JP2001048726A - Cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an oil-in-water emulsified cosmetic giving refreshing and comfortable feeling, and excellent in waterproofness, etc., by including a fluorine- based oil agent, powder treated with a fluorine compound and a specific water- soluble polysaccharide derivative so as to stably disperse both the oil agent aid powder in water. SOLUTION: This oil-in-water emulsified cosmetic is obtained by including (A) 1 to 50 wt.% of a fluorine-based oil agent, (B) 1 to 50 wt.% of powder treated with a fluorine compound and (C) 0.01 to 10 wt.% of a water-soluble polysaccharide derivative having both hydrophobic group and hydrophilic group; wherein the component C is preferably such one as to have >=8C hydrocarbon group, e.g. a derivative wherein at least part of the hydrogen atoms in the OH groups of a polysaccharide (derivative) is substituted with (i) substituent(s) having a hydraphobic group selected from a 8-40C alkyl group, alkenyl group, arylalkyl group and alkylaryl group and (ii) a substitent(s) having (OH substituted) (non)ionic hydrophilic parts, and the substitution degree ratio of the substituent i to the substituent ii is (1:100) to (100:1).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oil-in-water emulsion in which a fluorinated oil and a powder treated with a fluorine compound are uniformly and stably dispersed in water, which gives a refreshing, good feel, and excellent water resistance and oil resistance. Related to cosmetics.

[0002]

2. Description of the Related Art In order to impart water resistance and oil resistance to cosmetics, fluorinated oils and powders treated with fluorine compounds have been used (JP-A-4-91008, etc.). However, it is difficult to stably disperse these in oil-in-water type cosmetics. For example, attempts have been made to use acrylic acid-based polymers in combination (Japanese Patent Application Laid-Open No. 9-143023). It was not yet satisfactory in terms of usability.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an oil-in-water type in which a fluorinated oil and a powder treated with a fluorine compound are stably dispersed in water, have a refreshing, good feel, and are excellent in water resistance and oil resistance. An object of the present invention is to provide an emulsified cosmetic.

[0004]

Means for Solving the Problems The present inventors have found that an excellent oil-in-water emulsified cosmetic which has solved the above-mentioned problems can be obtained by using a specific water-soluble polysaccharide derivative together with a fluorinated oil and a powder treated with a fluorine compound. It was found that it could be obtained.

The present invention provides an oil-in-water emulsion cosmetic containing (A) a fluorine-based oil, (B) a powder treated with a fluorine compound, and (C) a water-soluble polysaccharide derivative having a hydrophobic group and a hydrophilic group. Is what you do.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The fluorine-based oil component (A) used in the present invention is a perfluoro organic compound which is liquid at ordinary temperature, such as perfluorodecalin, perfluoroadamantane, perfluorobutyltetrahydrofuran, and the like.
Examples include perfluorooctane, perfluorononane, perfluoropentane, perfluorodecane, perfluorododecane, perfluoropolyether represented by the general formula (1), and fluorine-modified silicone.

[0007]

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Wherein R ¹ , R ³ , R ⁴ and R ⁵ are the same or different and each represents a fluorine atom, a perfluoroalkyl group or a perfluoroalkyloxy group, and R ² represents a fluorine atom or a perfluoroalkyl group. And a, b and c
Represents a number of 0 or more at which the molecular weight becomes 500 to 100,000.) Here, the perfluoro groups shown in parentheses need not be arranged in blocks in this order, but may be random. The perfluoropolyether is preferably a liquid having a viscosity of 5 to 5,000 mm ² / s at 20 ° C., for example, Fomblin HC-0.
4, HC-25, HC-R (all manufactured by Asimont)
And, Demnum S-20, S-65, S-100, S-2
A commercially available product such as 00 (both manufactured by Daikin Industries, Ltd.) can be used.

The fluorine-modified silicone includes, for example, a modified silicone having one or more structural units represented by the following general formulas (2) to (5) and a structural unit represented by the following general formula (6). .

