JP2014015426A - Silicone emulsion composition for bath agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organopolysiloxane composition for a bath agent, capable of imparting organopolysiloxane feeling by uniform and efficient adsorption of organopolysiloxane onto the skin even in the case of a use amount decreasing organopolysiloxane concentration in bath water.SOLUTION: An oil-in-water emulsion composition containing a cationized polymer having an imidazolinium group or a quaternary ammonium group in the structure, polyorganosiloxane as an oily component in a bath agent and as a feeling-imparting component, and a surfactant is used in a bath agent.

Description

  The present invention relates to a silicone emulsion composition that exhibits a touch-providing function when used in a skin care cosmetic such as a bath. In the present invention, the bathing agent refers to a body soap, body lotion, bathing agent that is directly poured into bath water, etc. used in bathing. The present invention relates to a silicone emulsion composition capable of imparting a smooth feeling, a film feeling and the like.

  So far, the addition of a cationized polymer and various oil components has been proposed for bathing agents for the purpose of imparting a feeling during and after bathing. For example, Patent Document 1 proposes that a bathing agent is blended with a cationized polymer, an oil component, and a nonionic surfactant, and it is said that a moist and smooth feeling after bathing is obtained. In Document 2, it is said that by adding a cationized polymer having a specific particle size, the bathing water is given a feeling of luster like a natural hot spring, and a moist feeling is obtained after the bathing.

  In addition, so-called organopolysiloxanes such as silicone are known to give a unique and free feeling when used in various cosmetics, and in Patent Document 1, silicone oil is exemplified as one of various oil components. However, in order to exert the effect of organopolysiloxane as a feel-imparting component of a bath agent, it has been necessary to use it at a relatively high concentration as with a general oil component. When organopolysiloxane is used as a feeling imparting component in a bath agent, it is difficult to reduce the amount of the feel imparting component used, that is, to obtain a feeling imparting effect with a low concentration of the feel imparting component in the bath water. It was. For this reason, bathing tank stains caused by high-concentration oily components in bath water, oil floating on the surface of bath water, and non-uniform oily components on the skin caused by oil floating on the surface of bath water There was a problem such as local stickiness due to the adhesion of.

Japanese Patent Laid-Open No. 2-115115 JP-A-9-315951

  In view of this situation, the object of the present invention is to uniformly and efficiently adsorb to the skin while using a relatively low concentration of organopolysiloxane in bath water, and to impart a feel of organopolysiloxane. Thus, an object of the present invention is to provide an emulsion composition for bathing agents that can solve various problems caused by using a high concentration of oily components.

  As a result of intensive studies to solve the above problems, the present inventors have made an oil-in-water emulsion using a specific cationized polymer, an organopolysiloxane as an oily component, and a surfactant, in the bath, after the bath. It has been found that a good feel can be obtained with the organopolysiloxane, and the present invention has been completed.

That is, the present invention
[1] A cationized polymer having an imidazolinium group or a quaternary ammonium group in the structure, an organopolysiloxane in which a siloxane unit is represented by the formula (1),
(R ¹ R ² R ³ SiO _1/2 ) _a (R ⁴ R ⁵ SiO _2/2 ) _b (R ⁶ SiO _3/2 ) _c (SiO _4/2 ) _d (1)
(Wherein R ^{1 to} R ⁶ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, or a hydroxyl group; a, b, c, d Represents the ratio of the number of moles of each unit, and a + b + c + d = 1, 0 ≦ a ≦ 1, 0.2 ≦ b ≦ 1, 0 ≦ c ≦ 0.7, and 0 ≦ d ≦ 0.7. And an oil-in-water emulsion composition for bathing agents containing a surfactant,
[2] The oil-in-water emulsion composition for bathing agents according to [1], wherein the cationized polymer is one or more selected from a cationic guar gum derivative, a cationic cellulose derivative, and a cationic starch derivative.
[3] In the formula (1) representing an organopolysiloxane, a, b, c and d are a + b + c + d = 1, 0 ≦ a ≦ 0.5, 0.5 ≦ b ≦ 1, 0 ≦ c ≦ 0. 3. An oil-in-water emulsion composition for bathing agents according to any one of [1] or [2], wherein 0 ≦ d ≦ 0.3,
[4] A bath agent using the oil-in-water emulsion composition according to any one of [1] to [3].

