JP2000256172A - Water-in-oil emulsion composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water-in-oil emulsion composition excellent in feeling of use when and after applying and emulsion stability by including a specific modified organopolysiloxane, a specific branched monoester, a specific polysiloxane and water. SOLUTION: This composition contains (A) more than one kind of a polyoxyalkylene-modified organopolysiloxane and/or an alkyl-modified polyoxyalkylene-modified organopolysiloxane [ex. ABIL EM97, ABIL EM90 (both are produced by Goldschmidt Corp.) or the like], (B) more than one kind of a branched monoester shown by formula I (R1 is an alkyl residual group of a 5-18C isocarboxylic acid; R2 is an alkyl residual group of a 3-18C isoalcohol), (C) more than one kind of a polysiloxane shown by formula II (x is 4-100), formula III (z is more than 1 and y+z is 1-100), formula IV (p is 3-7) or the like, and (D) water. Preferably the content of each component is 0.05-10 wt.% in the component A, 0.1-30 wt.% in the component B, 3-50 wt.% in the component C and 10-85 wt.% in the component D.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a water-in-oil emulsion composition, and more particularly to a water-in-oil type emulsifying composition, which gives a good and fresh feeling upon application to the skin, is smooth and smooth after application, and has good emulsion stability. The present invention relates to an excellent water-in-oil emulsion composition.

[0002]

2. Description of the Related Art Emulsified cosmetics are mainly classified into oil-in-water cosmetics and water-in-oil cosmetics. Since these emulsified cosmetics contain water, they give a refreshing feeling when applied to the skin and have less oily feeling than oil-based cosmetics.
In addition, the appearance is often liquid or creamy, has good spreadability on the skin, and has characteristics such that a uniform finish without unevenness is easily obtained. In particular, water-in-oil cosmetics leave a low moisture permeable oil film on the skin surface because the oil phase is a continuous phase compared to oil-in-water cosmetics, and protect the skin from drying for a long time, Even when in contact with water, re-emulsification rarely occurs and makeup collapse is unlikely to occur. In addition, it has the effect of more stably keeping relatively unstable water-soluble drugs such as water-soluble vitamins and cosmetic ingredients, and the film is retained for a long time by its water repellency when applied on the skin, so that the cosmetic effect Can be maintained more.

[0003]

However, the conventional water-in-oil type cosmetics often limit the amount of water for stabilization and use a highly viscous oil component to make it sticky. A strong feeling and oiliness were felt. It is known that a polysiloxane represented by the following general formula (2), (3) or (4) is blended in order to obtain a less sticky and refreshing feeling. However, these polysiloxanes have poor adaptation to the skin, have no skin softening effect to moisturize the skin, and have no emollient effect,
If the amount is too large, there is a disadvantage that an uncomfortable film is left on the skin. Further, these polysiloxanes have a disadvantage that they have poor compatibility with ordinary surfactants and other oil components. On the other hand, when an oil agent having a carbon skeleton, which is usually used in cosmetics, is used in a water-in-oil type cosmetic, it can provide a skin softening effect, but it is difficult to give a fresh and refreshing feeling of use, and it is sticky. was there.

In recent years, polyoxyalkylene-modified organopolysiloxanes and / or alkyl-modified polyoxyalkylene-modified organopolysiloxanes have been used as emulsifiers, and both polysiloxanes and oils having a carbon skeleton have been used in some cases. It was difficult to obtain a product having both a fresh and refreshing feeling in use and a skin softening effect for moisturizing the skin, and having good stability.

In order to impart a fresh feeling of use and coolness, it is conceivable to add ethanol. However, the addition of ethanol significantly lowers the stability of the system, and the addition of a large amount of ethanol causes rough skin. There was a case.

[0006]

Under these circumstances, the present inventors have conducted intensive studies and have found that a polyoxyalkylene-modified organopolysiloxane and / or an alkyl-modified polyoxyalkylene-modified organopolysiloxane is used as an emulsifier, and a silicone is used. By emulsifying the oil phase and the aqueous phase containing oil and a specific branched monoester, the skin adapts well during application, gives a refreshing feeling and a fresh feeling of use while reducing alcohol, and is smooth and smooth after application, It has been found that a water-in-oil emulsion composition having a skin softening effect and an emollient effect, hardly causing rough skin, and having excellent emulsion stability can be obtained.