[0010]

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[In the formula, Rf and Rf 'are the same or different and each is a linear or branched perfluoroalkyl group having 1 to 20 carbon atoms or the following formula: H (CF ₂ ) _t- (t is 1 R ¹¹ , R ¹⁴ and R ¹⁵ are the same or different, and represent an ω-H-perfluoroalkyl group represented by the following formula:
An aliphatic hydrocarbon group having 1 to 20 carbon atoms or 5 to 10 carbon atoms
Represents an alicyclic or aromatic hydrocarbon group; R ¹² represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms,
Alicyclic or aromatic hydrocarbon group of 10 to 10 carbon atoms
20 perfluoroalkyl group or the following formula: H (CF ₂ ) _t- (t
Represents an integer of 1 to 20); R ¹³ represents a divalent hydrocarbon group having 2 to 6 carbon atoms; X and Y represent a single bond; -CO- or a divalent hydrocarbon group having 1 to 6 carbon atoms; l represents a number of 2 to 16, m and n each represent a number of 1 to 16,
Represents a number of 1 to 200, r represents a number of 0 to 20, s
Represents a number from 0 to 200. ]

In the present invention, a preferred example of the fluorine-modified silicone is described in JP-A-5-247214 having structural units represented by the general formulas (3) and (6).
Fluorine-modified silicone having a degree of polymerization of 2 to 200 described in JP-A-6-184312, having structural units represented by general formulas (4) and (6). 200 fluorine-modified silicone, commercially available FSL-300 manufactured by Asahi Glass Co., Ltd., X-22-819, X-22-820, X-22-manufactured by Shin-Etsu Chemical Co., Ltd.
821, X-22-822 and FL-100, FS1265 manufactured by Dow Corning Toray Silicone Co., Ltd., and the like.

One or more fluorine-based oils of component (A) can be used, and 1 to 50% by weight, particularly 5
It is preferable to mix it in an amount of from 40 to 40% by weight, more preferably from 5 to 30% by weight, because it is more excellent in usability and emulsion stability.

The powder of the component (B) used in the present invention, which is treated with a fluorine compound, may be, for example, polyfluoroalkylphosphoric acid (US Pat. No. 3,632,744) or fluoroalkyldi (oxyethyl) amine phosphoric acid ester (Japanese Unexamined Patent Publication No. Sho 62). −
No. 250074), a resin having a perfluoroalkyl group (JP-A-55-167209), an ethylene tetrafluoride resin, a perfluoroalcohol, a perfluoroepoxy compound, a sulfoamide-type fluorophosphoric acid, a perfluorosulfate, a perfluorocarbon Acid salt, perfluoroalkylsilane (LP-1T, LP-
It is treated with a fluorine compound such as a silane coupling agent such as 4T and LP-8T by a conventional method.

The powder to be treated is not particularly limited as long as it is a substance substantially insoluble in water and oil, such as a pigment and an ultraviolet absorber. For example, titanium oxide, iron oxide, ultramarine, zinc white,
Inorganic pigments such as magnesium oxide, zirconium oxide, mica, sericite, talc, silica, kaolin, chromium hydroxide, and carbon black; organic powders such as nylon powder, polymethyl methacrylate, styrene-divinylbenzene copolymer, and polyethylene powder And ultraviolet absorbers such as fine-particle titanium oxide, fine-particle zinc oxide, and plate-like zinc oxide.

Although the amount of the fluorine compound to be treated varies depending on the type of the powder and the treating agent, the amount of the fluorine compound is from 0.1 to 50% by weight, especially from 2 to 20% by weight, in terms of water repellency and spreadability. Is preferred.

The fluorine compound-treated powder of the component (B) comprises 1
More than one kind can be used, and it is preferable to mix 1 to 50% by weight, particularly 1 to 30% by weight in the total composition, because the dispersibility of the powder is good.

