JP2012006893A - Cosmetic containing surface processing powder and specific composite powder - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a technology providing more excellent makeup lasting quality and being suitably used as powder cosmetic.SOLUTION: The cosmetic containing the following (1) and (2) is provided. (1) 0.1-40 mass% of the cosmetic of surface processing powder in which surface processing of particles is performed by a fluorine-containing copolymer made by copolymerizing a fluorine-containing monomer expressed by a formula (I) and an alkoxy group-containing monomer expressed by a formula (II), and (2) 0.1-50 mass% of the cosmetic of zinc oxide-coated composite powder in which zinc oxide is coated on the surface of lipophilic group powder particles, the ζ potential of the lipophilic group powder being negative with pH on the skin.

Description

  The present invention is an invention related to cosmetics, and more specifically, is an invention related to a technique that can provide better makeup and can be used as a powder cosmetic.

  Improving makeup lasting is a characteristic that can be particularly sought in makeup cosmetics, but it is not easy to make this compatible with the function of the powder component blended in cosmetics. In particular, in powder cosmetics that use a powder component as a main compounding ingredient, the longevity is essentially a required characteristic. However, pursuing specific functionality tends to sacrifice stability over time, and conversely, If sticking to stability, functionality tends to be limited.

  As a powder component having a specific function, for example, Patent Document 1 discloses a composite powder coated with zinc oxide under specific conditions that has good oil dispersibility and exhibits an excellent effect of improving and preventing rough skin. (Patent Document 2 discloses a technique related to Patent Document 1). Patent Document 3 discloses an acrylic acid fluorinated alkyl ester-treated powder that can be imparted with excellent hydrophilic oil repellency.

JP 2004-217621 A Japanese Patent No. 4149378 WO2009 / 142047 pamphlet

  An object of the present invention is to provide means for improving the longevity of cosmetics when blended with cosmetics while maintaining the excellent properties of the composite powder disclosed in Patent Document 1 above. It is.

  As a result of studying the above-mentioned problems, the present inventor has disclosed “zinc oxide-coated silicone resin-coated silicone rubber powder” among the composite powders disclosed in Patent Document 1 and Patent Document 3. The present inventors have found that it is possible to remarkably improve the longevity of the cosmetic by combining the surface-treated powder and blending it into the cosmetic. The present invention has been completed.

  That is, this invention is invention which provides the cosmetics (henceforth the cosmetics of this invention) containing following (1) and (2).

(1) A fluorine-containing copolymer obtained by copolymerizing a fluorine-containing monomer represented by the following formula (I) and an alkoxy group-containing monomer represented by the following formula (II) The surface-treated powder (hereinafter, also referred to as “surface-treated powder (1)”) that has been subjected to surface treatment of particles is 0.1 to 40% by mass of the cosmetic,

[Wherein R ¹ represents a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom,
CFR ⁴ R ⁵ group (provided that R ⁴ and R ⁵ may be the same or different and are a hydrogen atom, a fluorine atom or a chlorine atom), a cyano group, a linear or branched group having 1 to 20 carbon atoms A fluoroalkyl group, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group; R ² is —O— or —NH—; R ³ is a direct bond, —S— Or —SO ₂ —; R ^f is a fluoroalkyl group having 1 to 6 carbon atoms; m is a number from 1 to 10; n is a number from 0 to 10; and p is 0. Or it is 1. ]

[Wherein R ⁶ is a hydrogen atom or a methyl group; R ⁷ is a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms; R ⁸ is a hydrogen atom] An alkylene group having 2 to 4 carbon atoms in which some or all of the atoms may be substituted with a hydroxyl group; q is an integer of 1 to 50. ]

(2) A composite powder in which zinc oxide is coated on the surface of a lipophilic base powder particle, and the ζ potential of the lipophilic base powder is a negative value at a pH on the skin. 0.1-50 mass% of powder (hereinafter also referred to as zinc oxide composite powder (2)) based on cosmetics.

  The cosmetic composition of the present invention is a powder cosmetic composition that naturally contains powder in a broad sense. Examples of the powder cosmetic composition include white powder, solid white powder, paper white powder, water white powder, and white powder and dusting powders such as white powder. Baby powder, talcum powder, etc .; foundations such as powdery foundation, amphibious foundation, cake foundation, oil foundation, emulsified foundation, two-layer dispersion foundation; makeup base, body powder, whitening powder, emollient powder, fragrance powder, lipstick, Examples include blushers, eyebrows, eyeliners, eye shadows, eyebrows, and the like. Among these, powdery foundations (solid cosmetics) are suitable as objects to which the present invention is applied.

  According to the present invention, there is provided a cosmetic that is excellent in long-lasting makeup and that can exhibit an effect of improving and preventing rough skin, and that is particularly suitable for use as a powder cosmetic.

[Indispensable ingredients]
(A) Surface-treated powder (1)
As described above, the surface-treated powder (1) includes the fluorine-containing monomer represented by the above formula (I) and the alkoxy group-containing monomer represented by the above formula (II). It is a surface-treated powder in which particles are surface-treated with a fluorine-containing copolymer obtained by a copolymerization reaction. The manufacturing method and configuration of this surface-treated powder are disclosed in Patent Document 2. In addition, the fluorine-containing monomer (I) and the alkoxy group-containing monomer (II) serving as a group for the above copolymerization reaction are used alone or in combination of two or more, and the reaction is performed.

