetic acid betaine, “Anon BL” (manufactured by NOF Corporation), “Dehington AB-30” (Henkel Co., Ltd.) etc. are illustrated as a commercial item. As the sulfobetaine type amphoteric surfactant represented by the general formula: (Chemical Formula 12), “Lonzain-12CS” (manufactured by Lonza Co., Ltd.) and the like are exemplified as commercial products. Furthermore, examples of the imidazolinium type amphoteric surfactant represented by the general formula: (Chemical Formula 13) include 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium. “Obazoline 662-N” (manufactured by Toho Chemical Co., Ltd.), “Anon GLM” (manufactured by Nippon Oil & Fats Co., Ltd.), etc. Among these, coconut oil fatty acid amidopropyl betaine is particularly desirable.

式中、Ｒ^２８は炭素原子数１０〜１８のアルキル基またはアルケニル基を表す。 As the semipolar surfactant, all those usually used for cosmetic bases and the like are applied, but tertiary amine oxide type semipolar surfactants represented by the following general formula: Used for.

In the formula, R ²⁸ represents an alkyl group or an alkenyl group having 10 to 18 carbon atoms.

  Examples of the tertiary amine oxide semipolar surfactant represented by the above general formula: (Chemical Formula 14) include lauryl dimethylamine oxide, lauric acid amidopropyl dimethylamine oxide, and the like. “Unisafe A-LM” "" (Manufactured by NOF Corporation), "McAmin LAO" (manufactured by McIntyre Co., Ltd.), etc. Among these, lauric acid amidopropyldimethylamine oxide is desirable.

  These (F) detersive surfactants are contained in a proportion of 5 to 50% by weight, preferably 8 to 30% by weight, more preferably 10 to 25% by weight of the hair cosmetic composition.

  In the second embodiment of the present invention, a known conditioning agent can be used as the (C2) conditioning agent. Suitable (C2) conditioning agents include the aforementioned cationic surfactants, water-soluble cationic polymers, fatty compounds, non-volatile dispersed silicones, hydrocarbons, proteins and mixtures thereof. These conditioning agents are contained in a proportion of 0.1 to 20% by weight of the hair cosmetic composition.

  In the second embodiment of the present invention, the water as component (E) is (A) spherical silicone fine particles surface-treated with an amino group-containing organosilicon compound, and (B) has a viscosity at 25 ° C. of 1 to 100,000 Pa. Used as a dispersion medium for polyorganosiloxane of s, (F) detersive surfactant and (D2) conditioning agent. (E) A uniform hair cosmetic composition such as a shampoo composition can be obtained by blending water.

  According to the hair cosmetic composition of the first and the embodiments of the present invention, it exhibits an excellent conditioning effect on the hair and imparts an excellent slipping feeling and moist feeling to wet and dry hair. can do.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these Examples. In the examples, “part” represents “part by weight” and “%” represents “% by weight”.

[Synthesis of spherical silicone fine particles]
(Synthesis Example 1)
1800 parts of water having an electric conductivity of 0.96 μS / cm measured in an electric conductivity meter (manufactured by Toa Denpa Kogyo Co., Ltd .; CM-11P) in a reaction vessel equipped with a thermometer, a reflux device and a stirrer And hydrochloric acid was added thereto to adjust the conductivity to 4.80 μS / cm. While stirring this solution at 25 ° C., 300 parts of methyltrimethoxysilane was added thereto over 1 hour, and the stirring was continued for 2 hours for hydrolysis to obtain a silanol solution.

  The temperature of the resulting silanol solution was adjusted to 15 ° C., 13.2 parts of a 0.37% aqueous ammonia solution was added, and the mixture was stirred for 1 minute, and then stirred for 5 hours. Next, the reaction solution after standing was passed through a 200-mesh wire mesh, and then suction filtration was performed to obtain a wet cake-like white powder.

  The powder thus obtained was measured with a refractive index of 1.425 using a particle size distribution analyzer (manufactured by COULTER; LS100Q), and the average particle size was 5.6 μm. Further, when a part of the powder was dried at 200 ° C. and observed with an electron microscope, the particle shape was spherical.

