JP2016047812A - Surface-treated powder, process of producing the same and cosmetic containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface-treated powder which is excellent in water and oil repellency, gives a smooth touch, and has a good adhesion, when applied to the skin; to provide a process of producing the surface-treated powder in an inexpensive and easy operation; and to provide a cosmetic mixed with the surface-treated powder.SOLUTION: The invention relates to a surface-treated powder in which the surface of a base material powder is treated with a perfluoropolyether compound having an amino group represented by a general formula (1); and to a cosmetic mixed with the surface-treated powder.SELECTED DRAWING: None

Description

  The present invention relates to a surface-treated powder excellent in water repellency and oil repellency, and excellent in usability, and a cosmetic containing the powder.

  In cosmetics, various powders are used as cosmetic powders, and surface treatment is performed with various compounds as needed according to the purpose of use. In addition, research has been conducted on surface treatments for imparting water and oil repellency for the purpose of preventing makeup slippage due to sweat, tears, rain, etc., and makeup slippage due to sebum and cosmetic oil.

  Conventionally proposed powders treated with fluorine compounds with excellent water and oil repellency include, for example, water and oil repellent powders that have been surface treated with phosphoric acid esters having perfluoroalkyl groups (patents) Reference 1), water / oil repellent pigment treated with powder with perfluoroalkylsilane (Patent Document 2), cosmetic powder with surface of base powder treated with perfluoropolyetheralkylphosphoric acid and its salt, etc. (Patent Document 3), modified powder surface-treated with perfluoroalkyl / polyoxyalkylene co-modified silicone (Patent Document 4), and water- and oil-repellent cosmetic material surface-treated with a tridecafluorooctyltriethoxysilane compound Powder pigment (Patent Document 5), pigment powder coated with perfluoroacrylate copolymer (Patent Document 6), perfluoropolyether-modified poly Repellent cosmetic powders pigment surface-treated with urethane urethane (Patent Document 7), and the like, all of which are available as a powder for cosmetics.

  However, even with these fluorine compounds, the water repellency, oil repellency, and use feeling are not always satisfactory.

  On the other hand, the perfluoropolyether compound having an amino group represented by the general formula (1) focused on by the present inventors is a perfluoroalkylene having two or more ether oxygens bonded to perfluoroalkylene or perfluoroalkyl. A neutralized salt in which a polyperfluoropolyether chain derived from a repeating unit of an alkoxy group is incorporated in the structure, and a cationic amino group is present as a side chain in the terminal structure of the general formula (1) Is a water-soluble perfluoropolyether compound. In general, an organic compound having an amino group has adsorptivity, and is therefore used as a flocculant, a hair conditioning agent, a fabric surface modifier, and a paper sizing agent.

  The general formula (1) according to the present invention is a compound in which a perfluoropolyether chain is incorporated into a terminal amino group, and various derivatives (Patent Documents 8 to 10) using this as a raw material are surfactants and fire extinguishing agents. As reported. However, it is not used as a powder treatment agent and is not applied for cosmetic purposes.

Japanese Patent Application Laid-Open No. 06-079163 Japanese Patent Laid-Open No. 06-192594 Japanese Patent Application Laid-Open No. 08-133828 Japanese Patent Laid-Open No. 08-283605 JP 2008-37813 A JP 2008-50387 A JP 2012-51844 A U.S. Pat. No. 3,547,995 U.S. Pat. No. 3,839,425 US Pat. No. 3,550,089

  The present invention provides a surface-treated powder excellent in water repellency and oil repellency, having a smooth feel when applied to the skin and good adhesion, a method for producing the same, and a cosmetic containing the surface-treated powder. There is.

  As a result of diligent research, the present inventors have used a perfluoropolyether compound having an amino group represented by the chemical formula (1) as a surface treatment agent, so that this surface-treated powder is water-repellent and oil-repellent. As a result, the present inventors have found that it is possible to prevent makeup collapse due to sweat and sebum, and that the touch when applied to the skin is smooth and has good adhesion, and the present invention has been completed.