[Fluoromonomer]
In the fluorine-containing monomer (I), p is preferably 0, and R ¹ is preferably a hydrogen atom. ^Rf , which is a fluoroalkyl group having 1 to 6 carbon atoms, is a perfluoroalkyl group and / or a partially fluorinated fluoroalkyl group. The number of carbon atoms in R ^f is preferably 4 to 6, and 6 is optimal. Specific examples of R ^f _{is, -CF 3, -CF 2 CF 3} , -CF 2 CF 2 CF 3, -CF (CF 3) 2, -CF 2 CF 2 CF 2 CF 3, -CF 2 CF (CF _{3) 2, -C (CF 3} ) 3, - (CF 2) 4 CF 3, - (CF 2) 2 CF (CF 3) 2, -CF 2 C (CF 3) 3, -CF (CF 3) CF ₂ CF ₂ CF ₃ , — (CF ₂ ) ₅ CF _{3 and the} like.

  As the fluorine-containing monomer (I), any monomer may be used alone, or two or more monomers may be mixed and used.

Assuming that the above suitable conditions are taken into consideration, examples of the fluorine-containing monomer (I) include the following. The symbols in the following formula have the same meaning as the symbols given to the formula of the above-mentioned fluorine-containing monomer (I).
^{_{CH 2 = C (-R 1)}} -C (= O) -O- (CH 2) m -S- (CH 2) n -R f
^{_{CH 2 = C (-R 1)}} -C (= O) -O- (CH 2) m -SO 2 - (CH 2) n -R f
^{_{CH 2 = C (-R 1)}} -C (= O) -O- (CH 2) n -R f
^{_{CH 2 = C (-R 1)}} -C (= O) -NH- (CH 2) n -R f

[Alkoxy group-containing monomer]
The alkoxy group-containing monomer (II) is alkylene glycol (meth) acrylate, and q is preferably 1 to 30, more preferably 2 to 10, and most preferably 2 to 5. R ⁸ is preferably an ethylene group or a trimethylene group, and most preferably an ethylene group. Furthermore, R ⁸ may contain different alkylene groups in the same molecule. In that case, it is preferable that an ethylene group is contained in the different alkylene group. / Trimethylene group, ethylene group / tetramethylene group combination.

Assuming that the above suitable conditions are taken into consideration, examples of the alkoxy group-containing monomer (II) include the following. The symbols in the following formula have the same significance as the symbols given to the formula of the above-mentioned alkoxy group-containing monomer (II).
_{CH 2 = CHCOO- (CH 2 CH} 2 O) 9 -H
_{CH 2 = C (CH 3)} COO- (CH 2 CH 2 O) 9 -H
_{CH 2 = C (CH 3)} COO- (CH 2 CH 2 O) 23 -H
_{CH 2 = C (CH 3)} COO- (CH 2 CH 2 O) 50 -H
_{CH 2 = C (CH 3)} COO- (CH 2 CH (CH 3) O) 9 -H
_{CH 2 = CHCOO- (CH 2 CH} (CH 3) O) 9 -H
_{CH 2 = C (CH 3)} COO- (CH 2 CH (CH 3) O) 9 -H
_{CH 2 = C (CH 3)} COO- (CH 2 CH 2 O) 5 - (CH 2 CH (CH 3) O) 2 -H
_{CH 2 = C (CH 3)} COO- (CH 2 CH 20) 8 - (CH 2 CH (CH 3) O) 6 -H
^{_{CH 2 = CR 6 - (CH}} 2 CH 2 O) n -CH 3
^{_{CH 2 = CR 6 COO- (CH}} 2 CH (CH 3) O) n -CH 3
^{_{CH 2 = CR 6 COO- (CH}} 2 CH 2 O) 5 - (CH 2 CH (CH 3) O) 3 -CH 3

[Crosslinking monomer]
The fluorine-containing copolymer may contain a crosslinkable monomer. The crosslinkable monomer may be a compound having at least two reactive groups and / or carbon-carbon double bonds and not containing fluorine. The crosslinkable monomer can be a compound having at least two carbon-carbon double bonds or a compound having at least one carbon-carbon double bond and at least one reactive group. Examples of such reactive groups are hydroxyl groups, epoxy groups, chloromethyl groups, blocked isocyanates, carboxyl groups, and the like. Here, a monomer having an amino group is not used. The crosslinkable monomer is preferably a non-fluorine crosslinkable monomer, and specifically, di (meth) acrylate is more preferable.

 The crosslinkable monomer has the general formula (III):

[In the formula, R ⁹ and R ¹⁰ may be the same or different and each represents a hydrogen atom or a methyl group; R ¹¹ represents a carbon atom number 2 to which a part or all of the hydrogen atoms may be substituted with a hydroxyl group. 10 is an alkylene group; r is an integer of 1 to 50; ]

It is particularly preferable that the compound represented by the formula (alkylene glycol di (meth) acrylate). ^{Incidentally,} the carbon atoms of ^{R 11} are as 2-10 above, preferably 2 to 6, particularly preferably 2 to 4. R ¹¹ is most preferably an ethylene group. It can be imparted while adjusting the coating properties and film-forming ability of the copolymer to the powder particles, the dispersibility of the powder particles, and the moisture absorption / moisture retention ability. The mass average molecular weight of the fluorine-containing copolymer can be about 100 to 1000000, preferably about 5000 to 500000. When the molecular weight is less than 1000, the film forming ability is weak and is not suitable for the desired surface treatment, and when it is more than 1000000, the solubility of the polymer is deteriorated and the dispersibility of the surface-treated powder is deteriorated. In addition, this mass average molecular weight is the value calculated | required in polystyrene conversion with the gel permeation chromatography.

  For example, when the fluorine-containing copolymer contains 100 parts by mass of the fluorine-containing monomer (a), the amount of the alkoxy group-containing monomer (b) is 100% by weight. It is 10-400 mass parts with respect to a mass part, Preferably it is 25-150 mass parts, More preferably, it can be 43-100 mass parts. If the amount of the alkoxy group-containing monomer (b) is less than 10 parts by mass, hydrophilicity cannot be obtained, and if it is more than 400 parts by mass, the oil repellency is lowered. Further, when the crosslinkable monomer is contained as described above, the amount of the crosslinkable monomer is preferably 30 parts by mass or less with respect to 100 parts by mass of the fluorine-containing monomer (a). 1-20 mass parts is preferable, Most preferably, it can be 0.5-10 mass parts. When the amount of the crosslinkable monomer is larger than 30 parts by mass, a hard film is formed and the feeling of use in cosmetics is deteriorated. The fluorine-containing copolymer used in the present invention can be synthesized, for example, by the method disclosed in JP 2000-290640 A, but is not limited thereto. The polymerization method of the fluorine-containing copolymer is not particularly limited, and various polymerization methods such as bulk polymerization, solution polymerization, emulsion polymerization, and radiation polymerization can be selected. In general, for example, solution polymerization using an organic solvent or emulsion polymerization using water or an organic solvent in combination with water is selected. Generally, it is prepared into a treatment liquid by diluting with water after polymerization or emulsifying in water by adding an emulsifier.

  The surface treatment agent is preferably in the form of a solution, an emulsion or an aerosol. The surface treatment agent includes, for example, a fluorine-containing copolymer and a medium (for example, a liquid medium such as an organic solvent and water). The density | concentration of the fluorine-containing copolymer in a surface treating agent can be 0.01-50 mass%, for example.

  The coating amount of the surface treatment agent on the surface-treated powder varies depending on the chemical composition of the surface-treated powder and the presence or absence of its particle diameter bolus, oil absorption, water absorption, specific surface area, The amount is preferably 0.1 to 40 parts by mass, more preferably 0.5 to 35 parts by mass with respect to 100 parts by mass of the powder to be surface treated. When the coating amount is less than 0.1 parts by mass, a sufficient effect cannot be obtained. When the coating amount is more than 40 parts by mass, agglomeration of powder particles due to the polymer occurs, and the function of the surface-treated powder is deteriorated. The effect of the surface-treated powder in the material becomes insufficient, which is not preferable from the viewpoint of economy.

  The fluorine-containing copolymer further includes other fluorine-containing compounds other than the fluorine copolymer, organopolysiloxane, alkylsilane, polyether-modified silane, organic titanate, polyolefin, hydrogenated lecithin (including salt form), Acylated amino acids (including salt forms), acidic ester oils, fatty acids, dextrin fatty acid esters and the like can be contained as necessary. Examples of other fluorine-containing compounds other than the fluorine copolymer include perfluoroalkyl phosphate ester, perfluoropolyether phosphate ester, perfluoropolyether silane, perfluoroalkyl silane perfluoropolyether-modified polyurethane. Perfluoropolyether-modified acrylate, perfluoroalkyl-modified silicone, perfluoropolyether-modified silicone, and the like.

  The blending ratio (mass ratio) of the specific fluorine-containing copolymer (referred to as processing agent A) and the above-mentioned other components (referred to as processing agent B) to be surface-treated together with this is A: B Is preferably 39.0 to 0.1 parts: 0.1 to 39.0 parts. More preferably, A: B is 34.5 to 0.5 parts: 0.5 to 34.5 parts.

  As the material for the surface-treated powder, a powder material that can be used in cosmetics is selected. As the powder material, either inorganic or organic may be selected.

  For example, inorganic powder materials include boron nitride, sericite, natural mica, calcined mica, synthetic mica, synthetic sericite, alumina, mica, talc, kaolin, bentonite, smectite, calcium carbonate, magnesium carbonate, calcium phosphate, anhydrous silica. Acid, magnesium oxide, tin oxide, iron oxide, yttrium oxide, chromium oxide, titanium oxide, zinc oxide, cerium oxide, aluminum oxide, magnesium oxide, chromium hydroxide, bitumen, ultramarine, calcium phosphate, aluminum hydroxide, barium sulfate, sulfuric acid Magnesium, silicic acid, magnesium aluminum silicate, calcium silicate, barium silicate, magnesium silicate, aluminum silicate, strontium silicate, silicon carbide, magnesium fluoride, metal tungstate, aluminate Gnesium, magnesium aluminate metasilicate, chlorohydroxyaluminum, clay, zeolite, hydroxyapatite, ceramic powder, spinel, mullite, cordierite, aluminum nitride, titanium nitride, silicon nitride, lanthanum, samarium, tantalum, terbium, europium, neodymium, Mn-Zn ferrite, Ni-Zn ferrite, silicone carbide, cobalt titanate, barium titanate, iron titanate, lithium cobalt titanate, cobalt aluminate, antimony-containing tin oxide, tin-containing indium oxide, magnetite, aluminum powder, gold powder , Silver powder, platinum powder, copper powder, precious metal colloid, iron powder, zinc powder, cobalt blue, cobalt violet, cobalt green, low order titanium oxide, particulate acid Titanium, butterfly-like barium sulfate, petal-like zinc oxide, tetrapod-like zinc oxide, fine-particle zinc oxide, pearl pigments include titanium oxide-coated mica, titanium oxide-coated mica, titanium oxide-coated synthetic mica, titanium oxide-coated silica, titanium oxide coating Examples include synthetic mica, titanium oxide-coated talc, zinc oxide-coated silica, titanium oxide-coated colored mica, Bengala-coated mica titanium, Bengala / black iron oxide-coated mica titanium, carmine-coated mica titanium, and salmon-coated mica titanium.