As the water-soluble polysaccharide derivative having a hydrophobic group and a hydrophilic group of the component (C) used in the present invention, those having a hydrocarbon group having 8 or more carbon atoms are preferable, for example, a hydroxyl group of the polysaccharide or a derivative thereof. (A) a substituent having a hydrophobic part selected from an alkyl group, an alkenyl group, an arylalkyl group and an alkylaryl group having 8 to 40 carbon atoms, and (b) a hydroxyl group. Is substituted with a substituent having an ionic or nonionic hydrophilic portion which may be substituted, and the ratio of the degree of substitution between the substituent (a) and the substituent (b) is from 1: 1000 to 100: 1. And water-soluble polysaccharide derivatives.

Here, the substituent (a) includes, for example, an alkyl group having 8 to 40 carbon atoms, an alkenyl group, an arylalkyl group, an alkylaryl group, an alkyl ether group,
Examples thereof include an alkenyl ether group and an arylalkyl ether group, and a substituted glyceryl ether group having an alkyl group or an alkenyl group having 10 to 40 carbon atoms is particularly preferable. Specifically, 2-hydroxy-3-alkoxypropyl group, 2-alkoxy-1- (hydroxymethyl) ethyl group, 2-hydroxy-3-alkenyloxypropyl group, 2-alkenyloxy-1- (hydroxymethyl) Ethyl groups are mentioned.

Further, examples of the substituent (b) include a methyl group, a hydroxyethyl group, a hydroxypropyl group, a polyoxyethylene group, a polyglycerin group, a sulfoalkyl group and the like. Among these, a sulfoalkyl group having 1 to 5 carbon atoms which may be substituted by a hydroxyl group or a salt thereof is preferable, and specifically, a 2-sulfoethyl group,
A 3-sulfopropyl group, a 3-sulfo-2-hydroxypropyl group, a 2-sulfo-1- (hydroxymethyl) ethyl group, and the like. All or a part of the sulfo groups is an alkali metal, an alkaline earth metal, It may be in the form of a salt with an organic cation group such as an amine or an ammonium ion.

The degree of substitution of the substituent (a) is preferably from 0.001 to 1, more preferably from 0.002 to 0.5, even more preferably from 0.003 to 0.1 per constituent monosaccharide residue. (B)
Is preferably 0.01 to 2.5, more preferably 0.02 to 2, further preferably 0.1 to 1.5 per constituent monosaccharide residue. Further, the ratio of the degree of substitution between the substituent (a) and the substituent (b) is 1: 1000 to 100: 1, particularly 1: 500 to 10:
1, more preferably 1: 300 to 10: 1.

The basic skeleton of the polysaccharide derivative of the component (C) is selected from known polysaccharides, and cellulose, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose and hydroxypropyl cellulose are particularly preferred. The weight average molecular weight of these polysaccharides or derivatives thereof is
The range is preferably from 10,000 to 10,000,000, particularly preferably from 100,000 to 5,000,000, and more preferably from 300,000 to 2,000,000.

Such a water-soluble polysaccharide derivative can be prepared by sequentially or sequentially adding a hydrophobic substituent (a) and a hydrophilic substituent (b) to a polysaccharide or a derivative thereof according to the method described in JP-A-11-12119. Manufactured by simultaneous introduction.

Examples of the water-soluble polysaccharide derivative of the component (C) include modified cellulose ethers described in Examples 1 to 3 of JP-A-3-24001 and US Pat. No. 4,228,277.
Non-ionic long-chain alkylated cellulose ether described in US Pat.
ROSOL PLUS) 330 and Natrosol Plus C
Alkyl-modified hydroxyethylcellulose such as S (NATROSOL PLUS) D-67 (manufactured by Aqualon Co., Ltd.), and hydrophobized-modified sulfonated polysaccharide derivatives can also be suitably used.

One or more water-soluble polysaccharide derivatives of the component (C) can be used, and the total composition is 0.01 to 10% by weight, preferably 0.02 to 5% by weight, more preferably 0.05 to 3% by weight. weight%
It is preferable to mix them because sufficient dispersibility can be obtained and the feeling of use is good.