  Since the oil-in-water emulsion composition according to the present invention contains a cationized polymer in the emulsion particles, it can be efficiently adsorbed on the skin and effectively imparted with a feel by organopolysiloxane. Therefore, by prescribing the composition of the present invention to a bath agent, when the shower water such as rising hot water or the like is applied to the skin, the dry feeling peculiar to organopolysiloxane, the refreshing feeling, the film feeling, Good drainage can be imparted. Therefore, in the prior art, when organopolysiloxane is used as an oil component, a sufficient effect cannot be obtained unless it is added to bath water in an amount exceeding 100 ppm, whereas an effect is obtained at a concentration of about 10 ppm. Therefore, the blending of the oil-based component into the bath agent is more realistic than ever from the viewpoint of production cost and blending design in consideration of stability. It is also possible to suppress bathing tank stains caused by high concentrations of oily components in the bath water, oil floating on the bath water surface, and uneven adhesion to the skin associated therewith.

  The cationized polymer that is an essential component of the oil-in-water emulsion composition of the present invention needs to have an imidazolium group or a quaternary ammonium group in the structure. This is because the imidazolium group or the quaternary ammonium group exerts an effect of high adsorptivity by taking an action of affinity for keratin tissues such as anion-charged skin. As long as the cationized polymer that can be used in the present invention can be used in cosmetics, the structure of the polymer and the molecular weight thereof are not limited, and the basic skeleton of the polymer is generally known as an organic polymer skeleton, organopolysiloxane, etc. The inorganic polymer skeleton may be used. The cationized polymer of the present invention may be a mixture of these various cationized polymers. In order to obtain an emulsion composition with an organopolysiloxane and further efficiently adsorb it to keratinous tissues such as skin, the cationized polymer of the present invention comprises a cationic cellulose derivative, a cationic starch derivative, and a cationic guar gum derivative. Or a vinyl monomer having an imidazolium group or a quaternary ammonium group, such as dimethyldiallylammonium chloride or methylvinylimidazolium chloride, (meth) acrylamide, alkyl and dialkyl (meth) acrylamide, A copolymer with an alkyl (meth) acrylate, vinyl caprolactam, vinyl pyrrolidone or the like is preferred. In the latter group, what is known as "polyquaternium" in the market has been confirmed to be safe for use on the human body as a cosmetic raw material, so for example, polyquaternium-6, -7, -11, -16 , 28, -44, -46, -61 and the like are preferable.

  Among these cationized polymers, available ones are exemplified as cationic cellulose derivatives: O- [2-hydroxy-3- (trimethylammonio) propyl] hydroxyethylcellulose chloride, product name: Katinal HA-100. (Toho Chemical Co., Ltd.), as the cationic starch derivative, hydroxypropyltrimonium chloride starch, product name; SENSOMER CI-50 (manufactured by Nalco Company), as the cationic guar gum derivative, O- "2-hydroxy chloride -3- (trimethylammonio) propyl "guagam, product name: JAGUAR C13S, or JAGUAR C15, JAGUAR C16, JAGUAR C17, JAGUAR C162 (manufactured by Rhodia Inc), dimethy chloride Copolymer of rudiallylammonium and acrylamide, product name; ME polymer 09W (manufactured by Toho Chemical Co., Ltd.).

  From the viewpoint of the adsorption effect of the organopolysiloxane during bathing, the cationized polymer is more preferably selected from cationic cellulose, cationic starch and cationic guar gum derivatives, and may be a mixture thereof.

