JP4162587B2 - Oil-in-water emulsion composition - Google Patents

Description

  The present invention relates to an oil-in-water emulsion composition containing a liquid perfluoropolyether.

  As cosmetic needs, water resistance, sweat resistance, and sebum resistance are common specifications. As a method for imparting water resistance, sebum resistance, that is, water and oil repellency, to cosmetics, there may be mentioned the use of powders surface-treated with fluorine-based components such as fluorine-based oils or fluorine compounds. However, the fluorine-based oil agent and the fluorine compound-treated powder are excellent in water and oil repellency, but are not compatible with other components and are difficult to disperse uniformly. In particular, in an oil-in-water emulsion containing water, it is difficult to obtain emulsion stability.

Therefore, in order to perform stable emulsification, investigations have been made on oil agents and emulsifiers that are compatible with fluorine-based oil agents and on devising production methods. For example, Patent Document 1 discloses a perfluoro organic compound in which a fluorine-based surfactant such as perfluorohexyl hexadecane ether is dissolved in an oil component, and in which all hydrogen is substituted with fluorine having 6 to 20 carbon atoms. Perfluorodecalin etc.) is dispersed and emulsified to obtain a perfluoro organic compound type emulsion in oil, and this emulsion is further dispersed and emulsified in an aqueous solution of a nonionic surfactant to obtain a perfluoro organic compound phase / oil phase / An aqueous phase multiphase emulsified cosmetic is described. Further, Patent Document 2 includes a fluorinated oil agent, a fluorine compound-treated powder, a water-soluble polysaccharide derivative having a hydrophobic group and a hydrophilic group, and has excellent dispersion stability, water use and oil resistance. Oil-type cosmetics are described.
Japanese Patent Laid-Open No. 62-223105 Japanese Patent Laid-Open No. 2001-48726

  An object of the present invention is to provide an oil-in-water emulsion composition having good water and oil repellency, good feeling in use, and excellent emulsion stability.

  The present inventor has found that an oil-in-water emulsion composition obtained by using a vinyl-based water-soluble copolymer containing a large amount of a low-molecular-weight compound among perfluoropolyether compounds in an oil phase has sufficient water repellency. It has been found that it has oil repellency and is excellent in feeling of use and emulsion stability.

That is, the present invention contains 70% by mass or more of liquid perfluoropolyether having a molecular weight of 5000 or less in the oil phase, and contains a fluorinated ether compound of the general formula (1), a water-soluble vinyl copolymer, and water. Oil-in-water emulsion composition
Rf- (CH ₂ ) _n -OR ¹ (1)
(In the formula, Rf represents a linear or branched perfluoroalkyl group having 1 to 20 carbon atoms, R ¹ represents a linear or branched alkyl group or cycloalkyl group having 2 to 30 carbon atoms, and n represents 1. Or the number of 2 is shown.)
Is to provide.

  The oil-in-water emulsion composition of the present invention has good water and oil repellency, good feeling in use, and excellent emulsion stability.

  In the present invention, the oil phase contains a large amount of a perfluoropolyether having a low molecular weight as the fluorinated oil agent, and further uses a vinyl-based water-soluble copolymer. An oil-in-water emulsion composition having excellent dispersibility and emulsion stability is obtained. That is, by using a fluorinated ether compound of the general formula (1) and dispersing a low molecular weight perfluoropolyether with good usability in an aqueous vinyl polymer solution, the oil-in-water type has excellent usability and high water resistance. Can be blended. In addition, by using a water-soluble vinyl copolymer as a stabilizer, a fresher feel different from that of polysaccharides can be obtained.

The liquid perfluoropolyether of the present invention is liquid at 25 ° C. and has a molecular weight of 5000 or less. Moreover, it is preferable that the viscosity of 25 degreeC is 5-5,000 cSt.
Examples of such perfluoropolyethers include perfluoropolyethers represented by the following general formulas (2) and (3).