  Next, 30 parts of the obtained wet cake-like white powder (spherical polymethylsilsesquioxane particles having an average particle size of 5.6 μm) and 80 parts of ethanol were charged into a reaction vessel, and uniform using an ultrasonic dispersing device. A dispersion was prepared. Next, 2 parts of γ-aminopropyltriethoxysilane was charged into the reaction vessel and stirred while heating at 70 ° C. for 4 hours. Thereafter, the particles were separated and washed with 100 parts of acetone to obtain particles surface-treated with the aminosilane. Further, the particles were dried at 130 ° C. for 20 hours and pulverized using a jet mill.

  When the fine particles obtained in this way were observed with an electron microscope, the particle shape maintained a true spherical shape, and no condensation of particles was observed. The particle diameter was 6.0 μm.

(Synthesis Example 2)
Particles surface-treated with aminosilane were obtained in the same manner as in Synthesis Example 1 except that N-β (aminoethyl) γ-aminopropyltrimethoxysilane was used instead of γ-aminopropyltriethoxysilane. When the obtained fine particles were observed with an electron microscope, the particle shape retained a true spherical shape, and no condensation of particles was observed. The particle diameter was 6.1 μm.

(Synthesis Example 3)
750 parts of water having an electric conductivity of 1.09 μS / cm measured in a reaction vessel equipped with a thermometer, a refluxer and a stirrer using an electric conductivity meter (manufactured by Toa Denpa Kogyo Co., Ltd .; CM-11P) And hydrochloric acid was added thereto to adjust the conductivity to 5.40 μS / cm. While stirring this solution at 25 ° C., a mixture obtained by adding 2.8 parts of tetramethoxysilane to 100 parts of methyltrimethoxysilane was added over 1 hour, and the hydrolysis was further continued for 2 hours. And a silanol solution was obtained.

  The temperature of the obtained silanol solution was adjusted to 15 ° C., 1.64 parts of a 10% aqueous ammonia solution was added, stirred for 1 minute, and then stirred for 5 hours. The reaction solution after standing was passed through a 325-mesh wire mesh and suction filtered to obtain a wet cake-like white powder.

  The powder thus obtained was measured using a particle size distribution measuring apparatus (manufactured by COULTER; S100Q) with a refractive index of 1.425, and the average particle diameter was 2.1 μm. Further, when a part of the powder was dried at 200 ° C. and observed with an electron microscope, the particle shape was spherical.

  Subsequently, a partial hydrolyzate of N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane was prepared. That is, 50 g of N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane was charged into a 100 ml reaction vessel equipped with a thermometer, a stirrer, and a dropping device, and the temperature was adjusted to 25 ° C. To this, 4.4 g of water having an electric conductivity of 0.86 μS / cm measured using an electric conductivity meter was dropped over 30 minutes. The solution was heated up to 80 degreeC after completion | finish of dripping, and stirring was continued for 1 hour. Subsequently, the reaction solution was heated to 90 ° C., and methanol produced by hydrolysis was distilled off over 3 hours. Thereafter, the reaction solution was heated and stirred at 100 ° C. for 3 hours and then cooled to room temperature to obtain a partial hydrolyzate of N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane.

  Next, 30 parts of the previously obtained wet cake-like white powder (spherical polymethylsilsesquioxane particles having an average particle size of 2.1 μm) and 100 parts of methanol are charged into a reaction vessel, and an ultrasonic dispersion apparatus is used. Thus, a uniform dispersion was prepared. Next, 1.5 parts of a partial hydrolyzate of N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane was charged into a reaction vessel and stirred while heating at 65 ° C. for 5 hours. Thereafter, the particles were separated and washed with 100 parts of acetone to obtain particles surface-treated with the aminosilane. Further, the particles were dried at 130 ° C. for 20 hours and pulverized using a jet mill.

  When the fine particles obtained in this way were observed with an electron microscope, the particle shape maintained a true spherical shape, and no condensation of particles was observed. The particle diameter was 2.3 μm.