In the cosmetic of the present invention, in addition to the above-mentioned components, components to be blended with ordinary cosmetics, for example, surfactants, oils, humectants, film-forming agents, oil gelling agents, ultraviolet absorbers,
Color pigments, other hydrophobized powders, inorganic metal salts, organic metal salts, alcohols, chelating agents, pH adjusters, preservatives, other thickeners, medicinal ingredients, pigments, fragrances, water, etc. Can be blended.

The cosmetic of the present invention is prepared according to a usual method.
Prepared as an oil-in-water emulsion cosmetic, emulsion, cream,
It can be applied as a makeup base, foundation, sun care agent, lipstick, blusher, eyeshadow, leg makeup, arm makeup, neck makeup, finger makeup and the like.

The cosmetics of the present invention are excellent in water resistance. The criteria of the water resistance can be evaluated by the contact angle of water with respect to the cosmetic coating film. That is, prepare an artificial leather sheet (made of polyurethane, 10 cm square),
A sample (80 mg) is applied by a finger so as to be uniform on the surface 5 cm square (25 cm ² ), and dried at 40 ° C. and 50% humidity for 1 hour. Thereafter, the sheet is divided into equal parts using a cutter so that the sheet can be inserted into the contact angle measuring device.
In a 50% humidity environment, one drop of ion-exchanged water is dropped onto the sample surface from the tip of the microsyringe, and the contact angle (degree) at that time
Is measured after 1 minute.

In the present invention, it is possible to obtain a highly water-resistant cosmetic having a contact angle thus determined of 60 degrees or more.

In the present invention, a highly oil-resistant cosmetic having a contact angle similarly required of 30 ° or more using squalane can be obtained.

[0031]

The oil-in-water emulsified cosmetic composition of the present invention has a fluorine-based oil and a fluorine compound-treated powder dispersed uniformly and stably in water, and has a refreshing, good feel and excellent water resistance and oil resistance. It is a thing.

[0032]

EXAMPLES Production Examples 1 to 12 Water-soluble polysaccharide derivatives were produced using the starting polysaccharides, hydrophobizing agents and sulfonating agents shown in Table 1 in accordance with the method described in JP-A-11-12119.

[0033]

[Table 1]

Production Example 13 A vessel was charged with 105 g of powder and 500 mL of water, and the fluoroalkyl phosphate dioxyethylamine salt [(C _{9
F 19 C 2 H 4 O)} y P (= O) (ONH 2 (CH 2 CH 2 OH) 2) 3-y] (2>y> 1)
Was added and stirred at 40 ° C. Next, 1N-hydrochloric acid was added to lower the pH of the aqueous solution to 4, and fluoroalkyl phosphoric acid was precipitated on the powder surface. This was filtered, washed with water, and dried to obtain a fluorine compound-treated powder.

Production Example 14 ₁₇ g of (C ₈ F ₁₇ CH ₂ CH ₂ O) ₂ P (O) OH and 1500 g of isopropyl alcohol were placed in a container, dissolved by heating at 60 ° C., and 150 g of powder was added thereto. And mix for 4 hours. Thereafter, isopropyl alcohol was distilled off under reduced pressure at 50 to 60 ° C. and dried to obtain a fluorine compound-treated powder.

Examples 1 to 13 and Comparative Examples 1 to 12 Foundations having the compositions shown in Tables 2 to 4 were prepared and evaluated for emulsifying properties, storage stability, feeling of use, water resistance and oil resistance. The results are shown in Tables 2 to 4.

(Preparation method) At room temperature, a water-soluble polysaccharide derivative is dissolved in purified water, and then another aqueous phase component is added and mixed. On the other hand, the powder component is added to the oil phase, and strongly dispersed using a disper. Transfer the aqueous phase to Ajihomomixer and add 50
The mixture of the powder and the oil phase component was slowly added while stirring at a high speed at ℃, and the mixture was stirred at a high speed for 30 minutes to obtain a foundation.