  Specifically, MERCK's IRIODIN (registered trademark) series, TIMIRON (registered trademark) series, COLORONA series (registered trademark) series, DICHRONA (registered trademark) series, XIRONA (registered trademark) series, RONASSTAR (registered trademark) series , BASF's DESRTREFLECTIONS series, TIMICA series, FLAMENCO series, CLOIZONENE series, DUOCROME series, GEMTONE series, CELLINI series, MEARLMID series, REFECKS series, CHROMA-LITE series, COSTMISI series, ECKARTP (Registered trademark) series, IRAGE series, Nippon Sheet Glass Co., Ltd. of Metashiyain (registered trademark), Japan Koken's PROMINENCE (registered trademark), CQV's Cosmetica White Pear1 series, Sharon Pear1 series, include Precioso White Peartescent Pigments series such as Taizu company. Effect pigments such as aluminum flakes, silica flakes, alumina flakes, glass flakes, Bengala coated mica, carmine, titanium oxide coated borosilicate (sodium / calcium), titanium oxide coated borosilicate (calcium / aluminum), bismuth oxychloride, fish scale foil , Stainless steel powder, tourmaline powder, powder crushed gemstones such as sapphire and ruby, mango violet, glass fiber, carbon fiber, silicon carbide fiber, alumina fiber, β-wollastonite, zonolite, potassium titanate fiber, aluminum borate fiber , Basic magnesium sulfate fiber, silicon nitride fiber and the like.

  Examples of organic powder materials include metal soap, N-mono long-chain acyl basic amino acid, amidosulfonic acid polyvalent metal salt, straw powder, carbon black, tar pigments raked, natural pigments raked Polyamide powder, Polyester powder, Polyethylene powder, Polyurethane powder, Polypropylene powder, Polystyrene powder, Penzoguanamine powder, Polymethylpenzoguanamine powder, PTFE powder, Cellulose powder, Silk powder, Silicone powder, Divinylbenzene / Styrene Polymer, vinyl resin, urea resin, phenol resin, fluororesin, silicon resin, acrylic resin, melamine resin, epoxy resin, polycarbonate resin and other synthetic resin powder, nylon fiber, polyester Microcrystalline fiber powder, starch powder such as fibers, CI Pigment Yellow, CI Pigment Orange, and the like.

  As the tar pigment, red No. 3, red No. 10, red No. 106, red No. 201, red No. 202, red No. 204, red No. 205, red No. 220, red No. 226, red No. 227, red No. 228, red 230 No., red 401, red 505, yellow 4, yellow 5 yellow 202, yellow 203, yellow 204, yellow 401, blue 1, blue 2 blue 201, blue 404, green 3 No., Green No. 201, Green No. 204, Green No. 205, Orange No. 201, Orange No. 203, Orange No. 204, Orange No. 206, Orange No. 207, etc .; natural pigments include carmine, laccaic acid, calsamine, brushlin, crocin And powders of natural pigments such as chlorofoil, β-carotene, safflower powder and the like. The shape of the powder particles may be powder or fiber. The particle diameter is in the range of about 1 nm to 2000 μm as long as it can be blended in cosmetics.

  The powder particles may be powder particles in which two or more kinds of powder particles are combined. For example, powder (Excel Mica JP-2 or Excel Pearl: Miyoshi Kasei Co., Ltd.) with aluminum hydroxide on the surface of mica or pearl pigment particles, or hydroxyapatite and zinc oxide on the surface of sericite or pearl pigment. Powder (Powder Ravi: Miyoshi Kasei Co., Ltd.), powder in which fine titanium oxide and fine zinc oxide are dispersed and mixed (TZ-POWDER TYPEl: Miyoshi Kasei), powder in which talc, fine zinc white and fine titanium oxide are dispersed and mixed (TZ-POWDER TYPE2: Miyoshi Kasei Co., Ltd.), Dimethicone / vinyl dimethicone and silica mixture (Dow Corning 9701 Cosmetic Powder), Dimethicone / vinyl dimethicone and titanium oxide mixture (Dew Corning EP-9261 TI Cosme) ic Powder), a mixture of dimethicone / vinyl dimethicone and alumina (Dow Corning EP-9293 AL Cosmetic Powder), a mixture of dimethicone / vinyl dimethicone and lauroyl lysine (Dow Corning EP-9289LL Cosmetic Powder), JGC Catalysts & Chemicals COVERLEAF series, CONCELIGHT series, and the like.

  In addition, the powder particles are made of, for example, aluminum, calcium, magnesium, cerium, silicon zirconium, titanium, zinc, iron, cobalt, manganese, nickel, and tin in order to improve affinity with the surface treatment agent and adhesion. It may be previously coated with at least one oxide or hydrous oxide.

  The method for coating the above-mentioned fluorine-containing copolymer on the powder particles is not particularly limited and can be carried out by a known method. Surface treatment methods are roughly classified into dry methods and wet methods. For example, using a mixer, ball mill, jet mill, kneader, planetary mixer, pony mixer, sand mill, ad writer, ribbon blender, disper mixer, homo mixer, extruder, etc. The surface treatment agent and powder used in the present invention are treated by mixing and contacting for a certain time. At this time, the treatment may be performed while applying energy such as mechanochemical mechanical force, plasma, flame, ultraviolet ray, electron beam, superheated steam, laser beam, electromagnetic wave or the like. As a wet method, the treatment can be performed by dispersing the powder and the surface treatment agent in water, a solvent, or a supercritical fluid (water, carbon dioxide, etc.), bringing them into contact with each other, and then evaporating the solvent.

  In addition, in the case where the surface treatment is performed in combination with the above-mentioned fluorine-containing copolymer and another compound other than the above-mentioned fluorine-containing copolymer, similarly to the case where the surface treatment is performed only with the fluorine-containing copolymer. The powder can be surface-treated by mixing and contacting the surface-treating agent further containing the compound. Powders to be coated with properties (liquid, solid, gel, etc.) and physical properties (melting point, boiling point, glass transition temperature, solubility, reactivity, etc.) of the compound selected for composite surface treatment Depending on the type, an optimal coating production method may be selected and is not particularly limited by the production method.

  In the case of composite surface treatment, after coating the above-mentioned fluorine-containing copolymer first, a method of coating other surface treatment agent components other than the fluorine-containing copolymer, the fluorine-containing copolymer and the Examples thereof include a method of coating other surface treatment agent components simultaneously, a method of coating other surface treatment agent components other than the fluorine-containing copolymer, and then coating the fluorine-containing copolymer.

  A preferred coating method is that the powder particles to be coated are preliminarily placed in the air or in a liquid or other powders in both cases where the surface treatment is performed only with the fluorine-containing copolymer and when the surface treatment is performed in combination. It is a method of coating after dispersing in the coexistence or simultaneously coating.

  Since the fluorine-containing copolymer has an oil-repellent group and a hydrophilic group in the molecule, water and oil-repellency is exhibited when only the oil-repellent group is exposed from the surface of the powder particles. Hydrophilic oil repellency is advantageous in order to obtain excellent affinity and dispersibility of the surface-treated powder having oil repellency with other components blended in the cosmetic preparation. The fluorine-containing copolymer can expose both the oil-repellent group and the hydrophilic group on the powder particle surface depending on the coating method and the coating amount, thereby realizing the hydrophilic oil-repellency.

  As a coating method for obtaining hydrophilic oil repellency, surface treatment powder having hydrophilic oil repellency can be obtained by surface treatment with a coating amount larger than the coating amount capable of obtaining water / oil repellency in one coating process. The fluorine-containing copolymer can be easily treated with a high hydrogen bond strength and film-forming strength with the powder base material because the optimum amount of polyalkylene glycol is introduced into the molecule. When the coating amount on the particles is relatively small, water and oil repellency is exhibited. However, when the coating amount increases, free polyalkylene glycol chains become excessive, and molecular mobility depends on the environment in which the powder particles are placed. , It exhibits hydrophilicity when in contact with water. Also, depending on the type of powder, desired hydrophilic oil-repellent particles can be obtained by a method of treating the powder with an acidic or alkaline pH during the surface treatment or a method of controlling the temperature during the treatment. .

  Another coating method for obtaining hydrophilic oil repellency includes a plurality of coating treatments. That is, hydrophilic and oil-repellent particles can be obtained by coating the surface-treated powder coated with the fluorine-containing copolymer and imparted water and oil repellency with the same or different fluorine-containing copolymers.

  The outermost surface of the first treatment layer of the surface-treated powder particles exhibiting water and oil repellency is exposed so that the fluoro chain is exposed, and the surface is further coated, so that the polymer fluoro chain of the second treatment layer is the first treatment layer. When the treatment layer is coated so as to face the fluoro chain, the polyalkylene glycol chain is exposed on the outermost surface of the particle and exhibits hydrophilic oil repellency. By repeating this operation, it is possible to control hydrophilic oil repellency and water / oil repellency.

  As a method for evaluating water / oil repellency and hydrophilic oil repellency, there is a method of measuring a contact angle with water or squalane. According to this method, the water and oil repellency of the surface-treated powder (1) is preferably 70 ° or more in terms of contact angle with water or squalane. The hydrophilic oil repellency of the surface-treated powder (1) is such that the contact angle with water is 20 ° or less, the contact angle with squalane is preferably 80 ° or more, and more preferably the contact angle with water is 10 ° or less. The contact angle by squalane is 10 ° or more.

  The contact angle of the surface-treated powder (1) with the squalane is such that the powder is filled in a metal pan, molded at a pressure of 6 MPa for 10 seconds, and dropped onto the molded surface of the powder. The angle between the squalane droplet and the powder surface. The larger the angle, the higher the effect of repelling the droplets, and the more liquid repellency, and the smaller the angle, the more lyophilic.