(In the formula, x and y represent numbers with a molecular weight of 5,000 or less, and x / y is 0.2 to 2)

F- (C ₃ F ₆ O) _z -C ₂ F ₅ (3)
(In the formula, z represents a number of 4 to 500)

  Moreover, as General formula (2), brand name FOMBLIN HC-04 (average molecular weight 1,500), HC-25 (average molecular weight 3,200) (above, AUSHIMON Co.); Commercial products of trade names demnum S-20 (average molecular weight 2,500) and S-65 (average molecular weight 4,500) (above, Daikin Industries, Ltd.) can be used.

A liquid perfluoropolyether can be used 1 type or in combination of 2 or more types. Further, from the viewpoint of water / oil repellency and usability, it is preferable to contain 70% by mass (hereinafter, simply expressed as%) or more, particularly 75 to 90% in the oil phase.
Moreover, in an emulsion composition, it is preferable that it is 3 to 40%, and especially it is preferable that it is 4 to 30%, and also that it is 4 to 25% since the stability of an emulsion composition can be improved more.

  In the present invention, the fluorinated ether compound of the general formula (1) is used for obtaining good emulsion stability in an oil phase containing a perfluoropolyether.

Rf represents a linear or branched perfluoroalkyl group having 1 to 20 carbon atoms, preferably a linear or branched perfluoroalkyl group having 2 to 14 carbon atoms, particularly a linear or branched carbon number of 4 to 12 carbon atoms. The perfluoroalkyl group is preferable. R ¹ represents a linear or branched alkyl group or cycloalkyl group having 2 to 30 carbon atoms, and a linear or branched alkyl group or cycloalkyl group having 3 to 9 carbon atoms is particularly preferable. Among these, a linear or branched alkyl group having 6 to 9 carbon atoms and a branched alkyl group having 6 to 9 carbon atoms are particularly preferable because of excellent compatibility with other solvents and emulsification ability. n is preferably a number of 2.

  Specifically, perfluorooctylethyl decyl ether, (2-perfluorohexyl) ethyl-1,3-dimethylbutyl ether, perfluorooctyl ethyl ethyl ether, perfluorostearyl methyl ethyl ether, perfluoropropyl ethyl octyl ether, Fluorooctyl ethyl octyl ether, perfluoro butyl ethyl hexyl ether, etc. are mentioned.

  These fluorine compounds can be used alone or in combination of two or more, and the blending amount of the component is 5 to 20% with respect to the oil phase, and 0.3 to 10% with respect to the total composition, particularly It is preferable to set it as 0.4 to 8%. The mass ratio of the liquid perfluoropolyether and these fluorinated ether compounds is preferably 8: 2 to 9: 1.

The fluorinated ether compound represented by the general formula (1) is represented by the general formula (4).
Rf- (CH ₂ ) _n -OH (4)
(Wherein Rf and n are as defined above) and a fluorine-containing hydroxy compound represented by the general formula (5)

(In the formula, R ² and R ³ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms. However, R ² and R ³ may be combined to form a ring. , R ² and R ^{3 have} a total carbon number of 2 to 8.)
It can manufacture by making the carbonyl compound represented by these, or its polymer react in hydrogen atmosphere in catalyst presence.

  The fluorine-containing hydroxy compound represented by the general formula (4) has a carbon number having a perfluoroalkyl group in which at least one hydrogen atom of a linear or branched alkyl group having 1 to 20 carbon atoms is substituted with a fluorine atom. Straight chain alcohols such as 2- (perfluorohexyl) ethanol, 2- (perfluorooctyl) ethanol, 2- (perfluorodecyl) ethanol, 2- (perfluorohexyl) ethanol, and 2- (perfluorodecyl) ethanol. Examples thereof include branched fluorine-containing alcohols such as fluoro-3-methylbutyl) ethanol and 6- (perfluoro-1-methylethyl) hexanol.

  The carbonyl compound represented by the general formula (5) includes not only a compound having a carbonyl group but also a compound that easily becomes a compound having a carbonyl group by acid or heating. Examples of such carbonyl compounds include chain ketones having 6 to 9 carbon atoms such as methyl isobutyl ketone (4-methyl-2-pentanone); octyl aldehyde, isononyl aldehyde (3, 5, 5-trimethylhexanal), and the like. Examples thereof include aliphatic aldehydes having 6 to 9 carbon atoms; cyclic ketones having 6 to 9 carbon atoms such as cyclohexanone.