(Evaluation method) (1) Emulsifiability: Each foundation was filled in a glass bottle containing 50 mL, and the appearance was visually evaluated according to the following criteria. ◎: good. ：: There is an oil film slightly on the surface. Δ: Slight separation (分離 2%). X: Separation (2% or more).

(2) Storage stability: After the emulsifying property was evaluated, the emulsifying property was evaluated in the same manner after storage at 40 ° C. for one month.

(3) Feeling of use: Ten specialized panelists made sensory evaluations of “freshness” and “no stickiness” when each foundation was actually used, and were judged according to the following criteria. ：: 7 or more evaluated good. Δ: 4 to 6 persons evaluated it as good. ×: Three or less evaluated as good.

(4) Water resistance: The contact angle with respect to water was measured by the method described above, and evaluated according to the following criteria. A: Contact angle of 80 degrees or more. ：: contact angle of 60 to less than 80 degrees. Δ: Contact angle of less than 40 to 60 degrees. X: Contact angle less than 40 degrees.

(5) Oil resistance: The contact angle with squalane was measured by the method described above, and evaluated according to the following criteria. A: Contact angle of 50 degrees or more. ：: contact angle of less than 30 to 50 degrees. Δ: Contact angle of less than 10 to 30 degrees. X: Contact angle less than 10 degrees.

[0043]

[Table 2]

[0044]

[Table 3]

[0045]

[Table 4]

As is evident from the results in Tables 2 to 4, all of the foundations of the present invention have excellent emulsifiability and emulsification stability, a good feeling in use, and high water resistance and oil resistance. Met. In contrast, when the water-soluble polysaccharide derivative was not used (Comparative Example 1), the emulsifiability was poor, and when the emulsifiability was improved by blending a hydrophilic surfactant at a high concentration (Comparative Examples 2 and 3). Although the emulsifying property was improved, the feeling of use and the water resistance were lowered. Further, when a water-soluble polymer conventionally known as a thickener is used (Comparative Examples 4 to 9), the emulsifiability and the emulsification stability are reduced. The use feeling and the water resistance were reduced. Further, when a hydrocarbon oil other than the fluorine oil was used (Comparative Example 11), the emulsifiability and the emulsion stability were good, but there was a sticky touch peculiar to the hydrocarbon oil, and the oil resistance was high. Was not obtained. When a silicone oil (Comparative Example 10) or a silicone-treated powder was used (Comparative Example 12), no oil resistance was obtained.

Example 14 (Sun care cream) A sun care cream having the following composition was produced.

(Table 5) (Components) (% by weight) (1) Water-soluble polysaccharide derivative (Production Example 10) 0.5 (2) Dimethylsiloxane / methyl (polyoxyethylene) siloxane polymer 2.0 (3) Polyoxyethylene (20EO) Sorbitan monooleate 0.5 (4) Perfluoropolyether (Fomblin HC-04, manufactured by Ausimont) 11.0 (5) Dextrin palmitate 0.5 (6) Octyldimethylparaaminobenzoic acid 4 0.0 (7) Fine particles of titanium oxide treated with a fluorine compound (Production Example 14) 5.0 (8) Acidic heteropolysaccharide 0.03 (9) Magnesium sulfate 0.5 (10) Glycerin 5.0 (11) Dibutylhydroxytoluene 0.05 (12) Water balance

(Preparation method) The component (1) is dissolved in purified water by stirring in a conventional manner, and the components (8) to (10) are added thereto. (7) and (1)
1) was slowly added and emulsified to obtain a sun care cream.

Example 15 (Decorative base) A decorative base having the following composition was produced.

(Table 6) (Components) (% by weight) (1) Water-soluble polysaccharide derivative (Production Example 11) 0.5 (2) Perfluoroalkyl-modified silicone (JP-A-6-184312, Example 4) 10 (3) Methylcyclopolysiloxane (2.3 mm ² / s) 10 (4) Methyl polysiloxane (2 mm ² / s) 5 (5) Cetyl alcohol 0.5 (6) Stearyl alcohol 0.5 (7) Perfume / preservative 8) Purified water balance (9) Glycerin 2 (10) Fluorine compound-treated cellulose powder (Production Example 13) 1

(Preparation method) The component (1) is stirred and dissolved at room temperature in purified water, and after adding the component (9), the components (2) to (7) and (10) was slowly added and emulsified to obtain a makeup base.