  The blending amount of the cationized polymer in the oil-in-water emulsion composition of the present invention is 0.1 to 2% by weight in the composition, and more preferably 0.5 to 1.5% by weight. When the amount is less than 0.1% by weight, the adsorption of the organopolysiloxane is poor, and when the amount is more than 2% by weight, the adsorption of the organopolysiloxane is good, but the viscosity increases so that it is difficult to handle the emulsion composition. .

Organopolysiloxane which is another essential component of the oil-in-water emulsion composition of the present invention may be a mixture of siloxane units represented by formula (1).
(R ¹ R ² R ³ SiO _1/2 ) _a (R ⁴ R ⁵ SiO _2/2 ) _b (R ⁶ SiO _3/2 ) _c (SiO _4/2 ) _d (1)
In formula (1), R ^{1 to} R ⁶ may be the same or different and are selected from a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, or a hydroxyl group, and a, b, c and d represent the ratio of the number of moles of each unit, and a + b + c + d = 1, 0 ≦ a ≦ 1, 0.2 ≦ b ≦ 1, 0 ≦ c ≦ 0.7, 0 ≦ d ≦ 0.7. .

The organopolysiloxane of the present invention may be a single polymer or a mixture, and in the case of being a mixture, in the formula (1), a, b, c and d are the average siloxane of the mixture This is the unit composition ratio. The organopolysiloxane used in the present invention is a linear organopolysiloxane having a D unit of (R ⁴ R ⁵ SiO _2/2 ) as a main component as a single or a mixture, and further three-dimensional crosslinking. (R ⁶ SiO _3/2 ) T unit having a structure and (SiO _4/2 ) Q unit may be included. The preferable ratios of the number of units are 0 ≦ a ≦ 0.5, 0.5 ≦ b ≦ 1, 0 ≦ c ≦ 0.3, and 0 ≦ d ≦ 0.3. When b is less than 0.5, it is difficult to obtain a smooth feel peculiar to the linear component organopolysiloxane. Moreover, the range where c and d exceed 0.3 each is not preferable because the blending amount of the linear component organopolysiloxane becomes relatively low, and it is difficult to obtain a smooth feel.

  The organopolysiloxane used in the present invention can be used alone or in combination of several kinds of compositions or different viscosities, and the preferred viscosity range at 25 ° C. is 10 to 100,000 mPa.s. s, more preferably 100 to 50,000 mPa · s. The viscosity is 10 mPa.s. If the viscosity is less than s, the organopolysiloxane has high volatility, so it does not remain on the skin and it is difficult to obtain a touch. On the other hand, if the viscosity is 100,000 mP · s or more, it is difficult to obtain a smooth feel of the organopolysiloxane. It is inferior in stability. In the case where the organopolysiloxane used in the present invention is a mixture having different viscosities, the composition is constituted so long as the viscosity of the mixture is within the above range and the volatilization rate of the organopolysiloxane from the mixture does not become excessive. The viscosity of the organopolysiloxane is 1 to 70,000,000 mPa.s at 25 ° C. It may be s.

R ^{1 to} R ^{6 in} the formula (1) of the present invention may be the same or different, and in the same structural unit, for example, (R ⁴ R ⁵ SiO _2/2 ) structural unit, as R ⁴ , a methyl group, It does not preclude simultaneous selection of three different groups as R ⁵ , that is, methyl, phenyl and hydrogen. Moreover, the structure for connecting each unit may take a form different from each unit structure.