That is, the present invention provides the following components (a) to (d)
Is a water-in-oil type emulsified composition characterized by containing as an essential component. (A) one or more of polyoxyalkylene-modified organopolysiloxane and / or alkyl-modified polyoxyalkylene-modified organopolysiloxane (b) one of the branched monoesters represented by the following general formula (1)
Species or two or more

[0008]

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(Wherein, R ¹ represents an alkyl residue of an isocarboxylic acid having 5 to 18 carbon atoms, and R ² represents an alkyl residue of an isoalcohol having 3 to 18 carbon atoms)

(C) One or more polysiloxanes represented by the general formula (2), (3) or (4)

[0011]

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[0012]

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[0013]

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(Where x is an integer of 4 to 100, z is an integer of 1 or more, y + z is an integer of 1 to 100, and p is an integer of 3 to 7.) (d) Water

Further, in addition to the above components (a) to (d),
Contains ethanol as a component (e), (d): (e)
Is a water-in-oil emulsion composition having a weight ratio of 70:30 to 100: 0.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The polyoxyalkylene-modified organopolysiloxane and / or alkyl-modified polyoxyalkylene-modified organopolysiloxane used as the component (a) in the present invention are represented by the general formulas (5) and (6). What is represented is preferable, and what contains a polyoxyalkylene group in a molecule | numerator 5-40% and a molecular weight is 2000 or more is used, and these can use 1 type (s) or 2 or more types. As commercially available products, for example, polyoxyalkylene-modified organopolysiloxanes include ABIL EM
97 (manufactured by Goldschmidt), SH-3772C,
SH3775C (manufactured by Dow Corning Toray Silicone Co., Ltd.), KF-6012, KF-6015, KF-601
6, KF-6017 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. Examples of the alkyl-modified polyoxyalkylene-modified organopolysiloxane include ABIL EM90 (manufactured by Goldschmidt).

The component (a) is preferably contained in the water-in-oil emulsion composition of the present invention in an amount of 0.05 to 10% by weight (hereinafter simply referred to as%), more preferably 0.1 to 5%. Is done. When the content is more than 10%, the effect has already reached saturation and it is uneconomical, and when it is less than 0.05%, the effect is weak, and especially the long-term stability is poor.

The component (b) of the present invention is one or more of the branched monoesters represented by the general formula (1),
By being blended, it is used to impart a moderate skin softening effect, emollient effect, good skin familiarity, etc. without losing freshness, refreshing feeling, good elongation, etc.It can also give stability improvement at the same time it can.

The component (b) is incorporated in the water-in-oil emulsion composition of the present invention preferably in an amount of 0.1 to 30%, more preferably 0.5 to 20%. If the content is more than 30%, the fresh and refreshing feel is lost,
If it is less than 0.1%, sufficient emollient effect and skin softening effect cannot be obtained.

The component (c) of the present invention comprises one or two or more of the polysiloxanes represented by the general formulas (2), (3) and (4). ) And (4), among which those represented by (4) are particularly preferred. In the water-in-oil emulsion composition of the present invention,
Preferably, the content is 3 to 50%, more preferably 7 to 30%. If the amount is more than 50%, an uncomfortable film feeling such as slipping occurs on the back skin, and if it is less than 3%, a fresh and refreshing feeling cannot be obtained.

The components (b) and (c) are 5: 9
It is desirable to mix at a weight ratio of 5 to 70:30.
Further, oil components other than the component (b) and the component (c) can be blended as long as the effects of the present invention are not impaired.

Water, which is the component (d) of the present invention, is blended for the purpose of giving moisture to the skin and giving a fresh and fresh feeling of use. In the water-in-oil type emulsion composition of the present invention, the amount is preferably 10 to 85%, more preferably 30 to 80%. When the content is more than 85%, it is difficult to secure emulsion stability, and when it is less than 10%, a fresh and refreshing feeling cannot be obtained.

