JP4667851B2 - Liquid detergent for skin - Google Patents

Description

  The present invention relates to a skin liquid cleaning agent, and more particularly, to a skin liquid cleaning agent that has good foaming and foam quality and excellent usability, and has a smooth and moist feeling after washing and drying.

  Conventionally, as a liquid cleaning agent for skin, one containing a higher fatty acid salt has been used. Such a cleaning agent is preferred in that it gives a refreshing feel after washing, but has a drawback that the feeling of skin tightness and dryness after use is very strong. This is considered to be caused by excessive washing of oil during washing.

  Therefore, recently, N-acylated amino acid surfactants have been used as surfactants with weak skin irritation. However, the skin cleanser containing such a surfactant has a problem that it has a feeling of tension after rinsing although it has a weak feeling after use, and lacks a refreshing feeling. In addition, with any of the cleaning agents, a smooth feel, that is, a so-called smooth feeling is not obtained after use.

  Furthermore, a skin cleanser formulated with silicone oil is also known in order to achieve both cleaning performance and a good feeling during use and after rinsing (smooth feeling, moist feeling, etc.). For example, a skin cleansing composition containing linear silicone has been proposed. (For example, refer patent document 1) Moreover, the detergent composition containing the non-hydrolyzable block copolymer which uses a linear polysiloxane polyoxyalkylene block as a repeating unit is also proposed. (For example, see Patent Document 2)

  However, in the cleaning composition containing the linear silicone, the feeling of use is improved, but the refreshing feeling at the time of rinsing is still insufficient. In addition, in the detergent composition containing polyorganosiloxane in which a part of dimethylsiloxane is modified with a polyether group or amino group, as described in Patent Document 2, one of feeling of use or refreshing is improved. , Couldn't satisfy both feels.

Furthermore, a liquid detergent for skin containing spherical silicone fine particles having a specific particle size has been proposed (see, for example, Patent Document 3), but the feeling during use and the smooth feeling after drying are improved to some extent. But still not enough.
JP-A-6-17097 JP-A-6-49486 JP 2003-267860 A

  The present invention was made in order to solve these problems, and has an object to provide a liquid cleaning agent for skin that has high cleaning performance and is excellent in use feeling after washing and drying, moist feeling, and the like. To do.

  As a result of diligent research to achieve the above object, the present inventors have found that blending spherical silicone fine particles whose surface is treated with an organosilicon compound containing an amino group has a feeling of use after washing and drying, and smoothness. The present invention was completed by finding that it is extremely effective in improving the feeling.

That is, the liquid detergent for skin of the present invention comprises (A) γ-aminopropyltriethoxysilane and its hydrolysis / condensate, N-β (aminoethyl) γ-aminopropyltrimethoxysilane and its hydrolysis / condensation. 0.1 to 15 weights of spherical polyorganosilsesquioxane fine particles that are surface-treated with at least one selected from the group consisting of N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane and its hydrolysis / condensation product %, (B) 2 to 40% by weight of fatty acid soap, (C) 0.01 to 20% by weight of a cation conditioning agent, and (D) water.

  The liquid detergent for skin of the present invention has good foaming and foam quality, has high cleanability on the skin, has a good feeling of use, and is excellent in a smooth feeling and a moist feeling after washing and after drying. ing.

  Hereinafter, embodiments of the liquid detergent for skin according to the present invention will be described. In the embodiment of the present invention, the skin liquid cleaning agent means a liquid cleaning agent directly used for cleaning the skin among general body cleaning agents. More specifically, it includes body soaps, body cleaners called body shampoos, palm soap hand soaps, and facial cleansers.

  The skin cleanser according to an embodiment of the present invention includes (A) 0.1 to 15% by weight of spherical silicone fine particles that are surface-treated with an amino group-containing organosilicon compound and / or a hydrolyzate / condensate thereof. , (B) 2-40 wt% fatty acid soap, (C) 0.01-20 wt% cation conditioning agent, and (D) water.

  In the embodiment, the spherical silicone fine particle as the component (A) is a component that characterizes the present invention, and can provide a good feeling of use, a smooth feeling and the like after washing and after drying.

