JP5731138B2 - Water-in-oil emulsifier composition, water-in-oil emulsified composition using the composition, and cosmetics - Google Patents

Description

  The present invention relates to a water-in-oil emulsified composition using an organically modified clay mineral and a cosmetic, and a water-in-oil emulsifier composition that can be produced without using a cyclic silicone oil in cosmetics. Stable water-in-oil emulsified composition capable of blending silicone oil excluding oil and hydrocarbon oil or ester oil in a ratio (mass ratio) of 100/0 to 20/80, and water-in-oil emulsifier composition usable for cosmetics Related to things. The present invention also relates to a water-in-oil emulsion composition and a cosmetic using the emulsifier composition.

  Conventionally, as a method for obtaining a stable water-in-oil emulsion composition, a water-in-oil emulsion composition using an organically modified clay mineral and a polyether-modified silicone oil has been provided (Patent Document 1). In many cases, a volatile silicone oil such as a cyclic silicone oil has been used in combination in order to obtain a water-in-oil emulsion composition having a fresh and refreshing feeling. And since cyclic silicone oil functions also as a compatibilizer of various oil components, cyclic silicone oil has been widely used in preparing water-in-oil emulsion compositions using organically modified clay minerals ( Patent Document 2).

  On the other hand, there is a demand for cosmetics not containing a cyclic silicone oil such as decamethylcyclopentasiloxane due to the recent increase in interest in volatile organic compounds. However, in a water-in-oil emulsion composition using an organically modified clay mineral, silicone oil, hydrocarbon oil or ester oil is used as a liquid oil component without using a cyclic silicone oil as a compatibilizer of various oil components. It was difficult to prepare a water-in-oil emulsion composition blended at a mass ratio of about 1: 1. In addition to polyether-modified silicone, it is extremely difficult to obtain a stable water-in-oil emulsion composition without using a cyclic silicone oil even when a hydrocarbon surfactant such as polyglycerin fatty acid ester is used in combination. It was difficult.

  In recent years, there is a report that silicone oil and hydrocarbon oil can be emulsified by using branched polyether-modified silicone (Patent Document 3). However, it is essential to blend cyclic silicone oil as an oil component, and hydrocarbon oil or ester oil cannot be blended at a mass ratio of about 1: 1 with respect to silicone oil as an oil component. As a result, it was not possible to obtain a water-in-oil emulsion composition using only silicone oil.

Japanese Patent Application Laid-Open No. 61-066752 JP-A-11-005712 JP 2009-143834 A

  The present invention provides a water-in-oil emulsion composition and cosmetics using an organically modified clay mineral, and a water-in-oil emulsion composition and a cosmetic without using a cyclic silicone oil. An object of the present invention is to provide a stable water-in-oil emulsified composition and a cosmetic that can contain silicone oil excluding cyclic silicone oil and hydrocarbon oil or ester oil in a ratio (mass ratio) of 100/0 to 20/80. Moreover, it is providing the water-in-oil type emulsifier composition which can be utilized for those water-in-oil type emulsion compositions and cosmetics manufacture.

  As a result of intensive research in view of the above circumstances, the present inventors have surprisingly found that the weight average represented by the general formula (1) in the water-in-oil emulsion composition and the cosmetic using the organically modified clay mineral By using a water-in-oil emulsifier composition in which a silicone compound having a molecular weight of 500 to 200,000 and branched silicone chains and a silicone compound represented by the general formula (5) are used, phases of various oil components Without using a cyclic silicone oil as a solvent, silicone oil and hydrocarbon oil or ester oil can be blended in a ratio (mass ratio) of 100/0 to 20/80 as an oil component, and the usability is excellent. It has been found that a water-in-oil emulsion composition and a cosmetic can be produced. In addition, even when only silicone oil is blended as an oily component, which has been difficult in the past, it has also been found that a water-in-oil emulsion composition and cosmetics with excellent stability and excellent usability can be produced. It was.

  That is, in a water-in-oil emulsion composition and a cosmetic containing silicone oil (excluding cyclic silicone oil), (A) a silicone chain having a weight average molecular weight of 500 to 200,000 represented by the general formula (1) Branched silicone compounds, (B) silicone compounds represented by general formula (5), (C) water-in-oil cosmetics and cosmetics using a water-in-oil emulsifier composition containing an organically modified clay mineral Has found that it can realize a skin external preparation having a dosage form with high emulsification stability, high moisture retention, good touch and rich variety, and has completed the present invention.