The water-in-oil emulsion composition of the present invention may further have a refreshing sensation and a fresh and refreshing feeling by adding ethanol as the component (e). Ethanol is preferably used in a weight ratio of water to ethanol: water in the range of 30:70 to 0: 100. If ethanol is added in a larger amount than this range, the skin may be roughened by humans.

The water-in-oil emulsion composition of the present invention may contain, in addition to the above essential components, components used in ordinary cosmetics, for example, powders, nonionic surfactants, anionic surfactants, Cationic surfactants, amphoteric surfactants, oily ingredients, humectants, thickeners, menthol, camphor and other fresheners, antioxidants, water-soluble vitamin C and its derivatives, vitamin A, E and its derivatives, etc. Various cosmetic ingredients, preservatives, fragrances, and the like can be blended within a range that does not impair the effects of the present invention.

The oily component other than the component (b) may be of any origin, such as animal oils, vegetable oils, synthetic oils and the like, and properties of solid oils, semi-solid oils, liquid oils, volatile oils and the like which are generally used in cosmetics. , Hydrocarbons, fats, waxes, hardened oils,
Examples include ester oils, fatty acids, higher alcohols, silicone oils, fluorinated oils, lanolin derivatives, oily gelling agents, lipophilic surfactants, and oil-soluble ultraviolet absorbers. Specifically, hydrocarbons such as liquid paraffin, squalane, petrolatum, polyisobutylene, polybutene, paraffin wax, ceresin wax, microcrystalline wax, mokurou, montan wax, fishtrophs wax, olive oil, castor oil, jojoba oil, Fats such as mink oil and macadamian nut oil, beeswax, lanolin, carnauba wax, candelilla wax, waxes such as gay wax, cetyl isooctanoate, isopropyl myristate, isopropyl palmitate, octyldodecyl myristate, trioctanoic acid Glyceryl, polyglyceryl diisostearate, diglyceryl triisostearate, glyceryl tribehenate, pentaerythritol rosinate, neopentyl dioctanoate , Cholesterol fatty acid esters, esters such as N- lauroyl -L- glutamic acid di (cholesteryl behenyl octyldodecyl), stearic acid, lauric acid, myristic acid,
Higher fatty acids such as behenic acid, isostearic acid, oleic acid, rosin acid, 12-hydroxystearic acid,
Higher alcohols such as stearyl alcohol, cetyl alcohol, lauryl alcohol, oleyl alcohol, isostearyl alcohol, behenyl alcohol, low polymerization degree dimethylpolysiloxane, high polymerization degree dimethylpolysiloxane, crosslinked organopolysiloxane, and silicones such as fluorine-modified silicone Fluorinated oils such as perfluoropolyether, perfluorodecane, perfluorooctane, lanolin derivatives such as lanolin, lanolin acetate, lanolin fatty acid isopropyl, and lanolin alcohol; dextrin fatty acid esters; sucrose fatty acid esters; starch fatty acid esters; Oily gelling agents such as aluminum hydroxystearate and calcium stearate, ethyl paraaminobenzoate, p-methoxycinnamic acid-2-ethyl Hexyl, 4-tert-butyl-4'-methoxydibenzoylmethane, oil-soluble ultraviolet absorbers such as oxybenzone, etc., and can be used in combination of at least these one or two.

Examples of humectants include propylene glycol, dipropylene glycol, 1,3-butylene glycol, glycerin, diglycerin, sorbitol,
Maltitol, polyethylene glycol, polyoxyethylene methyl glucoside, polyoxypropylene methyl glucoside, polyoxypropylene diglyceryl ether,
Examples include mucopolysaccharides and their salts, proteins such as collagen and their derivatives and their salts, pyrrolidonecarboxylic acid and its salts, and the like. Among these humectants, one or a combination of two or more can be used.

As the thickener, for example, gum arabic,
Carrageenan, quince seed, casein, dextrin, gelatin, sodium pectate, sodium alginate, methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxyethylcellulose,
Hydroxypropyl cellulose, polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone, sodium polyacrylate, carboxyvinyl polymer, alkyl-modified carboxyvinyl polymer, locust bean gum, guar gum, tamarint gum, xanthan gum, aluminum magnesium silicate, bentonite, hectorite, etc. No. Among these thickeners, one kind or a combination of two or more kinds can be used.