  According to the present invention, it is possible to provide a surface-treated powder that is excellent in water repellency and oil repellency, has a smooth feel when applied to the skin, and has good adhesion. Unlike the conventional water- and oil-repellent powders, the surface-treated powder of the present invention is excellent in miscibility with various powders used in cosmetics, and easily produces a high-functional cosmetic with excellent touch. Can be provided. Specifically, makeup cosmetics and UV protection cosmetics that do not easily lose makeup due to sweat, water, etc., cosmetics such as lipsticks and foundations that do not easily transfer to containers and clothes, etc. It is possible to provide a production method and a cosmetic containing the surface-treated powder.

（但し、ｍは０〜５の整数を表し、ｎは平均値で０〜２０の整数を表し、Ｒ１は炭素数２〜６のアルキレン基を表し、Ｒ２は水素原子または炭素数の合計が１〜８のアルキル基、アラルキル基、アリール基を表し、Ｒ３は水素原子または炭素数の合計が１〜８のアルキル基、アラルキル基、アリール基を表し、Ｘはフッ素原子、または炭素数１〜３のパーフルオロアルキル基を表し、ＺはＮＨまたはＮ−ＣＨ３または酸素原子を表す。）で示される、アミノ基を有するパーフルオロポリエーテル化合物によって基材粉体の表面が処理されていることを特徴とする表面処理粉体である。 Hereinafter, the surface-treated powder of the present invention will be described in detail.
The present invention relates to a general formula (1);

(However, m represents an integer of 0 to 5, n represents an integer of 0 to 20 on average, R1 represents an alkylene group having 2 to 6 carbon atoms, and R2 represents a hydrogen atom or a total of 1 carbon atoms. Represents an alkyl group, aralkyl group, or aryl group of ˜8, R3 represents a hydrogen atom or an alkyl group, aralkyl group, or aryl group having a total of 1 to 8 carbon atoms, and X represents a fluorine atom or a carbon number of 1 to 3 The surface of the base powder is treated with a perfluoropolyether compound having an amino group represented by Z), wherein Z represents NH, N—CH 3, or an oxygen atom. This is a surface-treated powder.

If X in the repeating structure in the perfluoropolyether compound having an amino group according to the present invention is a fluorine atom or a perfluoroalkyl group having 1 to 3 carbon atoms, the above effect is sufficiently exhibited. Is particularly preferably a trifluoromethyl group.
The perfluoropolyether compound having an amino group according to the present invention can be synthesized with reference to, for example, US Pat. No. 2,864,603 and US Pat. No. 3,250,808.

  It is an object of the present invention to obtain a powder having both oil repellency, touch, adhesion, and miscibility with other surface-treated powders, which are not conventionally obtained, by treating the surface treatment component. . Although it does not restrict | limit about a surface treatment amount, it is preferable that the surface treatment component of this invention is 1-50 mass parts with respect to 100 mass parts of base material powder.

The property of the perfluoropolyether compound having an amino group according to the present invention is liquid to solid at room temperature depending on the kind of X of the perfluoropolyether part or the molecular weight. Moreover, since it has an amino group, the neutralized salt is dissolved or dispersed in water.
The perfluoropolyether compound having an amino group according to the present invention exhibits a sufficient effect even if it is used as it is without pretreatment, but it is preferable to use a salt neutralized with an appropriate acidic substance.

  The acidic substance used for neutralization is not particularly limited, and examples thereof include the following acidic substance. These acidic substances may be used alone or in combination of two or more. Sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, silicic acid, carbonic acid, formic acid, acetic acid, propionic acid, benzoic acid, cinnamic acid, salicylic acid, oxalic acid, malonic acid, succinic acid, adipic acid, tartaric acid, malic acid, citric acid, glutar Acid, sebacic acid, fumaric acid, maleic acid, mesylic acid, tosylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, sorbic acid, glutamic acid, aspartic acid, ascorbine Examples include acids and erythorbic acid.