  In the water-in-oil emulsified composition containing silicone oil (excluding cyclic silicone oil) and the water-in-oil emulsifier composition used in cosmetics of the present invention, (A) the weight represented by the general formula (1) Water-in-oil emulsifier composition containing a silicone compound having a branched silicone chain having an average molecular weight of 500 to 200,000, (B) a silicone compound represented by the general formula (5), and (C) an organically modified clay mineral In the past, water-in-oil, which was not able to be produced without using cyclic silicone oil as a compatibilizer for various oils, had good temperature stability and safety, and excellent usability. Mold emulsion compositions and cosmetics can be provided. Also, emulsification was difficult even when cyclic silicone oil was used, and 100% silicone oil was blended, and hydrocarbon oil and ester oil were blended at a ratio (mass ratio) of 100/0 to 20/80 with respect to silicone oil. The water-in-oil emulsified composition and the cosmetics can be provided. Furthermore, by using this emulsified composition, an excellent water-in-oil emulsified cosmetic utilizing the feel of various oils such as sunscreens, hydrocarbon oils and ester oils containing UV absorbers at high concentrations can be obtained. Can be provided. These water-in-oil emulsion compositions and cosmetics have a good feeling of use, excellent moisturizing properties, and high stability.

  This invention contains the following (A)-(C) as an essential component in the water-in-oil type emulsifier composition utilized for the water-in-oil type emulsion composition containing silicone oil (except cyclic silicone oil). The present invention relates to a water-in-oil emulsifier composition.

で表されるオルガノシロキサンであって、Ｒ^４は炭素数４〜３０の炭化水素基又はＲ^６−（ＣＯ）−で示される有機基、Ｒ^５は水素原子もしくは炭素数１〜３０の炭化水素基又はＲ６−（ＣＯ）−で示される有機基、Ｒ^６は炭素数１〜３０の炭化水素基、前記一般式（４）中のＲ^１は前記一般式（１）中のＲ^１と同じである。ａ、ｂ、ｃはそれぞれ１．０≦ａ≦２．５、０．００１≦ｂ≦１．５、０．００１≦ｃ≦１．５であり、ｄ、ｅはそれぞれ０≦ｄ≦５０、０≦ｅ≦５０の整数であり、ｆ、ｇはそれぞれ２≦ｆ≦２００、０≦ｇ≦２００、かつｆ＋ｇが３〜２００の整数である。また、ｍは０≦ｍ≦１５の整数、ｈは０≦ｈ≦５００の整数であり、ｎは１≦ｎ≦５の整数である。］ The component (A) used in the present invention is a silicone compound having a weight average molecular weight of 500 to 200,000 represented by the following general formula (1) in which a silicone chain is branched.
R ¹ _a R ² _b R ³ _c SiO _{(4-a-b-c) / 2} (1)
[Wherein, R ¹ represents an alkyl group having 1 to 30 carbon atoms, an aryl group, an aralkyl group, a fluorine-substituted alkyl group, or the following general formula (2)
_{-C m H 2m -O- (C 2} H 4 O) d (C 3 H 6 O) e R 4 (2)
R ² is the same or different organic group selected from the organic groups represented by the following general formula (3):
_{-C m H 2m -O- (C 2} H 4 O) f (C 3 H 6 O) g -R 5 (3)
R ³ is a polyoxyalkylene group represented by the following general formula (4)

R ⁴ is a hydrocarbon group having 4 to 30 carbon atoms or an organic group represented by R ^6- (CO)-, R ⁵ is a hydrogen atom or a hydrocarbon having 1 to 30 carbon atoms group or R6- (CO) - organic group represented by, ^{R 6} is a hydrocarbon group having 1 to 30 carbon atoms, ^{R 1} in the general formula (4) are the same as ^{R 1} in the general formula (1) It is. a, b and c are 1.0 ≦ a ≦ 2.5, 0.001 ≦ b ≦ 1.5 and 0.001 ≦ c ≦ 1.5, respectively, d and e are 0 ≦ d ≦ 50, An integer of 0 ≦ e ≦ 50, f and g are integers of 2 ≦ f ≦ 200, 0 ≦ g ≦ 200, and f + g is 3 to 200, respectively. M is an integer of 0 ≦ m ≦ 15, h is an integer of 0 ≦ h ≦ 500, and n is an integer of 1 ≦ n ≦ 5. ]

  Although it is not specifically limited to HLB of (A) component, it is preferable that it is HLB10 or less, More preferably, it is HLB5 or less. The component (A) can be synthesized by the method described in JP-A-2001-39819. Examples of commercially available products include KF-6028 (PEG-9 polydimethylsiloxyethyl dimethicone) and KF-6038 (lauryl PEG-9 polydimethylsiloxyethyl dimethicone) manufactured by Shin-Etsu Chemical Co., Ltd. The type KF-6038 is more preferred.