[0028] The water-in-oil emulsion composition of the present invention includes various properties from a low viscosity liquid at room temperature to a cream or even a solid. Further, the water-in-oil emulsion composition of the present invention, particularly when the viscosity is relatively low,
When left still for a long time, the oil component layer may be slightly separated at the top, but can be homogenized by gentle shaking.

The use of the water-in-oil emulsion composition of the present invention is not particularly limited. For example, basic cosmetics such as emulsions, creams, packs, massages, makeup cosmetics such as foundations, eyeliners, mascaras and sunscreens And the like.

[0030]

The present invention will be further described with reference to the following examples, but the present invention is not limited thereto.

Examples 1 to 5 and Comparative Examples 1 to 6 Water-in-oil creams Water-in-oil creams having the compositions shown in Tables 1 and 2 were prepared.
The use of this cream, the presence or absence of a feeling of irritation, and the stability were evaluated by the following methods and criteria, and are shown in Tables 1 and 2.

[0032]

[Table 1]

[0033]

[Table 2]

Note 1: In the general formula (6), l = 8
-20, m = 5-15, n = 2-8, Q²= C₃H₆,
c = 5 to 15, d = 0, R⁹= H, e = 4, R¹⁰= C
₁₈H ₃₅belongs to.

(Production method) Components (1) to (9) are mixed and dispersed at room temperature. B. Components (10) to (12) are mixed and dispersed at room temperature. C. B was gradually poured into A and emulsified, followed by defoaming to obtain a water-in-oil cream.

(Evaluation Method) (1) The feeling of use and the presence or absence of irritation were evaluated by 15 female evaluation panels. Take an appropriate amount of the W / O type cream in hand, apply it to the face, evaluate skin familiarity, refreshing feeling, emollient effect, and non-irritating to skin by the following five grades, and obtain their average score. The following criteria were used for the determination.

(Judgment criteria): 4.5 or more points ○: 3.5 or more and less than 4.5 points Δ: 2.5 or more and less than 3.5 points ×: less than 2.5 points

(2) The stability was evaluated by observing the state of the samples of Examples and Comparative Examples left at 50 ° C. for one month. (Judgment criteria) ◎: No change at all ○: Minor change △: Slightly separated ×: Separated

From the results shown in Tables 1 and 2, the water-in-oil cream of the present invention showed a refreshing feeling, skin familiarity, emollient effect,
It was excellent in all aspects of non-irritating and stable skin. On the other hand, the water-in-oil cream of the comparative example did not satisfy all the items.

Example 6 Serum (Component) (%) (1) Polyoxyalkylene-modified organopolysiloxane 1.5 (KF-6015) (2) Alkyl-modified polyoxyalkylene-modified organo1.0 polysiloxane (ABIL EM90) (3) Sorbitan sesquiisostearate 0.5 (4) Decamethylcyclopentasiloxane 10.0 (5) Isononyl isomryristate 8.0 (6) Perfluoropolyether 0.5 (7) Methyl paraoxybenzoate (8) Perfume appropriate amount (9) Dextrin fatty acid ester 1.0 (10) Remaining purified water (11) Glycerin 3.0 (12) Propylene glycol 10.0 (13) Sodium lactate 3.0 (14) Sodium citrate 0.5

(Production method) Components (1) to (9) are mixed and dispersed at room temperature. B. Components (10) to (14) are mixed and dispersed at room temperature. C. B was gradually injected into A and emulsified, followed by defoaming to obtain a serum. This cosmetic solution was fresh and well-adapted to the skin, remained moist and sticky, had excellent usability and long-lasting beauty effects, and was stable at 50 ° C. for one month or more.