  In general, there are two methods for treating the surface of the base powder using a surface treating agent, a wet method and a dry method. In the wet method, a base powder is dispersed in a solvent or water / solvent solution, and a surface treatment agent is added to the solution while stirring. is there. In the dry method, a base powder is added to a Henschel mixer, a ball mill, etc., a surface treatment agent is added, and after mixing well, dried and heated to obtain a treated powder.

  The surface treatment method in the present invention is not particularly limited, but it is excellent in water repellency and oil repellency by using either a dry method or a wet method, and can give a touch when applied to the skin. . The wet method is more preferable for uniform surface treatment.

  Specifically, the perfluoropolyether compound having an amino group represented by the general formula (1) is dissolved in water under acidic conditions. Therefore, in order to treat the powder surface with the perfluoropolyether compound having an amino group represented by the general formula (1), the base powder is dispersed in water, and the surface treatment is performed under an acidity of pH 3.0 or less. The agent can be added, mixed well, filtered and dried to obtain a treated powder.

  The surface-treated powder of the present invention obtained as described above is excellent in water repellency and oil repellency, has a smooth feel when applied to the skin, and has excellent adhesion to the skin.

  Furthermore, in the surface treatment of the base powder according to the present invention, a surface treatment agent other than the general formula (1) is simultaneously or continuously surface-treated on the base powder within a range not impairing the effects of the present invention. be able to. Examples of the surface treatment agent that can be used in the present invention include perfluoropolyether-modified aminosilane, perfluorooctyltriethoxysilane, fluoroalcohol phosphate having 9 to 15 carbon atoms, trifluoropropylcyclopentasiloxane, and PEG8 trifluoropropyl dimethicone copolymer. Fluorine compounds other than the surface treating agent according to the present invention, such as hydrogen silicone, amino silicone, reactive organopolysiloxane, silicone compounds such as alkylsilane, organic titanate, polyolefin, lecithin and / or salt thereof, hydrogenated lecithin And / or lecithins such as salts thereof, acylated amino acids and / or salts thereof, acidic ester oils, fatty acids and / or salts thereof, dextrin fatty acid esters, fructooligosaccharide fatty acid esters Gen, higher alcohols, esters, waxes, and the like metal soaps, but not limited thereto.

  The perfluoropolyether-modified aminosilane can be synthesized by a method according to Japanese Patent Application Laid-Open No. 58-122979. Perfluorooctyltriethoxysilane is available from Gelest, Inc. The one made of can be used. The C9-15 fluoroalcohol phosphoric acid can be synthesized by a method according to Japanese Patent Application Laid-Open No. 2004-277389. As trifluoropropylcyclopentasiloxane, KF-5002 from Shin-Etsu Chemical Co., Ltd. can be used. As PEG8 trifluoropropyl dimethicone, FPD-6131 manufactured by Shin-Etsu Chemical Co., Ltd. can be used. Examples of reactive organopolysiloxanes include KF99 (methicone) and KF9901 (hydrogen dimethicone) from Shin-Etsu Chemical Co., Ltd., KF-9908 (triethoxysilylethyl polydimethylsiloxyethyl dimethicone), and KF-9909 (triethoxysilylethyl poly). Dimethylsiloxyethylhexyl dimethicone), KP-574 ((acrylates / tridecyl acrylate / triethoxysilylpropyl methacrylate / dimethicone methacrylate) copolymer), KF-7312 (mixture of trimethylsiloxysilicate and cyclopentasiloxane), KF-9001 (Decamethylcyclopentasiloxane 50% solution of trimethylsiloxysilicate) can be used. As the alkyl silane, Z-6341 (octyltriethoxysilane) manufactured by Dow Corning, F-8261 (tridecafluorooctyltriethoxysilane) manufactured by Degussa, or the like can be used. As the organic titanate, Ajinomoto Co., Ltd. Preneact KR-TTS (isopropyl triisostearoyl titanate) or the like can be used. As the polyolefin, for example, known compounds described in JP-A No. 63-179972, oxidized polyethylene obtained by oxidizing polypropylene, maleated polyethylene, polypropylene oxide, and the like can be used. As hydrogenated lecithin and / or salts thereof, for example, Resinol S-10 (hydrogenated soybean phospholipid) manufactured by Nikko Chemicals, egg yolk lecithin PL-100P (hydrogenated egg yolk phospholipid) manufactured by QP, etc. can be used. Examples of acylated amino acids and / or salts thereof include sarcosinate MN (sodium myristoylmethylaminoacetate), alaninate LN-30 (sodium lauroylmethylalanine), sarcosinate CN-30 (cocoylsarcosine sodium), sarcosinate OH (oleic acid) manufactured by Nikko Chemical Co., Ltd. Oil Sarcosine), Ajinomoto's Amisoft HS-21 (N-stearoyl-L-glutamate disodium), SEPPIC's SEPILIFT DPHP (dipalmitoyl hydroxyproline), and the like can be used.