  The effect of the present invention can also be expected by using KF-6105 (lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone), which is a polyglycerin-modified silicone (alkyl co-modified type) having a branched silicone chain.

［式中、Ａは炭素原子数１〜６のアルキル基、フェニル基であり、Ｂは下記一般式（６）
−Ｃ_３Ｈ_６Ｏ（Ｃ_２Ｈ_４Ｏ）_i（Ｃ_３Ｈ_６Ｏ）_j−Ｒ'
（式中、Ｒ'は水素原子、アシル基、あるいは炭素数１〜６のアルキル基であり、ｉ，ｊはそれぞれ、０≦ｉ≦５０、０≦ｊ≦２００、ただしｉとｊが同時に０となることはない。）であり、Ｒ^７はそれぞれ独立に炭素原子数１〜６のアルキル基あるいはフェニル基であり、ｐ，ｑはそれぞれ、５０≦ｐ≦１０００、０≦ｑ≦５０である。ただし、分子中に少なくとも１個はポリオキシアルキレン基を有する。］ The component (B) used in the present invention is a silicone compound represented by the following general formula (5).

[Wherein, A is an alkyl group having 1 to 6 carbon atoms and a phenyl group, and B is the following general formula (6)
_{-C 3 H 6 O (C 2} H 4 O) i (C 3 H 6 O) j -R '
(In the formula, R ′ is a hydrogen atom, an acyl group, or an alkyl group having 1 to 6 carbon atoms, i and j are 0 ≦ i ≦ 50 and 0 ≦ j ≦ 200, respectively, where i and j are 0 simultaneously. R ⁷ is independently an alkyl group having 1 to 6 carbon atoms or a phenyl group, and p and q are 50 ≦ p ≦ 1000 and 0 ≦ q ≦ 50, respectively. . However, at least one in the molecule has a polyoxyalkylene group. ]

  Although it is not specifically limited to HLB of (B) component, it is preferable that it is HLB10 or less, More preferably, it is HLB5 or less. About (B) component, there are many commercial items, for example, KF-6015 (PEG-3 dimethicone), KF-6016 (PEG-9 dimethicone), KF-6017, KF-6043 (made by Shin-Etsu Chemical Co., Ltd.) PEG-10 dimethicone), SS2910 (PEG-10 dimethicone), SH3775 (PEG-12 dimethicone), BY25-337 (mixture of PEG / PPG30 / 10 dimethicone and hydrogenated polyisobutene) manufactured by Toray Dow Corning It is done.

  The organically modified clay mineral which is the component (C) used in the present invention is not particularly limited as long as it is usually used for cosmetics and the like. Preferably, it is a cation-modified clay mineral treated with a quaternary ammonium salt type cationic surfactant, and examples thereof include dimethyl distearyl ammonium hectorite, dimethyl distearyl ammonium bentonite, and benzyl dimethyl stearyl ammonium hectorite. Examples of commercially available products include Benton 38VCG (dimethyl distearyl ammonium hectorite) manufactured by Elementis Japan.

  Silicone oils according to the present invention (excluding cyclic silicone oils such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane), except for cyclic silicone oils, are usually used in cosmetics and external preparations. For example, dimethylpolysiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, hexadecamethylheptasiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, tetramethyltetrahydrogenpoly Polysiloxanes other than siloxane, (A) and (B), amino-modified polysiloxane, alcohol-modified polysiloxane, acrylic-modified polysiloxane, fatty acid-modified polysiloxane, higher grades Lumpur modified polysiloxane, fluorine-modified silicone, crosslinked dimethylpolysiloxane include crosslinked methylphenyl polysiloxane. These may be used alone or in combination of two or more. Among these, for example, dimethylpolysiloxane, dimethylcyclopolysiloxane, and methylphenylpolysiloxane are preferably used.

  In the present invention, the ratio (mass ratio) of the components (A) to (C) is preferably (A) / (B) = 1/99 to 50/50, more preferably (A) / (B) = 5/95 to 45/55, and more preferably (A) / (B) = 10/90 to 40/60.