Example 16 (Emulsion type eye shadow) An emulsion type eye shadow having the following composition was produced.

(Component) (% by weight) Powder: (1) Mica treated with a fluorine compound (Production Example 13) 10.0 (2) Titanium mica 5.0 (3) Pigment 3.0 Oil phase: (4) Stearic acid 3.0 (5) Isopropyl myristate 3.0 (6) Perfluoroalkyl-modified silicone (Japanese Unexamined Patent Publication (Kokai) No. 6-184321, Example 4) 10.0 (7) Propylene glycol monolaurate 3.0 (8) Dibutylhydroxytoluene 0.02 Water phase: (9) Purified water balance (10) 1,3-butylene glycol 5.0 (11) Water-soluble polysaccharide derivative (modified cellulose described in JP-A-3-24001, Example 2) (Ether) 0.3 (12) ethyl paraben 0.2 (13) disodium edetate 0.1

(Preparation method) The powder portion is added to an aqueous phase portion which has been previously dissolved and mixed at 70 ° C., and highly dispersed by a disper. To this, the oil phase portion dissolved and mixed at 70 ° C. is added with stirring.
The mixture was uniformly dispersed and mixed with a homomixer, and cooled to room temperature to obtain an eye shadow.

Example 17 (Cream foundation): A cream foundation having the following composition was produced in the same manner as in Example 1.

[0054]

(Composition) (% by weight) (1) Fluorine compound-treated titanium oxide (Production Example 14) 6.0 (2) Fluorine compound-treated sericite (Production Example 14) 8.0 (3) Fluorine compound-treated oxidation Iron (red, yellow, black) (Production Example 14) 1.2 (4) Decamethylcyclopentasiloxane 15.0 (5) Fluorine-modified silicone (JP-A-5-247214, Example 5) 25.0 (6) ) Water-soluble polysaccharide derivative (Production Example 6) 0.2 (7) Dimethylpolysiloxane polyoxyalkylene copolymer 5.0 (8) Glycerin 2.0 (9) Water remaining amount (10) Fragrance trace amount

In each of the cosmetics obtained in Examples 14 to 17, the fluorine-based oil agent and the powder treated with the fluorine compound were uniformly and stably dispersed in water, and had a refreshing and good feel, and were also resistant to water and oil. Was excellent.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Tomohito Kitsuki 1334 Minato, Wakayama-shi, Wakayama Prefecture F-term (reference) 4C083 AB212 AB232 AB242 AB362 AB432 AC072 AC102 AC122 AC242 AC342 AC352 AC392 AC442 AC472 AC482 AC532 AC622 AD112 AD152 AD162 AD172 AD211 AD212 AD242 AD262 BB11 BB25 CC03 CC05 CC12 CC14 CC19 DD31 DD33 EE17

Claims (2)

[Claims] 1. An oil-in-water emulsion cosmetic containing (A) a fluorine-based oil, (B) a powder treated with a fluorine compound, and (C) a water-soluble polysaccharide derivative having a hydrophobic group and a hydrophilic group. 2. Component (C) is a polysaccharide or a derivative thereof, wherein a part or all of the hydrogen atoms of a hydroxyl group are (a) a linear or branched alkyl group or alkenyl group having 8 to 40 carbon atoms, A substituent having a hydrophobic moiety selected from an arylalkyl group and an alkylaryl group, and (b) a hydroxyl group substituted with a substituent having an ionic or nonionic hydrophilic moiety which may be substituted. The ratio of the degree of substitution between the group (a) and the substituent (b) is 1: 1000 to 100: 1.
The cosmetic according to claim 1, which is a water-soluble polysaccharide derivative represented by the formula: