JPH04210613A - Emulsion cosmetic - Google Patents

Abstract

PURPOSE:To provide an emulsion cosmetic containing a specific fluorine- containing polymer, a film-forming polymer and a volatile lubricant, having excellent oil resistance and water resistance, forming make-up resistant to water and sweat and giving good feeling to the skin. CONSTITUTION:The objective cosmetic contains 0.5-40wt.% of a fluorine- containing waxy polymer, 0.1-30wt.% of a film-forming polymer and 0.5-90wt.% of a volatile lubricant. It may be further compounded with proper surfactant, pigment, ultraviolet absorber, preservative, antioxidant, perfumery, etc. It is used in the form of a liquid make-up cosmetic such as eyeliner, eyebrow pencil and mascara or a make-up cosmetic such as foundation, face powder, rouge, eye shadow and lipstick.

Description

[Detailed description of the invention]

[00011

[Field of Industrial Application] The present invention relates to emulsified cosmetics, and more particularly to cosmetics that are emulsified but have excellent water resistance and do not remove makeup with water or sweat. [0002] [0002] Conventionally, makeup cosmetics have been divided into non-aqueous products that contain volatile oils such as isoparaffin and silicone oil, and emulsion-based products that contain water. be. Non-aqueous makeup cosmetics generally have sufficient resistance to water and sweat, that is, they are water resistant, but the coating film that is formed is mainly made of high-melting wax, and the makeup does not come off due to sebum or oil. However, the oil resistance was not sufficiently satisfactory. [0003] On the other hand, emulsified makeup cosmetics are superior to non-aqueous cosmetics in terms of feeling of use, but they are easily washed away by water, sweat, tears, etc., causing makeup to fade and a decrease in medicinal efficacy. There was a problem. To prevent this problem, various polymers have been added to form a film on the skin surface. As these film-forming polymers, synthetic resin emulsions such as polyvinyl acetate emulsion, polyacrylic acid ester emulsion, and copolymers thereof are known (for example, JP-A-62-281809 and JP-A-62-281809). No. 12606, 63
-192708, JP-A-1-261316, etc.). [0004]

[Problems to be Solved by the Invention] However, although these film-forming polymers form water-resistant films when used alone, they do not work well when used together with water-soluble surfactants and pigment dispersants to make emulsified cosmetics. may not be able to fully demonstrate its function, and the resulting cosmetic may have a phenomenon in which the film itself peels off due to water or sweat, resulting in poor adhesion.
I was not satisfied with the long-lasting makeup. [0005] Therefore, an emulsified cosmetic having not only oil resistance but also excellent water resistance has been desired. [0006]

[Means for Solving the Problems] Under the current circumstances, the present inventors have conducted intensive studies and found that by using a specific fluorine-containing polymer and a film-forming polymer in combination,
The present invention was completed based on the discovery that it is possible to obtain an emulsified cosmetic that has the excellent feeling of use peculiar to emulsified systems and has good not only oil resistance but also water resistance. [0007] That is, the present invention provides the following components (A) to (
C) An emulsified cosmetic composition characterized by containing (A) a waxy fluorine-containing polymer, (B) a film-forming polymer, and (C) a volatile oil agent. [00081 The wax-like fluorine-containing polymer (hereinafter referred to as "fluoropolymer") used in the present invention as component (A) is, for example, a long-chain alkyl (meth)acrylate and at least - hydrogen atoms are substituted with fluorine atoms. Examples include copolymers with (meth)acrylic acid esters bonded with alkyl groups. Here, the long-chain alkyl (meth)acrylate is preferably an ester of a straight or branched long-chain alkyl alcohol having 8 or more carbon atoms and (meth)acrylic acid, such as octyl alcohol, decyl alcohol, lauryl alcohol, cetyl alcohol. Examples include esters of long-chain alcohols such as , stearyl alcohol and behenyl alcohol, and (meth)acrylic acid. Among these, esters with long chain alcohols having 18 or more carbon atoms are particularly preferred. In addition, examples of the (meth)acrylic acid ester in which at least - hydrogen atoms bond an alkyl group substituted with a fluorine atom include known compounds having a polyfluoroalkyl group and a perfluoroalkyl group, For example, CH2
=CHC00C:! H4Cs F13, CH2= CHCOOC2H4Ca F l 7, CH
2=CHCOOC2H4CIOF21, CH2=CHCOOC2H4C12F25, CH2=C
(CH3) COOC2H4C6F+3, CH2=C(
CH3) COOC2H4Cs F1yCH2=C(C
H3) COOC2H4CIOF2+, CH2=C(C
H3) COOC2H4C12F25, CH2=CHC
OOC2H4(CF2) 4 H1CH2=CHC
OOC2H4(CF2) s -H1CH2=C(C
H3) COOC2H4(CF2) 5H1 CHz =C(CH3) COOC2H4(CF2)
Examples include s-H. The copolymerization ratio of these long-chain alkyl (meth)acrylates and (meth)acrylic acid esters in which at least - hydrogen atoms are bonded to alkyl groups substituted with fluorine atoms is determined in terms of solubility, sticky feeling, etc. to 10:1 to 1:5 (weight ratio), especially 7:1 to 1
:1 is preferable. In addition, the molecular weight of the copolymer is 1.000 to 2,000.0 from the viewpoint of friction resistance, sticky feeling, etc.
00, particularly preferably 10.000 to 500°000. [0009] The fluoropolymer can be used alone or in combination of two or more, and contains 0.5 to 40% by weight (hereinafter simply expressed as "%") in the total composition, especially 1,0 to 20% by weight. % is preferable. If it is less than 0.5%, the expected water and oil resistance will not be achieved, and if it exceeds 40%, the feeling of use may be impaired, such as spreading or stickiness, which is not preferable. [00101 (B) Component film-forming polymers include oil-soluble or ethanol-soluble polymers, aqueous polymer resin emulsions (latex), and the like. The oil-soluble or ethanol-soluble polymer may be anionic, cationic, amphoteric, or nonionic, and acrylic, vinylpyrrolidone, vinyl ether, and vinyl acetate polymers can be used. Among these, particularly preferred ones include, for example, the following formula:

A betaine type amphoteric polymer represented by [11] [Yukaformer AM-75 (manufactured by Mitsubishi Yuka Co., Ltd.)] is exemplified. [00111 Furthermore, as the aqueous polymer resin emulsion, any one having film-forming properties such as acrylic acid, vinyl acetate, styrene, synthetic rubber, olefin, alkyd, etc. can be used. , and may or may not have a charge. Among these, particularly preferred are vinyl acetate/butyl acrylate, styrene/octyl acrylate,
Mention may be made of copolymers such as ethyl acrylate/ethyl methacrylate, ethyl acrylate/methyl acrylate, methyl methacrylate/butyl acrylate/octyl acrylate, and the like. [0012] These film-forming polymers have a solid content of 0.1 to 30%, particularly 0.5 to 20% in the total composition.
It is preferable to mix them. [0013] Examples of the volatile oil agent of component (C) include hydrocarbons, silicones, etc., preferably linear or branched hydrocarbons with a boiling point of 260° C. or lower, and linear or cyclic silicones, such as isoparaffin or Examples include cyclic dimethylpolysiloxane. These volatile oil agents are preferably blended in an amount of 0.5 to 90%, particularly 1.0 to 40%, in the total composition. [0014] In order to emulsify the above components (A) to (C), it is preferable to blend a surfactant, particularly a surfactant [component (D)]. Examples of surfactants include polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitol fatty acid ester, dimethylsiloxane.・Methyl (polyoxyethylene) siloxane copolymer, etc. may be mentioned. These surfactants are preferably blended in an amount of 0.1 to 10%, particularly 0.2 to 4%, in the total composition. [0015] The emulsified cosmetic composition of the present invention can be made into a makeup cosmetic composition or a sunscreen agent with excellent water resistance by incorporating cosmetic powders [ingredient (E)] such as pigments and ultraviolet absorbers. can. Cosmetic powders are not particularly limited as long as they can be used for cosmetic purposes, such as titanium oxide, zinc oxide (zinc white), iron oxide, ultramarine, sericite, silica alumina, silica gel, kaolin, and talc. , mica, clay, nylon powder, titanium mica, magnesium oxide, chromium oxide, antimony oxide, magnesium carbonate, calcium carbonate, calcium phosphate, barium sulfate, aluminum hydroxide, boron nitride, chromium hydroxide, magnesium aluminate metasilicate, silicon Magnesium aluminate, polyethylene powder, red 202
No., Red No. 204, Red No. 226, Orange No. 201,
Examples include pigments such as Blue No. 404 and Yellow No. 401. Further, these pigments may be used in the form of fine particles, or a powder obtained by compounding two or more of these pigments using mechanochemical means may also be used. Furthermore, the surface of the above-mentioned powder may be treated with metal soap treatment, silicone treatment, dialkyl phosphate treatment, treatment with a perfluoro group-containing compound, amino acid treatment, lecithin treatment, collagen treatment, etc. and may be used. In addition to these pigments, powders of insoluble disinfectants, ultraviolet absorbers, etc. can also be used. Specifically, examples of insoluble disinfectants include trichlorocarbanilide, zinc pyrithione, etc., and examples of insoluble ultraviolet absorbers include Rfli.
Examples include those in which an organic ultraviolet absorber such as atomized titanium oxide, finely divided zinc oxide, and para-aminobenzoic acid is deposited as a polyvalent metal salt on the surface of a pigment such as mica. [0016] These cosmetic powders contain 5 to 9 in the total composition.
It is preferable to mix 5%, especially 10 to 95%. [0017] In addition, the above components (A) to (E) may include water alone or water and solvents that freely mix with water, such as lower alcohols such as ethanol and propatool, propylene glycol, dipropylene glycol, glycerin, 1, 3-
It is used by emulsifying it with a mixture of butanediol and the like (referred to as component (F), aqueous medium). This aqueous medium is
It is preferably blended in an amount of 0.5 to 90%, particularly 10 to 60%, in the total composition. [0018] Furthermore, in the present invention, in addition to the above-mentioned components, non-volatile oils, preservatives, antioxidants, fragrances, etc. used in ordinary cosmetics can be appropriately blended. Examples of non-volatile oils include straight-chain or branched-chain hydrocarbons (saturated or unsaturated), synthetic ester oils of higher alcohols and fatty acids, higher alcohols, higher fatty acids, waxes, and waxes. etc. Examples of the preservative include paraoxybenzoic acid alkyl ester, sodium benzoate, potassium sorbate, phenoxyethanol, and the like. Tocopherol as an antioxidant
Examples include cezamol, cezamorin, lecithin, and the like. [0019] The emulsified cosmetic of the present invention can be prepared by, for example, heating (A) a hook-like fluoropolymer, (C) a volatile solvent, and (D) a surfactant to about 60 to 90°C, and then adding it to the same temperature. After adding a part of the aqueous medium (F) and emulsifying it, and cooling it to room temperature, add the cosmetic powder (E) kneaded with a part of the aqueous medium (F), and (B) film-forming property on the body. It can be produced by adding polymers. [00201 The emulsified cosmetic of the present invention can be used not only for liquid makeup cosmetics such as eyeliner, eyebrow, and mascara, but also for foundation, white powder, blush, eye shadow,
It can be in the form of makeup cosmetics such as lipstick. [00211] [Effects of the Invention] The emulsified cosmetic composition of the present invention has excellent oil resistance and water resistance, does not remove makeup due to water or sweat, and has a good feel when used. [0022] [0022] Next, the present invention will be further explained with reference to Examples, but the present invention is not limited to these Examples. Reference Example 1 Perfluoroalkyl methacrylate (CH2=C(CH
3) COOC2H4C8F17) 26.7g, stearyl methacrylate so, o g, toluene 30
After dissolving and mixing, put 4 g of
．． After stirring under a nitrogen stream for 5 hours, 1.1 g of 2,2'-azobis-2,4-dimethylvaleronitrile was added, and polymerization was carried out at 65°C for 5 hours and then at 80°C for 1 hour under a nitrogen stream. A cloudy viscous solution was obtained. After polymerization, the copolymer was diluted with toluene and poured into ethanol to precipitate the copolymer, separated by filtration, and then dried under reduced pressure to obtain 102.4 g of a copolymer of perfluoroalkyl methacrylate and stearyl methacrylate. The monomer composition in the copolymer was almost the same as the charged composition (perfluoroalkyl methacrylate 2
(equivalent to 5.1%). [0023] Reference Example 2 Perfluoroalkyl methacrylate (CH2=C(CH
3) COOC2H4C8F17) 50g, stearyl methacrylate 50g, toluene 50g, 2.2'
-Azobis-2,4-dimethylvaleronitrile 1.0g
Copolymerization was carried out in the same manner as in Reference Example 1 except for using
96.0 g of a copolymer of perfluoroalkyl methacrylate and stearyl methacrylate was obtained. The perfluoroalkyl methacrylate in the copolymer was 49.6%, which was almost the same as the charged composition. [0024] Reference Example 3 Polyfluoroalkyl methacrylate (CH2=C(CH
3) COOC2H4C3F11CF2 H) 26.
Copolymerization was carried out in the same manner as in Reference Example 1 except that 7 g was used to obtain 101.4 g of a copolymer of polyfluoroalkyl methacrylate and stearyl methacrylate. Polyfluoroalkyl methacrylate in copolymer is 24.8%
The composition was almost the same as the preparation composition. [o o 25] Reference Example 4 Polyfluoroalkyl methacrylate (CH2=C(CH
3) COOC2H4C3FIL CF2H) 50
g, stearyl methacrylate 50g, toluene 50g
Copolymerization was carried out in the same manner as in Reference Example 1 except that 1.0 g of 2,2'-azobis-2,4-dimethylvaleronitrile was used to obtain 97.0 g of a copolymer of polyfluoroalkyl methacrylate and stearyl methacrylate. Obtained. The polyfluoroalkyl methacrylate in the copolymer is 5
It was 0.4%, which was almost the same as the charged composition. [0026] Reference Example 5 Copolymerization was carried out in the same manner as in Reference Example 1 except that stearyl methacrylate in Reference Example 1 was replaced with behenyl methacrylate to obtain 103.5 g of a copolymer of perfluoroalkyl methacrylate and behenyl methacrylate. The monomer composition in the copolymer was almost the same as the charged composition (perfluoroalkyl methacrylate was 24% based on F%).
(equivalent to 9%). [0027] Example 1 Mascara: (%) (1) Fluorine polymer (Reference example 1) (2) Polyoxyethylene (20) Sorbitol tetraoleate (3) Sorbitan monooleate (4) IP1620 (Low boiling point isoparaffin: (manufactured by Idemitsu Petrochemical) (5) water (6) xanthan gum (7) butylene glycol (8) black iron oxide (9) polymer resin emulsion (vinyl acetate/butyl acrylate). (10) Preservative book: Movinyl DM-5 (Hoechst Synthesis), solid content 53
% (Production method) (1) to (4) are heated and stirred to uniformly dissolve, and then cooled to room temperature. (A) Add (6) to (8) to (5) and uniformly disperse with a disperser. (B) After adding (A) to (B) and stirring well until the whole was uniform, (9) and (10) were added and stirred to obtain a black mascara. [0028] Example 2 Mascara: (1) Fluoropolymer (Reference Example 2/Reference Example 5 = 10/
1) (2) Polyoxyethylene (20) Sorbitan monooleate (3) Sorbitan monolaurate (4) IP1620 (5) Water (6) Bentonite (7) Glycerin (8) Black iron oxide (9) Polymer resin emulsion (Movinyl DM-5
) (10) Ampholytic polymer (Yukaformer AM-75:
(Mitsubishi Yuka). (11) Preservative *: Ethanol solution, solid content 30% (Production method) (1) to (4) are heated to 80℃ and stirred to uniformly dissolve, and while adding (5) heated to 80℃ little by little, After stirring with a homomixer, cool to room temperature. (6) to (1*1) were sequentially added to this to obtain. [0029] Stir with disper to make black mascara Example 3 Mascara: (%) (1) Fluoropolymer (Reference Example 1) (2) IP1620 (3) Octamethylcyclotetrasiloxane (4) Dimethylpolysiloxane methyl ( polyoxypropylene)
Siloxane copolymer [Toμ Silicone 5H3749
) (5) Water (6) Butylene gellicol (7) Bentonite (8) Hydroxyethyl cellulose (9) Black iron oxide (10) Red iron oxide (11) Yellow iron oxide (12) Polymer resin emulsion (ethyl acrylate/ethyl methacrylate )1 (13) Preservative*: Dydosol 5000AD (Daito Kasei), solid content 50% trace amount (manufacturing method) A brown mascara was obtained in the same manner as in Example 1. The mascaras obtained in Examples 1 to 3 were made of fluoropolymer,
Compared to products that do not contain any of the film-forming polymers, it spreads well, is easier to apply evenly to the eyelashes, and does not fall off due to sweat or tears, but does not easily crumble. [00301 Against friction such as blinking Example 4 Eyeliner: Fluorine polymer (Reference example 3) Polyoxyethylene (20) Sorbitan monooleate Polyoxyethylene (6) Sorbitan monooleate Sorbitan monolaurate (%) (5) IP1620 (6) Water (7) Bentonite (8) Butylene glycol (9) Polyoxyethylene hydrogenated castor oil (10) Black iron oxide (11) Red iron oxide (12) Red iron oxide (13) Yellow iron oxide (14) Polymer resin emulsion ( Daitosol 50
00AD) (15) Preservative (manufacturing method) Heat and stir (1) to (4) to 80°C to make them uniform. Add (5) heated to 80°C to this, stir thoroughly until the mixture becomes homogeneous, and then cool to room temperature. (7)～(1
2) is passed through a three-roll mill three times to crush and disperse the pigment to prepare a pigment paste. Add (6), pigment paste, (13) and (14) in order to the emulsion obtained from (1) to (5), and stir well with a disperser until the whole is uniform to obtain a brown eyeliner. Ta. The resulting eyeliner spread well and evenly, was easy to apply, did not come off with sweat after drying, and had high water and oil resistance. [00311 Example 5 Eyeliner: (%) (1) Fluoropolymer (Reference Example 4) (2) IP1620 (3) Octamethylcyclotetrasiloxane (4) Decamethylcyclopentasiloxane (5) Dimethylpolysiloxane methyl ( Polyoxypropylene) siloxane copolymer [Toμ Silicone 5H3749] (6) Water (7) Butylene gelicol (8) Bentonite (9) Black iron oxide (10) Red iron oxide (11) Yellow iron oxide (12) Titanium oxide (13) Polymer resin emulsion (ethyl acrylate/methyl methacrylate) (14) Ampholytic polymer (Yukaformer AM-75: Mitsubishi Yuka) (15) Preservative: Primal AC-33 (Nissin Chemical), solid content 40%
5.5 Trace amount (manufacturing method) A black eyeliner was obtained in the same manner as in Example 4 [0032 Example 6 Eyeliner: (%) Fluoropolymer (Reference Example 1) P1620 Octamethylcyclotetrasiloxane decamethylcyclopenta Siloxane dimethylpolysiloxane/methyl (polyoxypropylene) xane copolymer [Toμ Silicone 5H3749
) Hydroxyethyl cellulose bentonite white (9) Butylene glycol (10) Black iron oxide (11) Polymer resin emulsion (styrene/octyl acrylate) (12) Preservative *: Movinyl 935H (Hoechst Synthesis), solid content 51
% (Production method) A black eyeliner was obtained in the same manner as in Example 4. [0033] Example 7 Emulsified eyeshadow: (1) Fluoropolymer (Reference Example 1) (2) IP1620 (3) Polyoxyethylene (20) Sorbitan monooleate (4) Sorbitan monolaurate (5) Water ( 6) Propylene glycol (7) Bentonite (8) Hydroxyethyl cellulose (9) Mica titanium (10) Iron oxide (11) Kaolin (12) Talc (13) Ampholytic polymer (Yukaformer AM-75) (
14) Preservative (%) (Production method) Heat and stir (1) to (4) at 80°C to uniformly mix and dissolve. After adding (5) heated to 80°C to this and stirring with a homomixer, the mixture was cooled to room temperature. Add (6) to (8), (13) and (14) to this one after another and mix uniformly, then add (9) to (12), which have been uniformly ground and mixed in advance, and stir and mix uniformly. Got the eyeshadow. The resulting eyeshadow blends well into the skin and can be spread evenly. Furthermore, it did not cause makeup blemishes due to sweat, etc., and was highly water and oil resistant. [0034] Example 8 Emulsified eyeshadow: (%) (1) Fluoropolymer (Reference Example 1) (2) lI'1620 (3) Octamethylcyclotetrasiloxane (4) Decamethylcyclopentasiloxane (5) Dimethyl Polysiloxane/methyl (polyoxypropylene) xane copolymer [Toμ Silicone 5H3749] (6) Water (7) Butylene glycol (8) Bentonite (9) Carboxymethyl cellulose (10) Mica titanium (11) Iron oxide (12 ) Ultramarine (13) Talc (14) Ampholytic polymer (Yukaformer AM-75) (
15) Preservative residue 5.0 1.0 0.5 15.5 2.0 1.5 12.0 8.0 Trace amount (Production method) An eye shadow was obtained in the same manner as in Example 7.

Claims (1)

[Claims] Claim 1: The following components (A) to (C) (A) Waxy fluorine-containing polymer (B) Film-forming polymer (C) Volatile oil agent An emulsified cosmetic characterized by containing.