Example 7 Moisturizing Pack Material (Component) (%) (1) Alkyl-modified polyoxyalkylene-modified organo 3.0 polysiloxane (ABIL EM90) (2) Decamethylcyclopentasiloxane 5.0 (3) Isononanoic acid Isotridecyl 15.0 (4) Liquid paraffin 1.0 (5) Microcrystalline wax 0.5 (6) Suitable amount of methyl paraoxybenzoate (7) Suitable amount of perfume (8) Silicone-treated titanium oxide 5.0 (9) Silicone-treated oxidation Iron 0.2 (10) Nylon powder 1.0 (11) Ethanol 3.0 (12) Remaining purified water (13) Diglycerin 3.0 (14) 1,3-butylene glycol 15.0 (15) Lactic acid Sodium 1.0 (16) Red No. 106

(Production method) Components (1) to (10) are mixed and dispersed at 60 ° C. B. Components (11) to (16) are mixed and dispersed at 60 ° C. C. B was gradually injected into A, emulsified, cooled and defoamed to obtain a moisturizing pack material. This moisturizing pack material was smooth, had good skin familiarity, was moist and had no stickiness, had excellent usability and long-lasting cosmetic effects, and was stable at 50 ° C. for one month or more.

Example 8 Cleansing Milk (Component) (%) (1) Polyoxyalkylene-modified organopolysiloxane 1.5 (Note 2) (2) Alkyl-modified polyoxyalkylene-modified organo 1.0 polysiloxane (Note 1) (3) Isononyl isononanoate 10.0 (4) Octamethylcyclotetrasiloxane 10.0 (5) Dimethylpolysiloxane 5.0 (6) Cross-linked methylpolysiloxane (KSG16) (Note 3) 1.0 (7) Methyl paraoxybenzoate (8) Fragrance (9) Ethanol 15.0 (10) Remaining purified water (11) Polyethylene glycol 3.0 (12) Sodium monohydrogen phosphate 0.3 Note 2: The above formula ( In 5), j = 40 to 80, k = 0, R³= CH₃, G ¹ , G²= R⁴, R⁴Q inside¹= C₃H₆, A = 7-15, b = 0, R⁸= H. Note 3: Shin-Etsu Chemical Co., Ltd.

(Production method) Components (1) to (8) are mixed and dispersed at room temperature. B. Components (9) to (12) are mixed and dispersed at room temperature. C. B was gradually injected into A, emulsified, and defoamed to obtain cleansing milk. This cleansing milk had a refreshing sensation, was easily blended with dirt, had good dirt removal, had no stickiness after cleansing, had excellent usability, and was stable at 50 ° C. for one month or more.

Example 9 Sunscreen lotion (component) (%) (1) polyoxyalkylene-modified organopolysiloxane 1.0 (KF-6017) (2) dimethylpolysiloxane 5.0 (3) octamethylcyclotetrasiloxane 20.0 (4) Isotridecyl isononanoate 5.0 (5) Octyl methoxycinnamate 5.0 (6) Methyl parahydroxybenzoate (7) Suitable amount of fragrance (8) Silicone-treated fine particle titanium oxide 10.0 (9) Silicone Treated fine particle zinc oxide 10.0 (10) Trimethylsiloxysilicic acid 0.5 (11) Ethanol 10.0 (12) Purified water Remaining (13) Dipropylene glycol 3.0 (14) Salt 0.2

(Production method) Components (1) to (10) are mixed and dispersed at room temperature. B. Components (11) to (14) are mixed and dispersed at room temperature. C. B was gradually injected into A, emulsified, and defoamed to obtain a sunscreen lotion. This sunscreen lotion had a refreshing sensation, was fresh and well-adapted to the skin, had no stickiness, was excellent in usability, water resistance, and sustained the suncut effect, and was stable at 50 ° C. for one month or more.