Although the usage-amount of these surface treating agents is not limited, It is preferable to use it to such an extent that the characteristic of the surface treating agent of this invention is not impaired. Preferably, it is about 0.1 to 20% by mass.
The base powder used in the present invention is not particularly limited as long as it is a powder conventionally used as a cosmetic powder, and examples thereof include the following base powder. These base powders may be used alone or in combination of two or more.

  Iron oxide, zinc oxide, titanium oxide, cerium oxide, magnesium oxide, zirconium oxide, barium sulfate, chromium oxide, ultramarine, bengara, magnesium carbonate, calcium carbonate, mica, sericite, talc, silica, kaolin, chromium hydroxide, zinc Hana, carbon black, alumina, aluminum silicate, magnesium silicate, boron nitride, silica-alumina powder, bentonite, smectite and other inorganic pigments, nylon powder, polyurethane powder, polymethyl methacrylate, styrene-divinylbenzene copolymer, polyethylene Powder, silicone resin, Teflon (registered trademark) powder, silicone gum, silk powder, carnauba wax, rice wax, starch, organic powder such as microcrystalline cellulose, organic color such as rhodamine B , Red 201, black 401, yellow 4 and blue 1 such as zirconium, barium or aluminum lake and other organic colorants, composite powder such as mica titanium, iron oxide coated mica, surface treated powder The shape may be any shape as long as it is a shape or particle size usually used in cosmetics, such as a spherical shape, a plate shape, a needle shape, or a fiber shape.

Next, the cosmetic of the present invention will be described in detail.
The cosmetic of the present invention contains the above-mentioned surface-treated powder of the present invention, and its dosage form is arbitrary, and generally includes all cosmetics containing conventional cosmetic powders. Examples of such cosmetics include facial cosmetics such as foundations, concealers, white powders and blushers, makeup cosmetics such as eye shadows, mascaras, eyeliners, eyebrows, lipsticks, nail enamels, sunscreen cosmetics, and emulsions. And basic cosmetics such as lotions. In addition to cosmetics, it can also be suitably used for external preparations for skin, ointments for pharmaceutical use and the like.

  The compounding quantity of the surface treatment powder of this invention is 0.01-99.9 mass% normally, and it fluctuates | varies according to the form and target use of cosmetics. In order to blend other ingredients such as a fragrance as a cosmetic, sufficient water repellency, oil repellency and a favorable feel, the blend amount of the surface-treated powder is in the range of 0.1 to 99% by mass. It is preferable. More specifically, depending on the type of cosmetic, for example, 20-80% by mass for solid powder cosmetics, 5-50% by mass for creamy cosmetics, 2-30% by mass for emulsion cosmetics, More preferably, 2 to 20% by mass is added to the lotions.

  Components other than the surface-treated powder according to the present invention that can be blended in the cosmetics of the present invention are appropriately selected and used from the components blended in normal cosmetics, depending on the type of the target cosmetics. be able to. Examples of these components include hydrocarbons such as liquid paraffin and petrolatum, vegetable oils and fats, waxes, synthetic ester oils, silicone oil phase components, fluorine oil phase components, higher alcohols, lower alcohols, and fatty acids. , Thickener, ultraviolet absorber, powder, inorganic / organic pigment, colorant, various surfactants, polyhydric alcohol, sugar, polymer compound, physiologically active ingredient, transdermal absorption promoter, solvent, antioxidant , Fragrances, preservatives, various additives and the like, but are not limited thereto.

The cosmetic of the present invention can be produced according to a usual method. Cosmetics containing the cosmetic powder of the present invention are excellent in water resistance and sebum resistance, prevent makeup collapse due to sweat and sebum, etc., and have a smooth feel when the cosmetic is applied on the skin. It has excellent adhesion and gives a moist feeling.
EXAMPLES The present invention will be specifically described below with reference to examples, but the technical scope of the present invention is not limited to these examples.

1. Manufacturing method (Surface treatment agent manufacturing method 1)
1.5 g of hexafluoropropylene and 13.28 g of hexafluoropropylene oxide were mixed and dissolved in 60 g of m-xylene hexafluoride. In the presence of 0.1 g of cesium fluoride and 0.1 g of lithium chloride, 1.5 g of N, N-dimethyl-1,3-propanediamine was added in the presence of 0.1 g of sodium hydroxide to the polymer heat-polymerized at 80 ° C. Reaction and distillation purification were performed at 120 ° C. to obtain 15.2 g of the target surface treatment agent represented by the following chemical formula (2) having an average degree of polymerization n = 8.

(Surface treatment agent production method 2)
For a perfluoroalkylene compound having an arbitrary chain length, the perfluoroalkyl oxide compound is heated in m-xylene hexafluoride solvent in the presence of 0.1% by mass of cesium fluoride and 0.1% by mass of lithium chloride. N, N-dimethyl-1,3-propanediamine was reacted with the polymerized polymer in a sodium hydroxide catalyst and purified by distillation to obtain a target surface treatment agent represented by the following chemical formula (3). M, n, and X of the obtained surface treatment agent are as shown in Table 1 below.

(Surface treatment agent production method 3)
For a perfluoroalkylene compound having an arbitrary chain length, the perfluoroalkyl oxide compound is heated in m-xylene hexafluoride solvent in the presence of 0.1% by mass of cesium fluoride and 0.1% by mass of lithium chloride. By reacting the polymerized polymer with N, N-dimethyl-3-amino-1-ethanol in a sodium hydroxide catalyst and purifying by distillation, various target surface treatment agents shown in the following chemical formula (4) are obtained. It was. M, n, and X of the obtained surface treatment agent are as shown in Table 1 below.

(Method 1 for producing surface-treated powder)
Into a Henschel mixer, 950 g of pigmented titanium oxide was added, and 50 g of the surface treatment agent represented by the chemical formula (2) synthesized in the surface treatment agent production method 1 dissolved in 450 g of 3 wt% phosphoric acid aqueous solution was added and stirred. After stirring, the surface-treated powder obtained by drying at 110 ° C. for 4 hours and pulverizing the atomizer was designated as Product 1 of the present invention.

(Method 2 for producing surface-treated powder)
In a beaker, 95.0 g of pigmented titanium oxide was weighed, and 100 g of purified water was added and stirred well. Phosphoric acid was added thereto to adjust the pH to 3, and 5.0 g of the surface treatment agent shown in the chemical formula (2) synthesized by the surface treatment agent production method 1 was added, mixed for 30 minutes, and filtered. The surface-treated powder which was taken out and dried at 110 ° C. for 4 hours in a dryer and pulverized with an atomizer was designated as Product 2 of the present invention.

(Method 3 for producing surface-treated powder)
Into a Henschel mixer, 950 g of pigmented titanium oxide was added, and 50 g of the surface treatment agent represented by the chemical formula (3) synthesized by the surface treatment agent production method 2 dissolved in 450 g of 3 wt% phosphoric acid aqueous solution was added and stirred. After stirring, the surface-treated powders dried at 110 ° C. for 4 hours and pulverized with an atomizer were used as the inventive products 3 to 10 and comparative products 1 to 4. The types of surface treatment agents used are as shown in Table 1, below.

(Method 4 for producing surface-treated powder)
In a beaker, 95.0 g of pigmented titanium oxide was weighed, and 100 g of purified water was added and stirred well. Phosphoric acid is added to adjust the pH to 3, and the surface treatment agent synthesized by the surface treatment agent production method 2 is represented by the chemical formula (3) or the surface treatment agent represented by the chemical formula (4) synthesized by the surface treatment agent production method 3. 5.0 g of the agent was added, mixed for 30 minutes and filtered. The surface-treated powder obtained by taking it out and drying it at 110 ° C. for 4 hours in a dryer and pulverizing it with the atomizer was designated as Products 11 to 16 of the present invention and Comparative products 5 to 8. The types of surface treatment agents used are as shown in Table 1, below.

2. Evaluation method (water repellency, oil repellency)
The sample was put in a flat container, a flat surface was made with a force of 100 kg / cm ² , and a water drop and a squalane drop were gently dropped on this, and the contact angle was measured.

(Adhesiveness)
The sample was uniformly rubbed against the inner side of the upper arm, and when it was scraped off with a brush, it was visually observed, evaluated with the following five points, and the average was obtained.
5: Adhesion better than untreated powder 4: Relatively better adhesion than untreated powder 3: Same as untreated powder 2: Easier to break than untreated powder 1: Not yet Much easier to break than treated powder

(Feel) The smoothness at the time of application was evaluated by the following five points with five monitors, and the average was obtained.
5: Much better than untreated powder 4: Better than untreated powder 3: Same as untreated powder 2: Relatively inferior to untreated powder 1: Much worse than untreated powder

3. Evaluation results Table 1 shows the evaluation results. Good powders excellent in water repellency, oil repellency and feel were obtained by using any of the surface treatment methods, dry surface treatment and wet surface treatment. It was better to use dry processing for the feel, and better results were obtained using wet processing for water and oil repellency.
As shown in comparative products 1 to 8, when the degree of polymerization n is large, or when the perfluoroalkyl group m or X is too long, the adhesion and feel are extremely inferior, and there is no perfluoroalkyl group in the side chain, In the case of hydrogen atoms, the results showed that water repellency and oil repellency were remarkably inferior.

1. Manufacturing method (Surface treatment agent manufacturing method 4)
1.5 g of hexafluoropropylene and 13.28 g of hexafluoropropylene oxide were mixed and dissolved in 60 g of m-xylene hexafluoride. 1.5 mol equivalents of various amine compounds to polymer oxyfluoride having an average polymerization degree of 8 obtained by heat polymerization at 80 ° C. in the presence of 0.1 g of cesium fluoride and 0.1 g of lithium chloride Reaction was carried out at 120 ° C. in the presence of 0.1 g of sodium hydroxide, followed by distillation purification to obtain various target surface treatment agents represented by the following chemical formula (5). Z, R ¹ , R ² , and R ³ of the obtained surface treatment agent are as shown in Table 2 below.

(Method 5 for producing surface-treated powder)
In a beaker, 95.0 g of pigmented titanium oxide was weighed, and 100 g of purified water was added and stirred well. Phosphoric acid was added to adjust the pH to 3, and 5.0 g of the surface treatment agent represented by the chemical formula (5) synthesized by the surface treatment agent production method 3 was added, mixed for 30 minutes, and filtered. The surface-treated powder that was taken out and dried at 110 ° C. for 4 hours with a dryer and pulverized with an atomizer was designated as inventive products 17 to 32 and comparative products 9 to 12.

2. Evaluation method (water repellency, oil repellency)
The sample was put in a flat container, a flat surface was made with a force of 100 kg / cm ² , and a water drop and a squalane drop were gently dropped on this, and the contact angle was measured.

(Feel)
With five monitors, the smoothness at the time of application was evaluated with the following five scores, and the average was obtained.
5: Much better than untreated powder 4: Better than untreated powder 3: Same as untreated powder 2: Relatively inferior to untreated powder 1: Much worse than untreated powder

3. Evaluation results Table 2 shows the evaluation results. A powder having good water repellency, oil repellency and feel was obtained by using any of the amide and ester surface treatment agents. The N-ethylamide compound as the surface treatment agent is not excellent in touch, and when R1, R2, and R3 are long chain fatty acids, a significant decrease in oil repellency was observed.

1. Manufacturing method (Surface-treated powder manufacturing method 6)
In a beaker, 100.0 g of pigmented titanium oxide was weighed and 100 g of purified water was added and stirred well. The acid shown in the following Table 3 was added thereto as PH3 to add the surface treatment agent shown in the chemical formula (2) synthesized by the surface treatment agent production method 1, mixed for 30 minutes and then filtered. The surface-treated powder obtained by taking it out and drying it at 110 ° C. for 4 hours in a dryer and pulverizing the atomizer was designated as products 33 to 43 of the present invention.

2. Evaluation method (water repellency, oil repellency)
The sample was put in a flat container, a flat surface was made with a force of 100 kg / cm ² , and a water drop and a squalane drop were gently dropped on this, and the contact angle was measured.

(Feel)
With five monitors, the smoothness at the time of application was evaluated with the following five scores, and the average was obtained.
5: Much better than untreated powder 4: Better than untreated powder 3: Same as untreated powder 2: Relatively inferior to untreated powder 1: Much worse than untreated powder

3. Evaluation results Table 3 shows the evaluation results. Regardless of the kind of acidic substance, a powder having good water repellency, oil repellency and feel was obtained. Although there was no significant effect on the difference in water repellency, oil repellency, and touch depending on the type of acid during neutralization, it was more effective to use a neutralized surface treatment than non-neutralized. It was.

1. Manufacturing method (Surface-treated powder manufacturing method 6)
In a Henschel mixer, 94 g of pigmented titanium oxide was added, and 5 g of the surface treatment agent represented by the chemical formula (2) synthesized by the surface treatment agent production method 1 dissolved in 45 g of a 3 wt% phosphoric acid aqueous solution was added and stirred. Subsequently, 1 g of a surface treatment agent other than the general formula (1) referred to in the present invention was added separately and stirred again. After stirring, the surface-treated powders dried at 110 ° C. for 4 hours and pulverized with an atomizer were designated as products 44 to 49 of the present invention.

2. Evaluation method (water repellency, oil repellency)
The sample was put in a flat container, a flat surface was made with a force of 100 kg / cm ² , and a water drop and a squalane drop were gently dropped on this, and the contact angle was measured.

(Feel)
With five monitors, the smoothness at the time of application was evaluated with the following five scores, and the average was obtained.
5: Much better than untreated powder 4: Better than untreated powder 3: Same as untreated powder 2: Relatively inferior to untreated powder 1: Much worse than untreated powder

3. Evaluation results Table 4 shows the evaluation results. In many combinations, water repellency, oil repellency and feel similar to those of the perfluoropolyether compound alone were obtained. In this experiment as well, a synergistic improvement in function was observed when used in combination with a perfluoropolyether compound having an amino group.

1. Manufacturing method (Surface-treated powder manufacturing method 6)
A Henschel mixer was charged with 95 g of cosmetic pigment, and 5 g of the surface treatment agent represented by the chemical formula (2) synthesized by the surface treatment agent production method 1 dissolved in 45 g of a 3% by weight phosphoric acid aqueous solution was added and stirred. After stirring, the surface-treated powder dried at 110 ° C. for 4 hours and pulverized with an atomizer was designated as inventive products 50 to 63.

2. Evaluation method (water repellency, oil repellency)
The sample was put in a flat container, a flat surface was made with a force of 100 kg / cm ² , and a water drop and a squalane drop were gently dropped on this, and the contact angle was measured.

(Feel)
With five monitors, the smoothness at the time of application was evaluated with the following five scores, and the average was obtained.
5: Much better than untreated powder 4: Better than untreated powder 3: Same as untreated powder 2: Relatively inferior to untreated powder 1: Much worse than untreated powder

3. Evaluation results Table 5 shows the evaluation results. In many inorganic pigments and organic pigments, good water repellency, oil repellency and feel were obtained.