  Further, the ratio (mass ratio) of the sum of the components (A) and (B) and the component (C) is preferably [(A) + (B)] / (C) = 50/50 to 97/3, More preferably, [(A) + (B)] / (C) = 60/40 to 93/7, and still more preferably, [(A) + (B)] / (C) = 70/30 to 90 / 10. Within this range, the water-in-oil emulsion composition and the cosmetic can be prepared more stably.

  The water-in-oil emulsifier composition of the present invention may be composed of only the components (A) to (C), or an oily raw material may be used in combination. In that case, the preferable mixing ratio (mass ratio) of the both is oily raw material / [total amount of components (A) to (C)] = 1/99 to 99/1, more preferably 5/95 to 95/5. More preferably, it is 10/90 to 90/10. If it is this range, when manufacturing a water-in-oil emulsion composition and cosmetics, it is easier to handle than a water-in-oil emulsifier composition.

  The water-in-oil emulsifier composition of the present invention preferably contains 0.1 to 30% by mass with respect to the water-in-oil emulsion composition and the total amount of the cosmetic. More preferably, it is 0.3-20 mass%, More preferably, it is 0.5-10 mass%.

  As the liquid oily component other than silicone oil, any oily raw material generally used in cosmetics can be suitably used. Specifically, hydrocarbons such as squalane, liquid paraffin, vegetable oils such as olive oil, macadamian nut oil, jojoba oil, animal oils such as beef tallow, glyceryl triisooctanoate, tri (caprylic / capric) glyceryl, myristic acid Esters such as isopropyl, cetyl isooctanoate, isooctyl palmitate, 2-hydroxy-4-methoxybenzophenone, octyl paradimethylaminobenzoate, octyl paramethoxycinnamate, 4-t-butyl-4'-methoxydibenzoylmethane Organic UV absorbers such as octocrylene and ethylhexyltriazone.

  If the water-in-oil emulsifier composition containing (A) to (C) of the present invention is used, an oil using only silicone oil as a liquid oil that has been difficult to emulsify even when a cyclic silicone oil is used. Water-in-water emulsified compositions and cosmetics, and water-in-oil emulsified compositions and cosmetics in which hydrocarbon oils and ester oils are blended at a ratio (mass ratio) of 100/0 to 20/80 to silicone oil are provided. can do. Specifically, as a liquid oily component, the ratio of silicone oil and other oil is 100/0 to 20/80, more preferably 100/0 to 30/70, and still more preferably 100/0 to 50/50. It is possible to provide a water-in-oil emulsion composition and a cosmetic blended in (mass ratio).

  The water-in-oil emulsifier composition of the present invention is prepared by melting and mixing the components (A) to (C) and the oily raw material in advance into a uniform mixture, and cooling it to room temperature while stirring it to form a solid or paste It can be obtained as a composition. Moreover, if it is going to adjust the mixture ratio of (A)-(C) component and an oil-based raw material and to prepare the emulsified state and dosage form of cosmetics etc., it can also mix | blend with cosmetics etc. each independently.

  The water-in-oil emulsified composition and the cosmetic containing the water-in-oil emulsifier composition of the present invention are not only excellent in emulsion stability but also have high moisturizing properties. Moreover, the water-in-oil emulsified composition and cosmetics produced using the water-in-oil emulsifier composition can provide a skin external preparation with a variety of dosage forms.

  The water-in-oil emulsifier composition of the present invention, the water-in-oil emulsified composition containing the same, and the cosmetics are the surfactants and higher alcohols generally used in cosmetics as long as the effects of the present invention are not impaired. , Alkyl glyceryl ethers, fatty acids, oily raw materials, active ingredients, moisturizing ingredients, antibacterial ingredients, viscosity modifiers, dyes, fragrances and the like can be used in combination.

  Examples of these include surfactants such as POE sorbitan monooleate, POE sorbitan fatty acid esters such as POE sorbitan monostearate, POE sorbite fatty acid esters such as POE sorbite monolaurate and POE sorbite monooleate, and POE glycerin monoester. POE glycerin fatty acid esters such as stearate, POE glycerin monoisostearate, POE glycerin triisostearate, POE fatty acid esters such as POE monooleate and POE monoisostearate, POE lauryl ether, POE oleyl ether, POE isostearyl POE alkyl ethers such as ether and POE stearyl ether, POE / POP cetyl ether, POE / POP decyl tetradecyl ether POE / POP alkyl ethers such as sucrose, nonionic surfactants such as sucrose fatty acid esters and glycerin fatty acid esters, fatty acid soaps such as sodium laurate and sodium palmitate, sulfuric acid such as sodium lauryl sulfate and sodium POE lauryl sulfate Esters, acylated amino acid salts such as sodium lauroyl sarcosine, sodium cocoyl-N-methyltaurate, sodium lauryl glutamate, anionic surfactants such as phosphate ester salts such as sodium monolauryl phosphate, quaternary ammonium salts, etc. And cationic surfactants.

  Examples of higher alcohols include lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, and cetostearyl alcohol.

  Examples of the alkyl glyceryl ether include batyl alcohol, chimyl alcohol, cerachiral coal and fatty acid esters thereof.

  Examples of fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, 12-hydroxystearic acid, and isostearic acid.

  Examples of liquid oily materials include those described above.

  Active ingredients include ascorbic acid, magnesium ascorbate phosphate, ascorbyl palmitate, ascorbyl stearate, ascorbyl tetraisopalmitate, 3-O-cetyl ascorbic acid, ascorbyl glucoside, arbutin, ellagic acid, lucinol and other whitening Agents, NMF components such as amino acids, water-soluble collagen, elastin, glycyrrhizic acid, glycyrrhetinic acid, ceramide and other rough skin prevention agents, retinol, vitamin A acid and other anti-aging agents, various vitamins and their derivatives.

  Examples of the moisturizing component include polyethylene glycol, propylene glycol, 1,3-butylene glycol, dipropylene glycol, glycerin, sorbitol, xylitol, maltitol, chondroitin sulfate, hyaluronic acid, sodium pyrrolidone carboxylate and the like.

  When preparing a water-in-oil emulsified composition and a cosmetic using the water-in-oil emulsifier composition of the present invention, a normal emulsifying apparatus such as a paddle mixer or a homomixer can be used. The preparation method is a method in which the oily raw material and the water-in-oil emulsifier composition of the present invention are previously melt-mixed at 50 to 120 ° C, and hot water at 50 to 80 ° C is added while stirring with a homomixer or the like. A method in which a raw material or a water-in-oil emulsifier composition of the present invention melted and mixed at 50 to 120 ° C. is poured into warm water at 50 to 80 ° C. while stirring with a homomixer or the like. Can be mentioned.

  When preparing a water-in-oil emulsified composition containing a component (A) to (C) and silicone oil (excluding cyclic silicone oil) and cosmetics, ordinary emulsification such as paddle mixer, homomixer, etc. The device can be used. The preparation method is a method in which an oily raw material and components (A) to (C) are previously melt-mixed at 50 to 120 ° C., and hot water at 50 to 80 ° C. is added under stirring with a homomixer or the like. Alternatively, a method in which the components (A) to (C) that have been melt-mixed at 50 to 120 ° C. are poured into warm water at 50 to 80 ° C. while stirring with a homomixer or the like.

  A water-in-oil emulsified composition and a cosmetic using the water-in-oil emulsifier composition of the present invention are skin care cosmetics such as a moisturizing cream, an emollient cream, a massage cream, a moisturizing cosmetic liquid, a moisturizing lotion, and an emollient emulsion, or And can be suitably used for skin treatments such as ointments. In particular, if the water-in-oil emulsifier composition of the present invention is used, silicone oil and other liquid oil components can be added to 100/0 to 20 / without using cyclic silicone oil as a compatibilizer for various oil components. Since it is possible to provide a stable water-in-oil emulsion composition and cosmetics that can be blended at a ratio of 80, it can also be used in the manufacture of sunscreens and the like using organic UV absorbers and silicone oils in various ratios. Can be applied.

  The present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto. In the examples, “%” means “mass%”.

(1) Preparation of water-in-oil emulsifier composition Water-in-oil emulsifier compositions shown in Table 1 below were prepared. That is, a water-in-oil emulsifier composition was obtained by mixing the components listed in Table 1 with stirring in a stainless steel mixing container.