  The charging ratio of the fluorine-containing hydroxy compound and the carbonyl compound is not particularly limited, but is usually preferably fluorine-containing hydroxy compound / carbonyl compound (molar ratio) = 30/1 to 1/30, particularly 20/1 to 1/20, Furthermore, 10/1 to 1/10 is preferable. Examples of the catalyst used when the fluorine-containing hydroxy compound and the carbonyl compound are reacted include those having hydrogenation ability, for example, palladium-based catalysts, specifically supported on carbon, alumina, silica alumina, silica or zeolite. Palladium catalyst, palladium hydroxide or palladium oxide, particularly palladium catalyst supported on carbon is preferred.

The catalyst is preferably used in an amount of 0.1 to 10%, more preferably 0.5 to 5%, based on the fluorine-containing hydroxy compound or carbonyl compound used. Within this range, the reaction proceeds moderately. Moreover, the catalyst of pH 8-2, More preferably, pH 7.5-3 is good. Here, the pH of the catalyst refers to the pH of the aqueous solution when 2 g of the catalyst powder is dispersed in 30 g of ion-exchanged water. The reaction between the fluorine-containing hydroxy compound and the carbonyl compound is preferably carried out in a hydrogen atmosphere at a hydrogen pressure of 1 (atmospheric pressure) to 300 kg / cm ² .

  In the composition of the present invention, it is considered that the emulsion stability of the perfluoropolyether can be obtained by the presence of the water-soluble vinyl copolymer in the oil phase.

In the present invention, the components contained in the oil phase other than the above are liquid, semi-solid and solid, synthetic and natural oil components such as hydrocarbon oil, ester oil, ether oil, silicone oil, etc. Of oily ingredients.
Examples of liquid oils include vegetable oils such as jojoba oil; animal oils such as liquid lanolin; hydrocarbon oils such as liquid paraffin and squalane; ester oils such as fatty acid esters, polyhydric alcohol fatty acid esters, glycerin derivatives, and amino acid derivatives; Examples thereof include silicone oils such as siloxane, dimethylcyclopolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, and higher alcohol-modified organopolysiloxane.

  Further, perfluoropolyether which is liquid at 25 ° C. and has a molecular weight of more than 5000, for example, trade name FOMBLIN HC-R (average molecular weight 6,600) (AUSHIMON); trade name demnum S-100 (average molecular weight 5,600) ) And S-200 (average molecular weight 8,400) (above, Daikin Industries, Ltd.).

  Examples of solid or semi-solid oil components include vegetable oils such as jojoba wax; higher alcohols such as cetanol, stearyl alcohol, and behenyl alcohol; ceramides. Examples of ceramides include type I described in Robson KJ et al., J. Lipid Res., 35, 2060 (1994), Wertz PW et al., J. Lipid Res., 24, 759 (1983), and the like. Ceramides of VII to VII and ceramide-like compounds described in JP-A-62-228048 include ceramide III, ceramide IIIB, ceramide IIIA, ceramide IV, phytoceramide I (and above, Degussa) Ceramide II (Cedama Co., Ltd.), ceramide TIC-001 (Takasago Fragrance Co., Ltd.) and the like.

  In the present invention, the total of these oil phases is preferably 5 to 40%, particularly 10 to 30%.

The oil-in-water emulsion composition of the present invention uses a water-soluble vinyl copolymer. Water-soluble means that it dissolves in water at room temperature or by heating and shows a uniform appearance. Examples of such a water-soluble vinyl copolymer include (meth) acrylic acid copolymers and polyacrylamide copolymers.
Examples of (meth) acrylic acid copolymers include (meth) alkyl acrylate copolymers, (meth) acrylic acid / (meth) alkyl acrylate copolymers or salts thereof, (meth) acrylic acid / (meta ) Derivatives or salts of alkyl acrylate copolymers are included. The copolymer also includes a crosslinked type. In the present invention, “(meth) acryl” means “acryl and / or methacryl”.

  Commercially available products include alkyl acrylate copolymers such as Aculin 33 (ISP); acrylic acid / alkyl methacrylate copolymers (including cross-linked types) such as Pemlen TR-1, Pemlen TR-2, Carbopol 1382, Carbopol ETD2020, etc. (above, Novon INC.); ACPEC HV-501ER (Sumitomo Seika); (meth) acrylic acid / (meth) acrylic acid alkyl copolymer derivative or salt thereof, A polyoxyethylene alkyl ether ester of acrylic acid, methacrylic acid, alkyl acrylate, alkyl methacrylate, methacrylic acid, in which a polyoxyethylene alkyl ether is ester-bonded to a (meth) acrylic acid / (meth) acrylic acid alkyl copolymer. Polymer (eg alkyl acrylate, alkyl methacrylate, polyoxyethylene (20) steer) Ether copolymer (Aculyn 22 (ISP Corp.)), and the like.

Examples of the polyacrylamide copolymer include at least one cationic group-containing vinyl monomer (hereinafter, monomer (a ₁ )) and an amide group-containing vinyl monomer (hereinafter, monomer ( at least one of a ₂ )) and at least one cross-linkable vinyl monomer having two or more vinyl groups in the molecule (hereinafter referred to as monomer (a ₃ )) as essential constituent monomers And a cationic cross-linked copolymer obtained by radical polymerization.

As the monomer (a ₁ ), (meth) acrylic acid ester or (meth) acrylamides having a dialkylamino group, styrenes having a dialkylamino group, vinylpyridines, N-vinyl heterocyclic compounds, amino groups And a monomeric acid neutralized product or a quaternary ammonium salt, a diallyl-type quaternary ammonium salt, and the like. Specifically, quaternary ammonium salt quaternized with a quaternizing agent such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, or Dimethyl diallylammonium chloride and the like are included.

As the monomer (a ₂ ), the general formula (6) or (7)

(Wherein R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ and R ⁶ are the same or different and each represents a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 4 carbon atoms, R ⁵ and R ⁶ together represent — (CH ₂ ) _m — (m is an integer of 3 to 6) or — (CH ₂ ) ₂ —O— (CH ₂ ) ₂ —, and the adjacent nitrogen atom is Forming a ring containing)

(Wherein R ⁷ represents a hydrogen atom or a methyl group, and A ¹ represents — (CH ₂ ) ₁ — (l represents an integer of 2 to 5)). Specifically, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, Nt-butylacrylamide, N- (meth) acryloylmorpholine, N-vinyl piperidone, N-vinyl pyrrolidone and the like can be mentioned. Among these, a feeling of use is preferable when N, N-disubstituted acrylamide is used, and N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide and the like are more preferable.

Examples of the monomer (a ₃ ) include polyhydric alcohols or (meth) acrylic acid esters of unsaturated alcohols, acrylamides, divinyl compounds, polyallyl compounds, and the like. Among these, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, allyl etherified pentaerythritol, vinyl (meth) acrylate, allyl (meth) acrylate, and the like are preferable. .

A preferable blending ratio of the monomer (a ₁ ) and the monomer (a ₂ ) is 2/98 to 98/2 in terms of a molar ratio of (a ₁ ) / (a ₂ ), more preferably 3 / 97 to 60/40. It is preferable for the molar ratio to fall within this range since both the properties of thixotropic properties and the viscosity retention at a low shear rate will be appropriately exhibited. When the mixing ratio of the monomer (a ₁ ) exceeds the range shown here, the thixotropy tends to be lacking. Further, when the blending ratio of the monomer (a ₂ ) is excessive from the range shown here, the viscosity at the low shear rate tends to be lowered.

The ratio of the monomer (a ₃ ) is preferably 0.0002 to 2, more preferably 0.0002 to 1, and more preferably 0.0002 to 0.4 in terms of molar ratio with respect to the total amount of monomers. When the proportion of the monomer (a ₃ ) is in the above range, the hydrogel formed from the resulting copolymer has a sufficient viscosity, and the hydrogel feels soft and slippery.

  In addition to one or more of each of the above three types of vinyl monomers, the cationic cross-linked copolymer can contain other vinyl monomers copolymerizable with these as constituent components. Examples of other vinyl monomers include (meth) acrylic acid alkyl esters such as methyl (meth) acrylate and ethyl (meth) acrylate; anionic group-containing monomers such as acrylic acid and methacrylic acid; N- ( And betaines such as 3-sulfopropyl) -N-acryloyloxyethyl-N, N-dimethylammonium betaine and N-carboxymethyl-N-methacryloyloxyethyl-N, N-dimethylammonium betaine.

  A (meth) acrylamide / (meth) acrylic acid copolymer having a dimethylaminoethyl group as a cationic group is preferred, and in particular, N, N-dimethylaminoethyl diethyl sulfate / N, N-dimethylacrylamide / poly (dimethacrylate) polyethylene. Glycol copolymers are preferred.

Another example of a polyacrylamide copolymer is a copolymer obtained by copolymerizing 70 to 55 mol% acrylamide and 30 to 45 mol% sodium 2-acrylamido-2-methylpropanesulfonate. The Here, the crosslinking agent is used in a concentration of 10 ⁻⁴ to 4 × 10 ⁻⁴ mol per mole of the monomer mixture. The obtained polymer can use what is marketed by the name of SEPIGEL 305 by Sepic, for example as an aqueous dispersion.

  These water-soluble vinyl copolymers preferably increase in viscosity or form an aqueous gel when dissolved in water (a vinyl copolymer having a 1.0% aqueous solution viscosity at 25 ° C. of not less than 5000 cSt).

  These water-soluble vinyl copolymers can be used alone or in combination of two or more, and are 0.001 to 3% by weight, particularly 0.001 to 2% by weight, more preferably 0.001 in the total composition. It is preferable to add ˜1% by weight because a composition having better dispersibility and stability and good usability can be obtained.

  In the present invention, the content of the aqueous phase is preferably 35 to 90%, further 50 to 90%, and more preferably 60 to 90% in the total composition. Further, the aqueous phase may contain an aqueous base other than water, for example, alcohols such as lower alcohols having 1 to 4 carbon atoms such as ethanol and propanol, and water-soluble 2 to 4 valent polyhydric alcohols. . Examples of such polyhydric alcohol include glycerin, 1,3-butylene glycol, propylene glycol, dipropylene glycol, diglycerin, isopropylene glycol, xylit, sorbit, polyethylene glycol having an average molecular weight of 400 to 300,000, and the like. . Ethanol, glycerin, polyethylene glycol, and 1,3 butylene glycol are preferred from the viewpoints of emulsion stability, feeling of use, and refreshing and moist feeling.

The oil-in-water emulsion composition of the present invention can further contain a hydrophobized powder.
The mother powder to be hydrophobized includes substances substantially insoluble in water and oil such as pigments and ultraviolet absorbers. For example, titanium oxide coated mica, titanium oxide coated talc, colored titanium oxide coated mica, titanium oxide / silica / titanium oxide coated mica, titanium oxide coated glass powder, iron oxide / titanium oxide coated glass powder, titanium oxide coated silica powder, oxidized Pearl pigments such as iron-coated silica powder, titanium oxide-coated alumina, iron oxide / silica-coated aluminum powder, iron oxide / silica-coated iron oxide, titanium oxide-coated synthetic mica, iron oxide / titanium oxide-coated synthetic mica; iron oxide (Bengara) Inorganic pigments such as yellow iron oxide, black iron oxide, carbon black, titanium dioxide, ultramarine, and bitumen; talc, sericite, kaolin, mica, silica, zinc white, bentonite, barium sulfate, hydroxyapatite, boron nitride, etc. Inorganic powders: red 201, red 202, red 226, yellow 401 and blue 404 organic pigments; red 104, Lake No. 230, Yellow No. 4, Yellow No. 5, Blue No. 1, etc. lake pigments; nylon, polyester, polymethyl methacrylate, polyethylene, polyethylene terephthalate, polyurethane, silicone resin, silk, cellulose laminated film powder (note: lame material) ), Organic powders such as Nε-lauroyl-L-lysine; natural pigments and the like.

  Examples of the hydrophobization method include fats and oils adsorbed on the surface of the mother powder, or esterification and etherification using functional groups such as hydroxyl groups to make the powder lipophilic, fatty acids Examples thereof include a metal soap treatment method using a zinc salt or a magnesium salt, a silicone treatment method using dimethylpolysiloxane or methylhydrogen polysiloxane, and a treatment method using a fluorine compound having a perfluoroalkyl group.

Here, the fluorine compound having a perfluoroalkyl group used in the method of treating with a fluorine compound has the following general formula: (C _s F _{2s + 1} C _t H _2t O) _u PO (OH) _3-u (wherein , S is a number of 3 to 21, t is a number of 1 to 12, and u is a number of 1 to 3), fluoroalkyldi (oxyethyl) amine phosphorus represented by U.S. Pat. No. 3,632,744 Acid esters (Japanese Patent Laid-Open No. 62-250074), resins having a perfluoroalkyl group (Japanese Patent Laid-Open No. 55-167209), tetrafluoroethylene resins, perfluoroalcohols, perfluoroepoxy compounds, sulfoamide type fluorolins Examples thereof include acids, perfluorosulfates, perfluorocarboxylates, and perfluoroalkylsilanes (JP-A-2-218603).

  The hydrophobized powder can be used alone or in combination of two or more. The blending amount is preferably 5 to 25% in the composition, and it is particularly preferable to blend 5 to 20% since the blend can be stabilized without impairing the function of the powder.

  In the present invention, the emulsion stability is further improved by using a small amount of a nonionic surfactant. For example, glycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene castor oil, polyoxyethylene Hardened castor oil, ethylene glycol fatty acid ester, polyethylene glycol fatty acid ester, alkyl glyceryl ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl ether fatty acid ester, silicone surfactant and the like can be used.

  One or more of these nonionic surfactants can be used, and more preferably 0.001 to 3%, particularly 0.001 to 2%, and more preferably 0.001 to 1% in the total composition. This is preferable because a stable composition having good dispersibility can be obtained.

In addition to the above components, the oil-in-water emulsion composition of the present invention has medicinal ingredients, preservatives, antioxidants, moisturizers, ultraviolet absorbers, fragrances, etc., as long as the effects of the present invention are not impaired. Can be contained.
The composition of the present invention can be used as makeup cosmetics such as foundations, makeup bases, eye shadows, eye liners, and lipsticks.

Synthesis example 1
In a reaction vessel, N, N-dimethylaminoethyl diethyl methacrylate sulfate (MOEDES: Nitto Chemical Industries), N, N-dimethylacrylamide, polyethylene glycol dimethacrylate (NK-14G: Shin-Nakamura Chemical Co., Ltd.) A monomer aqueous solution previously substituted with nitrogen consisting of 350 g of ion-exchanged water at a ratio of 20/80 / 0.04 was added, nitrogen was further blown for 20 minutes, and the temperature of the reaction system was raised to 55 ° C. while purging with nitrogen. Next, 0.22 g of a polymerization initiator (2,2′-azobis (2-amidinopropane) dihydrochloride) was added. Polymerization started after 30 minutes to 1 hour, and the whole became a soft gel. Stirring was continued as it was, and the polymerization was stopped 4 hours after the addition of the polymerization initiator. The bowl-shaped contents were taken out, washed with stirring in 5 liters of ethanol for 10 minutes, and dried. Thereafter, the mixture was pulverized with a coffee mill and a jet mill, and the pulverized particles were classified with a high volta to obtain a cationic crosslinked copolymer.

Examples 1-4, Comparative Examples 1-5
Foundations having the compositions shown in Table 1 were produced by the following methods, and the dispersibility, stability, usability, and water / oil repellency were evaluated by the following methods. The results are also shown in Table 1.