  In the embodiment of the present invention, for example, fine particles made of polyorganosilsesquioxane can be used as the spherical silicone fine particles. Polyorganosilsesquioxane fine particles are finely cross-linked silicone resin fine particles having a three-dimensional network structure by siloxane bonds, and are excellent in solvent resistance that do 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 embodiment preferably have an average particle diameter of 1 to 30 μm, and more preferably 2 to 25 μm. When the average particle size is less than 1 μm, a squeaky sensation appears after washing and drying. When the average particle size is 30 μm or more, the foaming property is lowered, and the particles settle when the final product is a body shampoo or the like It becomes easy to do. 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 embodiment of the present invention, the amino group-containing organosilicon compound for treating the surface of such polyorganosilsesquioxane fine particles,
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 embodiment of the present invention, the polyorganosilsesquioxane fine particles described above using 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, any method may be used as long as the surface of the fine particles can be coated with the 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.

  The fatty acid soap of component (B) used in the embodiment of the present invention is preferably a saturated or unsaturated linear or branched fatty acid soap having 10 to 22 carbon atoms. The use of a fatty acid soap having 12 to 18 carbon atoms is more preferable, and particularly, the use of a fatty acid soap having a ratio of a fatty acid having 12 to 14 carbon atoms and a fatty acid having 16 to 18 carbon atoms is 1/1 to 10/1. . Specific examples of preferable fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and the like.

  Moreover, in preparing (B) fatty acid soap, examples of the cation used for neutralizing the fatty acid include alkali metal ions such as sodium and potassium, alkaline earth metal ions such as magnesium, triethanolamine, and ammonia. However, potassium ion or triethanolamine is more preferable. In the embodiment of the present invention, these fatty acid soaps may be used alone or in admixture of two or more. Moreover, although fatty acid soap may be prepared before mix | blending with the cleaning agent of this invention, it is good also as fatty acid soap by mix | blending both a fatty acid and an alkali with a cleaning composition, and making it react in a composition.

  In the embodiment of the present invention, the spherical silicone fine particles surface-treated with the amino group-containing organosilicon compound as the component (A) are 0.1 to 15% by weight, preferably 0.8%, based on the entire skin liquid detergent. It mix | blends in the ratio of 2-10 weight%. Moreover, the fatty acid soap which is (B) component is mix | blended in the ratio of 2 to 40 weight% with respect to the whole liquid detergent for skin, More preferably, it is 5 to 20 weight%, Most preferably, it is mix | blended in the ratio of 10 to 20 weight%. . The weight blending ratio of the (A) component and the (B) component ((A) component / (B) component) is preferably in the range of 1/200 to 1/5, and 1/100 to 1 / A range of 10 is more preferred. When the blending ratio is out of the range of 1/200 to 1/5, it is impossible to obtain a liquid detergent for skin that satisfies both the feeling of use and the feeling of smoothness and moistness after washing and after drying.

In the embodiment of the present invention, the cationic conditioning agent as component (C) is selected from the group consisting of a cationic surfactant, a cationic polymer, and a mixture thereof.
These (C) cationic conditioning agents are contained in the liquid detergent for skin in an amount of 0.01 to 20% by weight, preferably 0.05 to 8% by weight, more preferably 0.1 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. “CTFA” represents Cosmetics, Toiletry, and Fragrance Association, Inc.

  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%.

  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 (for example, Rubiquat 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); 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.

  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 (Formula 8).

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。

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.

  Of these (C) cationic conditioning agents, the use of cationic polymers is preferred.

  In an embodiment of the present invention, water as component (D) is used as a dispersion medium for (A) spherical silicone fine particles surface-treated with an amino group-containing organosilicon compound, (B) fatty acid soap, and (C) a cation conditioning agent. Used. (D) A uniform skin cleanser can be obtained by blending water.

  In the embodiment of the present invention, a liquid detergent composition can be prepared by mixing these components (A) to (D) according to a conventional method. In the composition, if necessary, a surfactant generally used in cosmetics can be blended, and optional components such as a viscosity modifier, preservative, disinfectant, fragrance, and pigment are added. be able to. The composition is preferably an emulsion and can be used as a skin cleanser, particularly a hand, face or whole body cleanser.

  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 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 to the solution over 1 hour, and stirring was continued for 2 hours to carry out 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 in 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, and the particles were further dried at 50 ° C. for 14 hours.