  As another method for evaluating hydrophilicity, water is put into a beaker, a small amount of powder is added thereto, and the powder floats on the water surface after stirring 50 times at a rate of 2 times per second with a spatula; This is possible by observing the state of the powder dispersed in the water layer. In the surface-treated powder (1) having hydrophilic oil repellency, the powder hardly disperses on the water surface and the powder is dispersed in the water layer.

  1 type, or 2 or more types can be mix | blended with the surface treatment powder (1) with respect to the cosmetics of this invention.

  The compounding quantity in the cosmetics of this invention of surface treatment powder (1) is 0.1-40 mass% with respect to cosmetics, Preferably it is 5-30 mass%, Most preferably, it is 10-26%.

  If the blending amount is less than 0.1% by mass with respect to the cosmetic, the smooth feeling of use of the cosmetic does not reach the desired level. Moreover, even if it mixes over 40 mass% with respect to cosmetics, the improvement of the smooth use feeling commensurate with the increase in a compounding quantity will not be recognized substantially, and a pick-up will worsen and usability will deteriorate. A trend is also observed.

(B) Zinc oxide composite powder (2)
As described above, the zinc oxide composite powder (2) is “a composite powder in which the surface of the lipophilic base powder particles is coated with zinc oxide, and the ζ potential of the lipophilic base powder is on the skin. "Zinc oxide-coated composite powder" having a negative value at the pH of

  Zinc oxide coated on the lipophilic base powder is also listed in the Japanese Pharmacopoeia, and as its pharmacological action, it binds with skin proteins to form a film, has astringent, anti-inflammatory, skin protective action, Moreover, as disclosed in Patent Document 1, the plasminogen activator on the skin is adsorbed to exhibit the effect of improving / preventing rough skin. The adsorption action of this plasminogen activator can be confirmed using the ζ potential of the lipophilic base powder at the pH (usually neutral to weakly acidic) on the skin as an index.

  When the powder particles have a charge in the liquid, in order to cancel this charge, ions of the opposite charge are attracted to the powder particles by electrostatic force to form an electric double layer. The outermost potential of the double layer is the ζ potential. The zeta potential is suitably used for evaluating the surface charge state of an object, and the ability to electrically adsorb an enzyme can be evaluated.

  The ζ potential is usually obtained from the Smolkovsky formula: ζ potential = 4πηU / ε (η: viscosity of the solvent, U: electrophoretic mobility, ε: dielectric constant of the solvent). In order to obtain the ζ potential, the velocity (V) and mobility (U) of the colloidal particles are obtained by electrophoresis. When an electric field (E) is applied to the charged colloidal particles, the particles move. V = L / t (L: moving distance, t: time), U = V / E.

  The ζ potential is measured by, for example, dispersing and sonicating a sample in a Tris-HCl buffer having a pH of 7.5, and then electrophoretic light scattering photometer (for example, LEZA-600 etc. is sold by Otsuka Electronics Co., Ltd.) Can be measured.

  As a result, the tendency that the adsorption action of plasminogen activator becomes stronger as the ζ potential is biased to the negative side, specifically, it is preferable that the pH on the skin is a negative value, particularly −10 mV or less. It is. Examples of the material of the lipophilic base powder particles exhibiting such values include silicone resin, silicone rubber, silicone resin-coated silicone rubber, polyamide, polymethyl methacrylate, and ethyl carbamate.

  Further, the shape of the lipophilic base powder particles is not particularly limited, and is generally spherical, plate-like, or indefinite, and the presence or absence of porosity is not limited. The spherical shape of the particles is one of the preferred embodiments in consideration of the light diffusion effect and the feeling of use. The average particle diameter of the particles is not particularly limited and is preferably about 0.01 to 500 μm. Furthermore, the coverage of zinc oxide with respect to the total surface area of the lipophilic base powder during oil dispersion is preferably 1 to 90% by mass.

  The zinc oxide that coats the lipophilic powder particles has an inhibitory action on plasminogen activator, and the composite powder particles are formed by the lipophilic base powder having the ζ potential, which becomes the base powder particles. Plasminogen activator is adsorbed on the surface, and the above-described inhibitory action of zinc oxide on plasminogen activator is efficiently exhibited.

  The coating of zinc oxide on the lipophilic base powder particles can be performed according to a conventional method. That is, a desired composite powder can be prepared by mixing and contacting zinc oxide and a lipophilic base powder in a dry or wet manner, for example, by performing mechanofusion treatment (belonging to a dry method). This mechano-fusion treatment is simpler than other compounding methods such as a wet method, has a wide range of combinations, and can control the particle shape. It is done.

  Examples of the mixing apparatus generally used for the complexing process include various ball mills, ong mills, screen mills, pot mills, mortars, attritors, hybridizers, Henschel mixers, and the like.

  The blending amount of the zinc oxide composite powder (2) in the cosmetic of the present invention is 0.1 to 50% by mass, preferably 0.1 to 10% by mass, most preferably 0.1 to 7% with respect to the cosmetic. % By mass. If this blending amount is less than 0.1% by mass with respect to the cosmetic, the cosmetic makeup will not reach the desired level. Moreover, when it exceeds 50% with respect to cosmetics, the tendency for makeup lasting to deteriorate is recognized on the contrary.