(2) Preparation of water-in-oil emulsion composition Water-in-oil emulsion compositions shown in Tables 2 and 3 below were prepared using the water-in-oil emulsifiers shown in Table 1 below. That is, in a 10-liter scraping and stirring stainless steel homomixer, components other than water were mixed and dispersed, heated as necessary, and stirred while stirring (5000 rpm), and water was gradually added thereto. . Furthermore, the mixture was stirred for 30 minutes under the same conditions, cooled to room temperature, and a water-in-oil type emulsion composition was obtained. The preparation scale of the water-in-oil emulsion composition was 5 kg.
(3) Storage stability evaluation of water-in-oil emulsion composition

Immediately after the preparation, the phase states after 2 weeks and 4 weeks at 45 ° C. were visually observed, and the stability was evaluated according to the following criteria.
A: Phase separation is not observed after 3 months storage at 45 ° C.
○ +: Phase separation is not observed after 3 months of storage at room temperature, but phase separation is observed after 3 months of storage at 45 ° C.
○-: Phase separation is not observed after 2 months of storage at room temperature, but phase separation is observed after 2 months of storage at 45 ° C.
Δ: Phase separation was observed within 4 weeks of storage at 45 ° C.
X: Phase separation was observed within 24 hours of storage at 25 ° C.

Oil-in-water dispersed cosmetic (sunscreen lotion)
A Silicone compounds with branched silicone chains (Note 1)
0.45 (%)
Silicone compound (Note 2) 1.05
Organically modified clay mineral (Note 3) 0.5
Dimethicone (10mm ² / s) 15.0
Glyceryl triethylhexanoate 10.0
Ethylhexyl methoxycinnamate 7.5
Ethylhexyl salicylate 0.25
t-Butylmethoxydibenzoylmethane 0.25
Jojoba oil 2.0
B Fine zinc oxide (Silica, methylpolysiloxane treated product)
8.0
Fine particle titanium oxide (methicone, alumina-treated product)
7.0
Silica 3.0
C 1,3-butylene glycol 10.0
Sodium citrate 0.15
Edetate trisodium 0.05
Preservative appropriate amount Purified water Remaining Note 1: KF-6038 (manufactured by Shin-Etsu Chemical Co., Ltd.)
Note 2: KF-6017 (manufactured by Shin-Etsu Chemical Co., Ltd.)
Note 3: Benton 38VCG (made by Elementis Japan)

(Preparation method)
C is heated to 70 ° C. and emulsified with a homomixer while gradually adding C to the mixed phase of A and B. Cool with paddle stirring and finish the preparation around 30 ° C.

Water-in-oil cosmetic (non-chemical sunscreen lotion)
A Water-in-oil emulsifier composition of Invention product 5 8.0 (%)
Decamethyltetrasiloxane 20.0
Dimethicone (6mm ² / s) 5.0
Methylphenylpolysiloxane 5.0
Cetyl 2-ethylhexanoate 3.0
Octyldodecanol 3.0
Kukui nut oil 1.0
Olive Squalane 1.0
(Alkyl acrylate / dimethicone) copolymer 1.5
Dl-α-tocopherol acetate 0.2
BHT 0.02
B Fine zinc oxide (treated with aluminum stearate)
6.0
Fine particle titanium oxide (treated with aluminum stearate)
15.0
C 1,3-butylene glycol 6.0
Glycerin 2.0
Dipropylene glycol 2.0
Sodium citrate 0.15
Dipotassium glycyrrhizinate 0.2
Edetate trisodium 0.05
Preservative appropriate amount Purified water balance

(Preparation method)
A is heated to 50 ° C. and B is added and mixed uniformly. The mixed phase of A and B and C are each heated to 70 ° C., and emulsification is performed with a homomixer while C is gradually added. Cool with paddle stirring and finish the preparation at around 30 ° C.

Water-in-oil cosmetic (sunscreen cream)
A Water-in-oil emulsifier composition of Invention product 4 5.0 (%)
Ethylhexyl palmitate 2.0
Butyloctyl salicylate 3.0
Olive oil 2.0
Dimethicone (6mm ² / s) 15.0
t-Butylmethoxydibenzoylmethane 5.0
Ethylhexyl triazone 0.5
Octocrylene 0.1
Ultrafine zinc oxide (hydrous silica, (dimethicone / methicone) copolymer treatment)
10.0
Fine particle titanium oxide (treated with aluminum stearate)
5.0
Hydrogenated retinol 0.1
Ascorbyl tetrahexyldecanoate 0.1
Tridohexyl decanoate pyridoxine 0.1
d-δ-tocopherol 0.1
B 1,3-butylene glycol 7.0
Pentylene glycol 3.0
Ergothioneine 0.1
Preservative appropriate amount Purified water balance

(Preparation method)
A is heated to 80 ° C. to uniformly disperse, and B is gradually added to A while slowly stirring with a homomixer or a dispermixer, followed by strong stirring and emulsification. Cool with paddle stirring and finish the preparation at around 30 ° C.