Examples of monovalent hydrocarbon groups that can be selected as R ^{1 to} R ⁶ include linear or branched alkyl groups or alkenyl groups having 1 to 30 carbon atoms, and cycloalkyl groups having 5 to 25 carbon atoms. Or a cycloalkenyl group, an aralkyl group having 6 to 25 carbon atoms, an aryl group, or a substituted hydrocarbon group thereof. Select from a halogen atom, hydroxyl group, alkoxy group, acyloxy group, ketoximate group, amino group, amide group, aminoxy group, mercapto group, alkenyloxy group, acid anhydride group, carbonyl group, saccharide, cyano group, etc. can do. Illustrative examples of preferred monovalent hydrocarbon groups for R ^{1 to} R ⁶ include straight chain or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and tertiary. Libutyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, isohexyl group, heptyl group, isoheptyl group, octyl group, isooctyl group, nonyl group, decyl group, octadecyl group, etc. A cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a dicyclopentyl group, a decahydronaphthyl group, etc., and a cycloalkenyl group such as a cyclopentenyl group ( 1- and 2-, 3-), cyclohexenyl group (1- Preliminary 2-, 3-), or the like, the aralkyl group and aryl group include a phenyl group, a naphthyl group, a tetrahydronaphthyl group, a tolyl group, ethylphenyl group.

The organopolysiloxane of the present invention can be produced by methods known to those skilled in the art. Specific examples of preferred organopolysiloxanes include dimethylpolysiloxane, phenyl-modified dimethylpolysiloxane, alkylaralkyl-modified polysiloxane, fluorine-modified dimethylpolysiloxane, amino-modified dimethylpolysiloxane, amino-modified polyether-modified dimethylpolysiloxane, and amide-modified. Dimethylpolysiloxane, various terminal-reactive dimethylpolysiloxanes, dimethylpolysiloxane wax, trimethylsiloxysilicic acid (consisting of M units and Q units of (R ¹ R ² R ³ SiO _1/2 ) _a ), polymethylsilsesqui Oxane, polyphenylsilsesquioxane, stearoxymethyl polysiloxane, and the like can be mentioned, and these a or a mixture of the formula (1) indicating the constituent ratio of the siloxane unit with respect to the mixture. b, c, d may, if within a certain range. Among these, it is particularly preferable to use linear or branched dimethylpolysiloxane, a mixture of these with trimethylsiloxysilicic acid, or phenyl-modified dimethylpolysiloxane in the composition for a bath agent of the present invention. Or a mixture thereof.

  The compounding amount of the organopolysiloxane that is an essential component of the oil-in-water emulsion composition of the present invention is 3 to 90% by weight, more preferably 5 to 70% by weight in the oil-in-water emulsion composition. When the amount is less than 3% by weight, the feel imparted by the organopolysiloxane component is insufficient, and when the amount exceeds 90% by weight, the viscosity of the emulsion becomes remarkably high, making handling difficult.

  The surfactant used in the present invention is not particularly limited as long as it is a surfactant that can be used in cosmetics. Specifically, nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene hydrogenated castor oil, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, fatty acid monoglyceride; C8-C24 alkyl Cationic surfactants such as trimethylammonium salt and di-C8-C24 alkyldimethylammonium salt; alkyl or alkenyl sulfate added with alkyl or alkenyl sulfate, ethylene oxide and / or propylene oxide, olefin sulfonate, alkane sulfone Anion fields such as acid salts, saturated or unsaturated fatty acid salts, α-sulfo fatty acid salt esters, amino acid type surfactants, phosphate ester type surfactants, taurine type surfactants Active agent, a sulfonic acid type amphoteric surfactants, amphoteric surfactants such as betaine type amphoteric surfactants can be exemplified. The surfactant of the present invention is a nonionic surfactant such as polyoxyethylene alkyl ether, polyoxyethylene hydrogenated castor oil, etc. in that the bath water does not foam when added to the bath water and maintains a stable emulsified state. It is preferable to use an agent.

  The surfactant of the present invention can be used singly or in combination of two or more as required, and the amount used is in the range of 0.5 to 15% by weight in the composition of the present invention. It is preferable from the point that bath water does not foam when added to, and 2 to 10% by weight is particularly preferable.

  In addition to the oil-in-water emulsion composition of the present invention, a pH adjuster, a refreshing agent, an antioxidant, a chelating agent, an absorption accelerator, an inorganic powder, a surfactant, an antiseptic, a fragrance, A colorant or the like can be blended within a range that does not impair the effects of the present invention.