  The blending ratio of the surface-treated powder (1) and the zinc oxide-coated composite powder (2) in the cosmetic of the present invention is the surface-treated powder within the range of the above individual blended amounts. (1): Zinc oxide coated composite powder (2) (mass ratio) is preferably 5: 1 to 2: 1, and is close to 3: 1 (the vicinity is rounded off to the first decimal place of this mass ratio. In the range of 3: 1).

[Other ingredients]
In addition to the above essential components, the powder cosmetic of the present invention contains water, powders other than the above, oils, surfactants, lower alcohols, polyhydric alcohols, moisturizers, preservatives, polymers (filming agents) as necessary. ), Antioxidants, UV protection agents, fragrances, and other various drugs, etc. can be contained in a qualitative and quantitative range that does not impair the intended effects of the present invention.

  In the cosmetic of the present invention, it is not always necessary that all the powder components blended therein are the surface-treated powder (1) and the zinc oxide composite powder (2). It can also be combined with a coloring material.

  Untreated powders include talc, kaolin, mica, sericite, muscovite, biotite, phlogopite, synthetic mica, permiculite, magnesium carbonate, calcium carbonate, aluminum silicate, barium silicate, calcium silicate. , Magnesium silicate, metal tungstate, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate, calcined gypsum, calcium phosphate, fluorapatite, hydroxyapatite, ceramic powder, etc .; polyamide resin powder, polyethylene powder, polymethacryl Organic powders such as methyl acid powder, polystyrene powder, styrene-acrylic acid copolymer resin powder, benzoguanamine resin powder, polytetrafluoroethylene powder and cellulose powder; inorganic white pigments such as titanium dioxide and zinc oxide; oxidation (Bengara), inorganic red pigments such as iron titanate; inorganic brown pigments such as γ-iron oxide; inorganic yellow pigments such as yellow iron oxide and loess; inorganics such as black iron oxide, carbon and low-order titanium oxide Black pigments; inorganic purple pigments such as mango violet and cobalt violet; inorganic green pigments such as chromium oxide, chromium hydroxide and cobalt titanate; inorganic blue pigments such as ultramarine and bitumen; titanium oxide-coated mica and titanium oxide Pearl pigments such as coated bismuth oxychloride, titanium oxide coated talc, colored titanium oxide coated mica, bismuth oxychloride, fish scale foil; metal powder pigments such as aluminum powder and copper powder; and the like.

  In the cosmetic of the present invention, for example, an oil is preferably blended in order to improve a moist feeling and a feeling of use. The oil component is liquid at 25 ° C., for example, avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, Sasanqua oil, castor oil, flaxseed oil, safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, teaseed oil, kaya oil, rice bran oil, cinnagiri oil, japanese kiri oil, jojoba oil, germ oil, triglycerin, Liquid oils and fats such as glycerin trioctanoate and glycerin triisopalmitate; hydrocarbon oils such as liquid paraffin, squalene, squalane and pristane; higher alcohol fatty acids such as oleic acid, tall oil and isostearic acid; lauryl alcohol, oleyl alcohol and isostearyl Higher alcohols such as alcohol and octyldodecanol; Silicone such as til polysiloxane, methylphenyl polysiloxane, methyl hydrogen polysiloxane, decamethyl polysiloxane; isopropyl myristate, hexyl laurate, oleyl oleate, decyl oleate, octyldodecyl myristate, hexyl decyl dimethyloctanoate, Examples include diethyl phthalate and dibutyl phthalate.

[Cosmetics of the present invention]
The cosmetics of the present invention can be produced by using the conventional methods according to the desired cosmetic form and dosage form. For example, when the cosmetic of the present invention is a powder cosmetic, both wet molding and dry molding in which a powder component to be blended is once slurried and a molding process is performed can be performed.

  The cosmetic of the present invention can take any product form within the category of cosmetics as long as the essential requirements described above are satisfied, but a preferred and typical embodiment is a powder cosmetic.

EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this is not intending limiting this invention. Moreover, a compounding quantity is the mass% with respect to a compounding object unless there is particular notice.
[Test method]
In order to evaluate the cosmetics of the present invention, “no powder drift over time”, “no powder float over time”, “no oil float over time”, and “good makeup ( Practical use test on “preference”) was conducted.

  Specifically, the test products shown in the following Table 1 (Example 1 and Comparative Example 1) were applied to the faces of six general women, and a questionnaire was conducted after 3 hours. Evaluation items are “no powder sag over time”, “no powder swell over time”, “no oil swell over time”, “good makeup (gradual evaluation according to taste)” Each of the evaluation items is evaluated with ± 2 points (the higher the evaluation point, the higher the evaluation), and the total score of the above six women is -10 points or less x, -9-3 points △, ± 2 points are given as △, +3 to 9 points as ○, and +10 points or more as ◎.

[Reference Example] Preparation of Zinc Oxide-Coated Silicone Resin-Coated Silicone Rubber Powder Zinc Oxide (Zinc Hana: Same Particle Size: 0.5 μm) and Silicone Resin-Coated Silicone Rubber Powder (KSP100 ^™ : ζ Potential-14.0 mV: Average Were mixed so that the coverage was 10% by mass and composited by mechanofusion treatment (2600 rpm, 2 minutes) to obtain a composite powder.

[Test example]
Each test product was prepared according to the formulation shown in Table 1. The test product was prepared by mixing and stirring all the blended components using a Henschel mixer, pulverizing with a pulverizer, and molding to obtain the test product (powder foundation).