Water-in-oil cosmetic (emollient cream)
A Silicone compounds with branched silicone chains (Note 1)
0.5 (%)
Silicone compound (Note 2) 1.5
Organically modified clay mineral (Note 3) 0.3
Dimethicone (30mm ² / s) 2.0
Octamethyltrisiloxane 6.0
Perfluoropolyether 1.0
Tri (caprylic / capric) glyceryl 9.0
Macadamia nut oil 0.5
Jojoba oil 0.5
Behenyl alcohol 1.0
Batyl alcohol 0.3
B Preservative appropriate amount 1,3-butylene glycol 5.0
Glycerin 6.0
C ethanol 3.0
Sodium hyaluronate (1% aqueous solution) 1.5
Trisodium citrate 0.2
L-Hydroxyproline 0.2
Edetate trisodium 0.05
Purified water balance Note 1: KF-6038 (Shin-Etsu Chemical Co., Ltd.)
Note 2: SH3775 (Toray Dow Corning)
Note 3: Benton 38VCG (made by Elementis Japan)

(Preparation method)
A and B are heated to 70 ° C. and uniformly dissolved. Emulsify with a homomixer while gradually adding B to C and gradually adding the mixed phase of B and C to A. Cool with paddle stirring and finish the preparation around 30 ° C.

Oil-in-water dispersed cosmetic (milky lotion)
A Water-in-oil emulsifier composition of Invention product 10 3.5 (%)
Liquid paraffin 3.0
Hexyldecyl isostearate 4.0
Glyceryl triethylhexanoate 4.0
Meadow Home Oil 1.0
Hydrogenated jojoba oil 1.0
Dimethicone (6mm ² / s) 7.0
Tocopherol acetate 0.2
B 1,3-butylene glycol 7.0
Sorbitol (70% aqueous solution) 1.0
Sodium hyaluronate (1% aqueous solution) 1.0
Preservative appropriate amount Purified water balance

(Preparation method)
Each of A and B is uniformly dispersed at room temperature, and B is gradually added to A while slowly stirring with a homomixer, a dispermixer or a paddle, and then the mixture is vigorously stirred and emulsified.

Oil-in-water cosmetic (eye essence)
A Water-in-oil emulsifier composition of the product 1 of the present invention 5.0 (%)
Dimethicone (6mm ² / s) 15.0
Octamethyltrisiloxane 10.0
Cetostearyl alcohol 0.2
B 1,3-butylene glycol 10.0
Glycerin 15.0
Citric acid 0.1
Aspartic acid 0.1
Glycine zinc complex 0.2
Camellia extract 0.1
Horsetail extract 0.1
α-glucan oligosaccharide 0.1
Edetate trisodium 0.02
Preservative appropriate amount Purified water balance

(Preparation method)
Emulsify with a homomixer while gradually adding B to warm A and B to 70 ° C. to make them uniform. Cool with paddle stirring and finish the preparation at around 30 ° C.

Oil-in-water cosmetic (medicated whitening cream)
A Silicone compounds with branched silicone chains (Note 1)
0.8 (%)
Silicone compound (Note 2) 1.0
Organically modified clay mineral (Note 3) 0.4
Dimethicone (2mm ² / s) 10.0
Glyceryl triethylhexanoate 10.0
Olive Squalane 3.0
Rosehip oil 0.1
Ceramide 2 0.2
Natural vitamin E 0.1
B L-ascorbyl magnesium phosphate 3.0
Glycerin 10.0
1,3-butylene glycol 2.0
Sodium hyaluronate (1% aqueous solution) 1.0
Sodium glutamate 0.3
Preservative appropriate amount Purified water Remaining Note 1: KF-6038 (manufactured by Shin-Etsu Chemical Co., Ltd.)
Note 2: BY25-337 (Toray Dow Corning)
Note 3: Benton 38VCG (made by Elementis Japan)

(Preparation method)
Each of A and B is uniformly dispersed at room temperature, and B is gradually added to A while slowly stirring with a homomixer or a disper mixer, and then emulsified by vigorous stirring.