  The emulsion composition of the present invention can be prepared by a known method, and its production method is not particularly limited. Specifically, using a conventional mixer suitable for production of an emulsion, such as a homogenizer, a colloid mill, a homomixer, a high-speed stator rotor agitator, etc., cationized polymer, organopolysiloxane, surfactant, purification It can be produced by mixing and emulsifying water and other components.

  Preferred examples of preparing the emulsion composition of the present invention include an organopolysiloxane, a surfactant, a small amount of water, for example, the same amount of water as the surfactant, and a cationized polymer. After making the water-in-water emulsion, add a small amount of water here and stir with a high-speed stator rotor stirrer to change the phase to an oil-in-water type, and further dilute with water to an arbitrary concentration. The phase inversion emulsification method to obtain is mentioned. In this phase inversion emulsification method, the cationized polymer may be added to the water-in-oil emulsion from the organopolysiloxane, the surfactant, and a small amount of water before phase inversion.

  The phase inversion emulsification method is preferred because it is easy to adjust the emulsion particle size by the stirring speed at the time of phase conversion from the water-in-oil emulsion to the oil-in-water emulsion. In addition, when preparing a water-in-oil emulsion at the initial stage of emulsification, the stirring conditions are not particularly limited, and an anchor mixer, a four-blade propeller, a homogenizer, a colloid mill, a homomixer, It can be performed using a high-speed stator rotor stirring device or the like.

  The oil-in-water emulsion composition of the present invention can be used by blending with other components of the bathing agent as a bathing feel imparting component, and its production method is not particularly limited. When blended in the bath agent, for example, an ordinary mixer such as propeller stirring, turbine stirring, paddle stirring, anchor stirring, homomixer stirring, homodisper stirring, homogenizer stirring, and adi-homomixer stirring can be used.

  Examples of the present invention will be described in detail below, but the present invention is not limited to the following examples. The preparation method of the emulsion and the bath test method in the examples are as follows. All viscosity values are for a temperature of 25 ° C.

<Method for preparing emulsion>
<Emulsions A to J>
Add the organopolysiloxane component and surfactant shown in Table 1 and purified water in the same amount as the surfactant and cationized polymer, and stir at 500 rpm for 5 minutes using a 4-blade propeller. After that, use IKA, Ultra Tarrax T50 Basic, Shaft Generator G45G, stir for 5 minutes at 3000 rpm, add the remaining purified water in the formulation shown in Table 1 and stir for 5 minutes. To prepare emulsions A to I according to the present invention which are oil-in-water emulsions. Emulsion J not according to the present invention shown in Table 1 was prepared in the same manner as Emulsions A to I except that the cationized polymer was not used. The numerical values of the blending components in Table 1 are parts by weight of preparation.

  As the organopolysiloxane, dimethylpolysiloxane, phenyl-modified dimethylpolysiloxane, and trimethylsiloxysilicic acid were used. The dimethylpolysiloxane is composed only of a dimethylsiloxy group (D unit) whose end is blocked with a trimethylsiloxy group (M unit), and has a viscosity of 10 mPa · s, 350 mPa · s, 300,000 mPa · s, 30, Four types of 000,000 mPa · s were used. The phenyl-modified polydimethylsiloxane has a terminal blocked with a trimethylsiloxy group (M unit), dimethylsiloxy (D unit) as a main component and a trifunctional phenylsiloxy group (T unit), and has a viscosity of 1,000 mPa · s was used.

  As a cationic guar gum derivative, product name; JAGUAR C13S (manufactured by Rhodia Inc); as a cationized cellulose derivative, product name; ), A copolymer of dimethyldiallylammonium chloride and acrylamide, product name; ME polymer 09W (manufactured by Toho Chemical Co., Ltd.).

  As the surfactant, polyoxyethylene hydrogenated castor oil having an ethylene oxide addition mole number of 200, product name: BROWNON CW200 (Aoki Yushi Kogyo Co., Ltd.) was used.