  From the results of Table 1, Example 1 in which the surface-treated powder (1) and the zinc oxide composite powder (2) were blended was able to obtain the desired effect with respect to the long-lasting makeup. Example 1 is excellent in the absence of dusting, non-floating of powder, and non-floating of oil over time, and this can remarkably suppress “thinning of cosmetics” over time. Is shown. On the other hand, a comparative example different from this combination, specifically, comparative example 1 in which perfluorooctyltriethoxysilane-treated talc is blended in place of the surface-treated powder (1) is an example of evaluation items in general. Was inferior.

Claims (14)

Cosmetics containing the following (1) and (2).
(1) A fluorine-containing copolymer obtained by copolymerizing a fluorine-containing monomer represented by the following formula (I) and an alkoxy group-containing monomer represented by the following formula (II) The surface-treated powder in which the surface treatment of the particles is performed is 0.1 to 40% by mass of the cosmetic,

[Wherein, R ¹ represents a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFR ⁴ R ⁵ group (provided that R ⁴ and R ⁵ may be the same or different; A fluorine atom or a chlorine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group; R ² is —O— or —NH—; R ³ is a direct bond, —S— or —SO ₂ —; R ^f is a fluoroalkyl group having 1 to 6 carbon atoms. M is a number from 1 to 10; n is a number from 0 to 10; p is 0 or 1. ]

[Wherein R ⁶ is a hydrogen atom or a methyl group; R ⁷ is a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms; R ⁸ is a hydrogen atom] An alkylene group having 2 to 4 carbon atoms in which some or all of the atoms may be substituted with a hydroxyl group; q is an integer of 1 to 50. ]
(2) A composite powder in which zinc oxide is coated on the surface of a lipophilic base powder particle, and the ζ potential of the lipophilic base powder is a negative value at a pH on the skin. Powder is 0.1-50 mass% of cosmetics. The cosmetic according to claim 1, wherein R ^{1 in} formula (I) is a hydrogen atom.   The cosmetic according to claim 1 or 2, wherein the surface-treated powder (1) has hydrophilic oil repellency. The cross-linking monomer represented by the following formula (III) is included as an object of copolymerization in the copolymerization of the fluorine-containing copolymer in the surface-treated powder (1). Cosmetics according to crab.

[In the formula, R ⁹ and R ¹⁰ may be the same or different and each represents a hydrogen atom or a methyl group; R ¹¹ represents a carbon atom number 2 to which a part or all of the hydrogen atoms may be substituted with a hydroxyl group. 10 is an alkylene group; r is an integer of 1 to 50; ]   The cosmetic according to any one of claims 1 to 4, wherein a mass average molecular weight of the fluorine-containing copolymer in the surface-treated powder (1) is about 1000 to about 1000000. In the fluorine-containing copolymer in the surface-treated powder (1), the content of the alkoxy group-containing monomer (II) is 10 to 400 mass with respect to 100 mass parts of the fluorine-containing monomer (I). The cosmetic according to any one of claims 1 to 5, which is a part. The coating amount of the fluorine-containing copolymer in the surface-treated powder (1) is 0.01 to 40 parts by mass with respect to 100 parts by mass of the powder to be surface-treated. Cosmetics described in 1.   The fluorine-containing copolymer in the surface-treated powder (1) further includes other fluorine-containing compounds other than the fluorine copolymer, organopolysiloxane, alkylsilane, polyether-modified silane, organic titanate, polyolefin, hydrogenated lecithin. Any one of the compounds selected from the group consisting of (including salt forms), acylated amino acids (including rim forms), and dextrin fatty acid esters, Cosmetics according to crab.   The other fluorine-containing compound is one kind selected from the group consisting of a perfluoroalkyl phosphate ester having 6 or less carbon atoms, a perfluoroalkyl silane, a perfluoropolyether phosphate ester, and a perfluoropolyether silane. The cosmetic according to claim 8, wherein there are two or more kinds. The surface-treated powder (1) comprises 0.01 to 39.99 parts by mass of a fluorine-containing copolymer and 100% by mass of the surface-treated powder, and other fluorine-containing materials other than the fluorine copolymer. Group consisting of compounds, organopolysiloxanes, alkyl silanes, polyether modified silanes, organic titanates, polyolefins, hydrogenated lecithins (including salt forms), acylated amino acids (including rim forms), and dextrin fatty acid esters The cosmetic according to any one of claims 1 to 9, wherein the surface treatment is carried out with one or two or more compounds selected from 39.9 to 0.01 parts by mass.   The surface-treated powder in the surface-treated powder (1) is made of sericite, mica, kaolin, talc, silica, barium sulfate, boron nitride, titanium oxide, zinc oxide, iron oxide, and pearl pigment. Cosmetics in any one of Claims 1-10 which are 1 type, or 2 or more types chosen from these.   The material of the lipophilic base powder particles of the zinc oxide-coated composite powder (2) is one selected from the group consisting of silicone resin, silicone rubber, silicone resin-coated silicone rubber, polyamide, polymethyl methacrylate, and ethyl carbamate. Cosmetics in any one of Claims 1-11 which are 2 or more types.   The cosmetic according to any one of claims 1 to 12, wherein the cosmetic is a powder cosmetic.   The cosmetic according to claim 13, wherein the powder cosmetic is a solid cosmetic.