External preparation (ointment formulation)
Water-in-oil emulsifier composition 35.0 (%) of the product 7 of the present invention
POE (30) cetyl ether 2.0
Glyceryl monostearate 9.0
Liquid paraffin 9.0
Dimethicone (10mm ² / s) 5.0
White petrolatum 5.0
Cetanol 6.0
Propylene glycol 10.0
Preservative appropriate amount Purified water balance

(Preparation method)
An emulsified composition was prepared according to a conventional method for producing an ointment composition.

  In the storage stability evaluation described in Example 1, the cosmetics or external preparations of Examples 2 to 9 were confirmed to have no phase separation after 4 weeks of storage at 45 ° C.

Claims (7)

In a water-in-oil emulsifier composition used for a water-in-oil emulsified composition containing silicone oil (excluding cyclic silicone oil), the following water-in-oil type containing the following (A) to (C) as essential components: Emulsifier composition.
(A) the following general formula silicone compound weight average molecular weight represented by (1) is _{^{500~200,000 R 1 a R 2 b R}} 3 c SiO (4-a-b-c) / 2 (1)
[Wherein, R ¹ represents an alkyl group having 1 to 30 carbon atoms, an aryl group, an aralkyl group, a fluorine-substituted alkyl group, or the following general formula (2)
_{-C m H 2m -O- (C 2} H 4 O) d (C 3 H 6 O) e R 4 (2)
R ² is the same or different organic group selected from the organic groups represented by the following general formula (3):
_{-C m H 2m -O- (C 2} H 4 O) f (C 3 H 6 O) g -R 5 (3)
R ³ is a polyoxyalkylene group represented by the following general formula (4)

R ⁴ is a hydrocarbon group having 4 to 30 carbon atoms or an organic group represented by R ^6- (CO)-, R ⁵ is a hydrogen atom or a hydrocarbon having 1 to 30 carbon atoms group, or ^R 6 - (CO) - organic group represented by, ^{R 6} is a hydrocarbon group having 1 to 30 carbon atoms, ^{R 1} in the general formula (4) in the ^{R 1} in the general formula (1) The same. a, b and c are 1.0 ≦ a ≦ 2.5, 0.001 ≦ b ≦ 1.5 and 0.001 ≦ c ≦ 1.5, respectively, d and e are 0 ≦ d ≦ 50, An integer of 0 ≦ e ≦ 50, f and g are integers of 2 ≦ f ≦ 200, 0 ≦ g ≦ 200, and f + g is 3 to 200, respectively. M is an integer of 0 ≦ m ≦ 15, h is an integer of 0 ≦ h ≦ 500, and n is an integer of 1 ≦ n ≦ 5. ]
(B) Silicone compound represented by the following general formula (5)

Wherein, A is an alkyl group, a phenyl group having 1 to 6 carbon atoms, B is represented by the following general formula _{(6) -C 3 H 6 O} (C 2 H 4 O) i (C 3 H 6 O) _j −R ′ (6)
(Wherein R ′ is a hydrogen atom, an acyl group, or an alkyl group having 1 to 6 carbon atoms, i and j are 0 ≦ i ≦ 50 and 0 ≦ j ≦ 200, respectively, where i and j are simultaneously R ⁷ is independently an alkyl group having 1 to 6 carbon atoms or a phenyl group, and p and q are 50 ≦ p ≦ 1000 and 0 ≦ q ≦ 50, respectively. is there. However, at least one in the molecule has a polyoxyalkylene group. ]
(C) Cation-modified clay mineral
The ratio of the components (A) to (C) is
(A) / (B) = 1/99 to 50/50
The water-in-oil emulsifier composition according to claim 1, wherein [(A) + (B)] / (C) = 50/50 to 97/3.
The water-in-oil emulsifier composition according to claim 1 or 2, comprising silicone oil and other liquid oil components in a ratio (mass ratio) of 100/0 to 20/80.
The water-in-oil emulsion composition containing silicone oil (except cyclic silicone oil) containing the water-in-oil emulsifier composition according to any one of claims 1 to 3.
A water-in- oil emulsified cosmetic containing a silicone oil (excluding a cyclic silicone oil) containing the water- in- oil emulsifier composition according to any one of claims 1 to 3.
A water-in-oil emulsion composition containing the components (A) to (C) according to claim 1 and silicone oil (excluding cyclic silicone oil).
A water- in- oil emulsified cosmetic comprising the components (A) to (C) according to claim 1 and silicone oil (excluding cyclic silicone oil).