(Synthesis Example 4)
1800 parts of water having an electric conductivity of 0.96 μS / cm measured in an electric conductivity meter (manufactured by Toa Denpa Kogyo Co., Ltd .; CM-11P) in a reaction vessel equipped with a thermometer, a reflux device and a stirrer And hydrochloric acid was added thereto to adjust the conductivity to 4.80 μS / cm. While stirring this solution at 25 ° C., 300 parts of methyltrimethoxysilane was added thereto over 1 hour, and the stirring was continued for 2 hours for hydrolysis to obtain a silanol solution.

  The temperature of the resulting silanol solution was adjusted to 15 ° C., 13.2 parts of a 0.37% aqueous ammonia solution was added, and the mixture was stirred for 1 minute, and then stirred for 5 hours. The reaction solution after standing was passed through a 200-mesh wire mesh and suction filtered to obtain a wet cake-like white powder.

  The powder thus obtained was dried at 150 ° C. overnight and then pulverized using a jet mill to obtain a white powder (spherical polymethylsilsesquioxane fine particles).

  When this powder was measured using a particle size distribution measuring apparatus (manufactured by COULTER KK; LS100Q) with a refractive index set to 1.425, the average particle size was 5.6 μm. When this powder was observed with an electron microscope, the particle shape was spherical.

[Preparation of emulsion]
(Preparation Example 1)
The viscosity at 25 ° C. is 3,000 Pa.s. 24 parts of polydimethylsiloxane (dimethicone) of s, 30 parts of isoparaffin (trade name Isosol 400S, manufactured by Nisseki Chemical Co., Ltd.), and 6 parts of the surface-treated spherical silicone fine particles obtained in Synthesis Example 1, After uniformly mixing at 70 ° C., 3.0 parts of polyoxyethylene (4) lauryl ether and 2.5 parts of polyoxyethylene (23) lauryl ether were added and stirring was continued at 70 ° C. for 1 hour to make the system homogeneous. I made it.

  Next, 4.0 parts of water was added thereto, and the mixture was stirred for 3 hours to invert the phase to obtain a transparent grease. Thereafter, 30 parts of water and 0.5 part of salicylic acid were added and stirred for 1 hour to obtain a uniform O / W emulsion (E-1).

  When the particle size of the emulsion (E-1) was measured using a particle size distribution measuring device (manufactured by COULTER KK; LS100Q) with a refractive index set to 1.45, the average particle size was 6.4 μm. . When this emulsion was allowed to stand at 50 ° C. for 1 month, no settling of silicone fine particles to the bottom and separation of the emulsion were observed.

(Preparation Example 2)
A uniform O / W emulsion (E-2) was prepared in the same manner as in Preparation Example 1 except that the spherical silicone fine particles obtained in Synthesis Example 2 were used instead of the spherical silicone fine particles obtained in Synthesis Example 1. )

  When the particle size of the emulsion (E-2) was measured using a particle size distribution analyzer (manufactured by COULTER, LS100Q) with a refractive index set to 1.45, the average particle size was 6.1 μm. . When this emulsion was allowed to stand at 50 ° C. for 1 month, no settling of silicone fine particles to the bottom and separation of the emulsion were observed.

(Preparation Example 3)
The viscosity at 25 ° C. is 80 Pa. After mixing 54 parts of hydroxypolydimethylsiloxane (dimethiconol) at both ends of s and 6 parts of the surface-treated spherical silicone fine particles obtained in Synthesis Example 3 at 70 ° C., polyoxyethylene (4) lauryl ether 3 0.0 part and 2.5 parts of polyoxyethylene (23) lauryl ether were added, and stirring was further continued at 70 ° C. for 1 hour to make the system uniform.

  Next, 4.0 parts of water was added thereto, and the mixture was stirred for 3 hours to invert the phase to obtain a transparent grease. Thereafter, 30 parts of water and 0.5 part of salicylic acid were added and stirred for 1 hour to obtain a uniform O / W emulsion (E-3) having a silicone content of 60%.