  When the fine particles (S-1) obtained in this way were observed with an electron microscope, the particle shape retained a true spherical shape, and no condensation of particles was observed.

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

(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. Next, 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 diameter of 2.1 μm) and 100 parts of methanol are placed in a reaction vessel, and an ultrasonic dispersion apparatus is used. Thus, a uniform dispersion was prepared. Next, 1.5 parts of N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane partial hydrolyzate was charged into the 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, and the particles were further dried at 50 ° C. for 14 hours.

  When the fine particles (S-3) 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.

(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 overnight at 150 ° C. and then pulverized using a jet mill to obtain a white powder (spherical polymethylsilsesquioxane fine particles) (S-4). When this powder (S-4) was measured using a particle size distribution analyzer (manufactured by COULTER, Inc .; LS100Q) with a refractive index of 1.425, the average particle size was 5.6 μm. When this powder was observed with an electron microscope, the particle shape was spherical.

(Synthesis Example 5)
Charge 360 parts of distilled water having an electric conductivity of 0.90 μS / cm measured using an electric conductivity meter (manufactured by Toa Denpa Kogyo Co., Ltd .; CM-11P) to a reaction vessel, add dilute hydrochloric acid, The electric conductivity was adjusted to 4.50 μS / cm. Next, 30 parts of cyclohexanol was added to this solution, 90 parts of methyltrimethoxysilane was further added with stirring, and stirring was continued for another 4 hours at room temperature.

  Next, the liquid temperature of the mixed solution was cooled to 18 ° C., and 2 parts of a 0.38% aqueous ammonia solution was added to the solution while stirring, followed by further stirring for 5 minutes. Next, stirring was stopped and the mixture was allowed to stand at room temperature for 12 hours, followed by suction filtration to obtain a wet cake. This wet cake was dried at 150 ° C. overnight to obtain 41 parts of a white dry powder (S-5).

  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 diameter was 22.3 μm. When this powder was observed with an electron microscope, the particle shape was spherical.

Examples 1-3, Comparative Examples 1-4
Using the spherical silicone particles (S-1) to (S-4) and silicone oils (s-1) and (s-2) obtained in Synthesis Examples 1 to 5, the compositions shown in Table 1 (% by weight) ) To prepare a body soap. Next, for the body soap thus prepared, 10 panelists were given the following “foaming”, “moist” and “smooth” during cleaning, and “moist” and “smooth” after washing, respectively. The average value was calculated by scoring 5 levels on the basis of. These evaluation results are shown in Table 1.

In addition, as silicone oil (s-1) and (s-4), what was shown below was used, respectively.
s-1: Polydimethylsiloxane having a viscosity (25 ° C.) of 500 mPa · s s-2: Amino-modified silicone oil (TSF4703 manufactured by our company)

[Evaluation criteria]
(Bubbles)
5: Good ⇔ 1: Bad (moist feeling)
5: Yes ⇔ 1: No (smooth feeling)
5: Slip comfortable ⇔ 1: Not slippery

  As is apparent from Table 1, the body soaps obtained in Examples 1 to 3 have good foaming and are extremely excellent in moist feeling and smooth feeling after washing and after drying.

  The liquid detergent for skin of the present invention has good foaming and excellent usability, and also has excellent moist feeling and smooth feeling after washing and after drying, so it can be used for whole body like body soap and body shampoo. Suitable for detergents, hand soaps for washing palms, face wash, etc.

Claims (2)

(A) γ-aminopropyltriethoxysilane and its hydrolysis / condensation product, N-β (aminoethyl) γ-aminopropyltrimethoxysilane and its hydrolysis / condensation product, N-β (aminoethyl) γ-amino 0.1 to 15% by weight of spherical polyorganosilsesquioxane fine particles that are surface-treated with at least one selected from propylmethyldimethoxysilane and hydrolyzed / condensed products thereof ,
(B) 2-40% by weight fatty acid soap,
(C) 0.01-20% by weight of a cation conditioning agent,
(D) A liquid detergent for skin, which contains water.   The liquid detergent for skin according to claim 1, wherein the spherical polyorganosilsesquioxane fine particles have an average particle diameter of 1 to 30 µm.