Example 10 Cream Eye Shadow (Component) (%) (1) Polyoxyalkylene-modified organopolysiloxane 1.0 (KF-6017) (2) Dimethylpolysiloxane 7.0 (3) Octamethylcyclotetrasiloxane 10.0 (4) Isostearyl isononanoate 6.0 (5) Methyl parahydroxybenzoate (6) Cetanol 0.5 (7) Beeswax 1.0 (8) Flavor (9) Palmitic acid-treated titanium oxide 0 (10) Iron oxide treated with palmitic acid 0.2 (11) Titanium mica treated with palmitic acid 10.0 (12) Ethanol 8.0 (13) Remaining purified water (14) Dipropylene glycol 3.0 (15) Salt 0.2 (16) Xanthan gum 0.1

(Production method) The components (1) to (12) are mixed and dispersed at 50 ° C. B. The components (12) to (16) are mixed and dispersed at 50 ° C. C. B was gradually poured into A, emulsified, cooled, and defoamed to obtain a cream eyeshadow. This cream eyeshadow had a refreshing sensation, had good skin familiarity, was excellent in usability without leaving stickiness, had good makeup lasting, and was stable at 50 ° C. for one month or more.

[0050]

Industrial Applicability The water-in-oil emulsion composition of the present invention has good skin familiarity, is fresh, has a refreshing sensation, is not sticky, is excellent in use feeling and cosmetic effect, and is also excellent in stability.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4C083 AA082 AB051 AB052 AB212 AB232 AB242 AB282 AB332 AB432 AC012 AC072 AC101 AC102 AC122 AC302 AC351 AC352 AC442 AC482 AC842 AC912 AD042 AD072 AD151 AD152 AD161 AD162 AD171 AD172 AD352 CC04 CC05 CC07 CC14 DD32 EE01

Claims (3)

[Claims] 1. A water-in-oil emulsion composition comprising the following components (a) to (d) as essential components. (A) one or more of polyoxyalkylene-modified organopolysiloxane and / or alkyl-modified polyoxyalkylene-modified organopolysiloxane (b) one of the branched monoesters represented by the following general formula (1)
Species or two or more species (In the formula, R ¹ represents an alkyl residue of an isocarboxylic acid having 5 to 18 carbon atoms, and R ² represents an alkyl residue of an isoalcohol having 3 to 18 carbon atoms.) (C) The following general formulas (2) and (3) ) Or one or more of the polysiloxanes represented by (4) Embedded image Embedded image (Where x is 4 to 100, z is an integer of 1 or more, and y + z
Represents an integer of 1 to 100, and p represents an integer of 3 to 7. (D) Water 2. A polyoxyalkylene modified component (a).
The organopolysiloxane is represented by the following general formula (5),
Modified polyoxyalkylene-modified organopolysiloxane
Is represented by the following general formula (6).
Emulsion composition. Embedded image[Wherein, R³Is an alkyl group having 1 to 5 carbon atoms or phenyl
Represents a group. R⁴Is -Q ¹-O- (C₂H₄O)_a−
(C₃H₆O)_b-R⁸Or-(C₂H₄O)_a− (C
₃H₆O)_b-R⁸And Q¹Is 2 having 1 to 5 carbon atoms
A divalent hydrocarbon group;⁸Is a hydrogen atom, having 1 to 5 carbon atoms
Represents an alkyl group or an acetyl group. a is an integer of 1 to 50
The number b is an integer of 0 to 50. G¹, G²Are the same
May be different and each R³Or R⁴Is shown. j is 0
Integer of ~ 150, k is an integer of 0 ~ 50. However,
When k = 0, G¹Or G²At least one is R⁴In
You. ][Wherein, R⁵Is an alkyl group having 1 to 5 carbon atoms or phenyl
Represents a group. R⁷Is -Q ²-O- (C₂H₄O)_c−
(C₃H₆O)_d-R⁹And Q²Has 1 to 5 carbon atoms
A divalent hydrocarbon group of⁹Is hydrogen atom, carbon number 1
5 to 5 alkyl groups or acetyl groups. c is 1 to 50
And d is an integer of 0 to 50. R⁶Is-(C₃H
₆O)_e-R¹⁰And e is an integer of 0 to 5, R¹⁰
Is an alkyl group having 6 to 18 carbon atoms. l is 5-150
M is an integer of 5 to 40, n is an integer of 2 to 40
You. ] 3. The water-in-oil type according to claim 1, further comprising ethanol as the component (e), wherein (d) :( e) is 70:30 to 100: 0 by weight. Emulsion composition.