<Bathing test method>
The emulsion or mixture is poured into a bathing bath at 40 ° C. and 200 L so as to have a predetermined concentration, and bathing for 10 minutes makes the bathing water slimy, the hot water (shower) drains, and the skin just after bathing. Sensation, dry skin feeling after drying, and skin feeling on skin were confirmed. Evaluation was made based on the following criteria.
<Evaluation>
Equivalent to white hot water A little better than 0 point white hot water 1 better than white hot water 3 points better than 2 hot water

<Example>
The results of the bath test using the prepared organopolysiloxane emulsions A to J are shown in Table 2 together with the emulsion concentration in the bath water. The emulsion compositions obtained by emulsifying the organopolysiloxane with the cationized guar gum derivative all obtained a result that the dry feeling of the skin immediately after the bath and after drying was better than that of white water (Examples 1 to 11). Examples 3, 4, 7, and 8 using emulsions B, E, and F containing dimethylpolysiloxane with a high degree of polymerization mainly composed of D unit were evaluated in four items except for bath water slime. Was higher than the other examples. Among them, Example 8, which uses an emulsion F containing trimethylsiloxysilicic acid mainly composed of M unit and Q unit, has a lower concentration than that of Example 4 and is capable of running out of hot water, feeling smooth after drying, The film feeling on the skin showed the highest evaluation score.

<Comparative example>
In order to examine the addition method of the organopolysiloxane not according to the present invention, four blades of dimethylpolysiloxane, polyoxyethylene hydrogenated castor oil, cationic guar gum derivative and purified water having the same composition as the emulsion B in Table 1 A mixture was prepared by stirring at 500 rpm using a propeller. When the obtained mixture was added to bath water so as to have a concentration of 25 ppm, remarkable oil floating was observed on the surface of the hot water, and uniform diffusion was difficult. Organopolysiloxane was excluded from the evaluation because it was unevenly adhered to the skin surface and undesirable stickiness was observed at the site of adhesion. Therefore, as comparative examples, an organopolysiloxane emulsion J (Comparative Example 1) not according to the present invention, a combination of the emulsion J with a 1% by weight aqueous solution of a cationized polymer (Comparative Examples 2 to 6), A bath test of only a 1% by weight aqueous solution of a cationized polymer (Comparative Examples 7 to 10) was performed, and the evaluation results are shown in Table 3. In Comparative Examples 1 to 6, although the effect of organopolysiloxane (smooth feeling, drainage of rising hot water) was not felt, the slimy feeling of the bath water could be felt. This slimy feeling was equivalent to the test (Comparative Examples 7 to 10) in which only the 1% by weight aqueous solution of the cationized polymer was added.

Claims (4)

A cationized polymer having an imidazolinium group or a quaternary ammonium group in the structure, an organopolysiloxane in which the siloxane unit is represented by the formula (1),
(R ¹ R ² R ³ SiO _1/2 ) _a (R ⁴ R ⁵ SiO _2/2 ) _b (R ⁶ SiO _3/2 ) _c (SiO _4/2 ) _d (1)
(Wherein R ^{1 to} R ⁶ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, or a hydroxyl group; a, b, c, d Represents the ratio of the number of moles of each unit, and a + b + c + d = 1, 0 ≦ a ≦ 1, 0.2 ≦ b ≦ 1, 0 ≦ c ≦ 0.7, and 0 ≦ d ≦ 0.7. And an oil-in-water emulsion composition for bathing agents containing a surfactant. The oil-in-water emulsion composition for bath agents according to claim 1, wherein the cationized polymer is one or more selected from cationic guar gum derivatives, cationic cellulose derivatives, and cationic starch derivatives. In the formula (1) representing an organopolysiloxane, a, b, c and d are a + b + c + d = 1, 0 ≦ a ≦ 0.5, 0.5 ≦ b ≦ 1, 0 ≦ c ≦ 0.3, 0 The oil-in-water emulsion composition for bath agents according to claim 1, wherein ≦ d ≦ 0.3. The bath agent using the oil-in-water emulsion composition in any one of Claims 1-3.