  When the particle size of this emulsion (E-3) was measured using a particle size distribution analyzer (manufactured by COULTER KK; LS100Q) with a refractive index set to 1.45, the average particle size was 1.9 μm. . When this emulsion was allowed to stand at 50 ° C. for 1 month, no settling of silicone fine particles to the bottom and separation of the emulsion were observed.

(Preparation Example 4)
Nitrogen content 0.1%, viscosity at 25 ° C. 80 Pa. 54 parts of N- (2-aminoethyl) -3-aminopropyl group-containing polydimethylsiloxane (amodimethicone) and 6 parts of the surface-treated spherical silicone fine particles obtained in Synthesis Example 3 were uniformly distributed at 60 ° C. After mixing, 6 parts of cocoamidopropyl betaine (30% aqueous solution) was added and stirred well at 60 ° C. Thereafter, the mixture was stirred while gradually adding 33 parts of ion exchange water.

  Subsequently, 1 part of lactic acid was added thereto and stirred to obtain a milky white silicone emulsion (E-4) having a silicone content of 60%.

  When the particle size of this emulsion (E-4) was measured using a particle size distribution analyzer (manufactured by COULTER, LS100Q) with a refractive index set to 1.45, the average particle size was 2.5 μm. .

(Preparation Example 5)
A uniform O / W emulsion (E-5) was prepared in the same manner as in Preparation Example 1 except that the spherical silicone fine particles obtained in Synthesis Example 4 were used instead of the spherical silicone fine particles obtained in Synthesis Example 1. )

  When the particle size of this emulsion (E-5) was measured using a particle size distribution analyzer (manufactured by COULTER KK; LS100Q) with a refractive index set to 1.45, the average particle size was 6.3 μm. . When this emulsion was allowed to stand at 50 ° C. for 1 month, no settling of silicone fine particles to the bottom and separation of the emulsion were observed.

(Preparation Example 6)
The viscosity at 25 ° C. is 3,000 Pa.s. s dimethicone 30 parts and isoparaffin (trade name Isosol 400S) 30 parts uniformly mixed at 70 ° C., then 3.0 parts of polyoxyethylene (4) lauryl ether and 2.5 parts of polyoxyethylene (23) lauryl ether The mixture was further stirred at 70 ° C. for 1 hour to make the system uniform. Next, 4.0 parts of water was added thereto, and the mixture was stirred for 3 hours to invert the phase to obtain a transparent grease. Thereafter, 30 parts of water and 0.5 part of salicylic acid were added and stirred for 1 hour to obtain a uniform O / W emulsion (E-6).

  When the particle size of the emulsion (E-6) was measured using a particle size distribution analyzer (manufactured by COULTER KK; LS100Q) with a refractive index set to 1.45, the average particle size was 4.2 μm. . When this emulsion was allowed to stand at 50 ° C. for 1 month, no separation of the emulsion was observed.

Examples 1-4, Comparative Examples 1-3 [Hair conditioner composition]
Using the silicone emulsions (E-1) to (E-6) obtained in Preparation Examples 1 to 4 and the silicone fine particles obtained in Synthesis Example 1, hair conditioner compositions were prepared with the compositions shown in Table 1. . And about the prepared conditioner composition, the characteristic evaluation was performed according to the method and reference | standard shown below.

[Evaluation methods]
Each of the 12 panelists dipped 10 g of 25 cm long hair in 40 ° C. water, spread 2 g of the conditioner composition on the wet hair, and rinsed with 40 ° C. water for 30 seconds after 1 minute. Subsequently, it dried with the dryer and the hair sample was created. In the hair sample preparation stage, each panelist was given a five-point score based on the following criteria: “No squeaky feeling when rinsing”, “Finger feeling after drying” and “Moist feeling after drying”. The average value was calculated.
[Evaluation criteria]
5 ... excellent 4 ... excellent 3 ... good 2 ... slightly inferior 1 ... poor evaluation results are shown in Table 1.