(Manufacturing method)
Using a propeller stirrer, the components (5) to (11) are dissolved, the component (13) is further added, and the aqueous phase (i) is mixed. Component (12) is added to a mixture of components (1) to (4) in advance, and is strongly dispersed using a disper to obtain oil phase (ii). The aqueous phase (i) was transferred to an Ajihomo mixer, and the oil phase (ii) was slowly added while stirring at 50 ° C. at high speed, followed by high-speed stirring for 30 minutes to obtain a foundation.

(Evaluation methods)
(1) Dispersibility:
Each foundation was filled in a glass bottle containing 50 mL, and the appearance was visually determined according to the following criteria.
A: Especially emulsified droplets are fine, uniform and good.
○: The emulsified droplets are fine and good.
Δ: Uneven overall.
X: Large emulsified droplets are visible.

(2) Stability:
Each foundation was stored at 40 ° C. for 1 month and then evaluated for emulsification.
A: Good.
○: There is an oil film on the surface.
Δ: Slightly separated (˜5%).
X: Separation (5% or more).

(3) Usability:
Ten expert panelists made a sensory evaluation of “freshness” and “no stickiness” when each foundation was actually used, and judged according to the following criteria.
○: Seven or more people evaluated it as good.
(Triangle | delta): Four to six persons evaluated it as favorable.
X: Three or less people evaluated it as favorable.

(4) Water and oil repellency:
80 mg of the obtained sample (foundation) is applied uniformly on an artificial leather sheet (made of polyurethane, 5 cm square) and dried at room temperature for 2 hours. Then, one drop of ion-exchanged water or squalane is dropped from the microsyringe onto the sample application surface, and the contact angle with the ion-exchanged water (water repellency) after 1 minute and the contact angle with the squalane (oil repellency) are measured by a contact angle measuring device. (Device name: Kyowa Interface Chemical FACE CA-X type).
A: Contact angle with water is 80 ° or more and contact angle with squalane is 50 ° or more.
○: Contact angle with water is 80 ° or more and contact angle with squalane is 30 to less than 50 °.
(Triangle | delta): The contact angle with water is 80 degree | times or more, and the contact angle with squalane 20-30 degrees.
X: The contact angle with water is less than 80 degrees or the contact angle with squalane is less than 20 degrees.

The foundations of Examples 1 to 4 were good in emulsion stability (dispersibility and stability over time), feeling in use, and water / oil repellency.
Comparative Example 1 having a low content of low-molecular weight perfluoropolyether was particularly poor in dispersibility and stability. Comparative Example 2 not containing a low molecular weight perfluoropolyether in the oil phase and Comparative Example 3 not containing a water-soluble vinyl copolymer were inferior in all cases. Comparative Example 4 containing a water-soluble polymer that is not a vinyl copolymer as an emulsifier was inferior in dispersibility, stability, and feeling in use. Comparative Example 5 containing no fluorinated ether compound was inferior in dispersibility, stability, and usability.

Claims (6)

The molecular weight of 5000 or less of a liquid perfluoropolyether comprises more than 70 wt% of the oil phase, the fluorinated ether compounds of the general formula (1), a vinyl copolymer water-soluble and oil-in-water containing water Emulsified composition.
Rf- (CH ₂ ) _n -OR ¹ (1)
(In the formula, Rf represents a linear or branched perfluoroalkyl group having 1 to 20 carbon atoms, R ¹ represents a linear or branched alkyl group or cycloalkyl group having 2 to 30 carbon atoms, and n represents 1. Or the number of 2 is shown.)   The oil-in-water emulsion composition according to claim 1, wherein the mass ratio of the liquid perfluoropolyether having a molecular weight of 5000 or less and the fluorinated ether compound of the general formula (1) is 8: 2 to 9: 1.   The oil-in-water emulsion composition according to claim 1 or 2, comprising 5 to 40% by mass of an oil phase and 35 to 90% by mass of an aqueous phase.   The oil-in-water emulsion composition according to any one of claims 1 to 3, further comprising 5 to 25 mass% of a hydrophobized powder.   Furthermore, the oil-in-water type emulsion composition of any one of Claims 1-4 containing a nonionic surfactant.   A makeup cosmetic comprising the oil-in-water emulsion composition according to any one of claims 1 to 5.