Examples 5-8, Comparative Examples 4-6 [Shampoo Composition]
Using the silicone emulsions (E-1) to (E-6) obtained in Preparation Examples 1 to 6 and the silicone fine particles obtained in Synthesis Example 1, shampoo compositions having the compositions shown in Table 2 were prepared. And about the prepared shampoo composition, the characteristic evaluation was performed according to the method and reference | standard shown below.

[Evaluation methods]
Each of the 12 panelists soaked 10 g of 25 cm long hair in 40 ° C. water, washed with 2 g of shampoo composition for 1 minute, rinsed with 40 ° C. water for 30 seconds, and dried with a drier to prepare a hair sample. . At the hair sample preparation stage, each panelist was given 5 levels of “no squeaking feeling during washing and rinsing”, “feeling of fingering after drying” and “moist feeling after drying”. The score was calculated and the average value was calculated.
[Evaluation criteria]
5 ... excellent 4 ... excellent 3 ... good 2 ... slightly inferior 1 ... poor evaluation results are shown in Table 2.

  The hair cosmetic composition of the present invention can impart a smooth and moist feel to the hair, and is particularly excellent in slipperiness against damaged hair during washing and rinsing, and excellent fingering on dry hair. Since it is possible to impart a motility and a moist feeling, it is suitable as a hair conditioner or shampoo.

Claims (4)

(A) 0.05 to 10% by weight of spherical polyorganosilsesquioxane fine particles surface-treated with an organosilicon compound containing an amino group represented by the following formula and / or a hydrolysis / condensation product thereof ; B) 0.1 to 30% by weight of a polyorganosiloxane having a viscosity of 1 to 100,000 Pa · s at 25 ° C., and (C) 0.1 to 15% by weight of a high melting point aliphatic compound having a melting point of 25 ° C. or more, (D1) a cationic conditioning agent 0.1 to 10% by weight, and (E) water ,
A hair cosmetic composition wherein the weight ratio of the (A) spherical polyorganosilsesquioxane fine particles to the (B) polyorganosiloxane is 1/9 to 1/4 .
H ₂ NCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ ,
H ₂ NCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ NHC ₃ H ₆ Si (OCH ₃ ) ₃ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH (CH ₃ ) CH ₂ Si (OCH ₃ ) ₃ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH (CH ₃ ) CH ₂ Si (OCH ₂ CH ₃ ) ₃ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH (CH ₃ ) CH ₂ SiCH ₃ (OCH ₃ ) ₂ ,
H ₂ NC ₆ H ₄ Si (OCH ₃ ) ₃ ,
C ₆ H ₅ NHCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ (A) 0.05 to 10% by weight of spherical polyorganosilsesquioxane fine particles surface-treated with an organosilicon compound containing an amino group represented by the following formula and / or a hydrolysis / condensation product thereof ; B) 0.1 to 30% by weight of a polyorganosiloxane having a viscosity of 1 to 100,000 Pa · s at 25 ° C., (F) 5 to 50% by weight of a detersive surfactant, and (D2) a conditioning agent of 0.1 Each containing ~ 20 wt% and (E) water ;
A hair cosmetic composition wherein the weight ratio of the (A) spherical polyorganosilsesquioxane fine particles to the (B) polyorganosiloxane is 1/9 to 1/4 .
H ₂ NCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ ,
H ₂ NCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ NHC ₃ H ₆ Si (OCH ₃ ) ₃ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH (CH ₃ ) CH ₂ Si (OCH ₃ ) ₃ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH (CH ₃ ) CH ₂ Si (OCH ₂ CH ₃ ) ₃ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH (CH ₃ ) CH ₂ SiCH ₃ (OCH ₃ ) ₂ ,
H ₂ NC ₆ H ₄ Si (OCH ₃ ) ₃ ,
C ₆ H ₅ NHCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ The hair cosmetic composition according to claim 1 or 2, wherein the spherical polyorganosilsesquioxane fine particles have an average particle size of 1 to 30 µm. The oil-in-water type silicone emulsion containing the spherical polyorganosilsesquioxane fine particles as the component (A) and the polyorganosiloxane as the component (B) is contained. The hair cosmetic composition according to Item.