Makeup base (prescription) (mass%)
A Water balance Glycerin 5.0
Stearoxy PG hydroxy PG hydroxyethyl
Sodium sulfonate 2.0
B Perfluoroalkyl (C4-14) ethoxydimethicone 13.0
Cyclomethicone 10.0
Dimethicone 6.0
Octyl methoxycinnamate 4.0
Ethanol 3.0
Isostearyl glycerin 3.0
1,3-butylene glycol 2.0
Carbomer (4% aqueous solution) 2.0
Nylon 12 2.0
Surface treatment 12-nylon powder (present product 62) 2.0
Surface-treated titanium oxide (Invention product 2) 2.0
Surface treatment bengara (product 55 of the present invention) 0.5
Surface-treated iron oxide (Product 56 of the present invention) 0.5
Surface-treated iron oxide (Invention 57) 0.1
(Preparation method) If phase A was stirred with a homomixer at room temperature, phase B was added and emulsified.
(Results) A makeup base with SPF30 / PA ++, excellent water repellency and oil repellency, and good touch was obtained.

Powder foundation (prescription) (mass%)
A Surface-treated mica (Invention product 52) Remainder Surface treatment talc (Invention product 51) 15.0
Surface-treated sericite (Invention product 53) 10.0
Nylon 12 10.0
B Dimethicone 7.0
Isocetyl myristate 5.0
Octyl methoxycinnamate 5.0
(Diphenyl Dimethicone / Vinyl Phenyl Dimethicone /
Silsesquioxane) Crosspolymer 3.0
Tri (capryl / capric acid) glyceryl 3.0
Hydrogenated polyisobutene 3.0
(Preparation method) The component B was mixed well, the component A was added and further mixed until uniform, and filled into a container to obtain a product.
(Result) An SPF25 / PA ++ foundation having excellent water and oil repellency and good touch was obtained.

Liquid foundation (prescription) (mass%)
A Purified water Remaining Butylene glycol 5.0
Glycerin 2.0
Carbomer 0.1
Phenoxyethanol 3.0
B cyclopentasiloxane 20.0
Surface-treated titanium oxide (Invention product 1) 5.0
Surface-treated zinc oxide (present product 50) 6.0
PEG-9 polydimethylsiloxyethyl dimethicone 2.0
(Acrylic Sunalkyl / Dimethicone) Copolymer 2.0
(Dimethicone / Vinyl Dimethicone) Cross Polymer 2.0
Phytosterol isostearate 1.0
Colorant Appropriate amount (Preparation method) Phase B was mixed well with a disper, and then added to phase A in a uniform solution while stirring with a homomixer and emulsified.
(Results) An emulsion foundation excellent in water repellency and oil repellency was obtained. The UV protection ability also showed high values such as SPF20 and PA ++.

W / O UV protection cosmetics (Surface treatment powder production method 7)
Into a Henschel mixer, 95 g of fine particle zinc oxide was added, and 5 g of the surface treatment agent represented by the chemical formula (2) synthesized by the surface treatment agent production method 1 dispersed in 15 g of a 3 wt% methanol phosphate solution was added and stirred. What was dried at 110 ° C. for 4 hours after stirring was designated as Product 64 of the present invention.

(Method 8 for producing surface-treated powder)
In a Henschel mixer, 95 g of fine particle titanium oxide was added, and 5 g of the surface treatment agent represented by the chemical formula (2) synthesized by the production method 1 of the surface treatment agent was dispersed in 15 g of a 3 wt% methanol phosphate solution and stirred. What was dried at 110 ° C. for 4 hours after stirring was designated as Product 65 of the present invention.

(Prescription) (mass%)
A Dimethicone 10.0
Diphenylsiloxyphenyl trimethicone 5.0
(Dimethicone / Methicone) Copolymer 6.0
Ceresin 5.0
Trimethylolpropane trioctanoate 5.0
Sorbitan sesquiisostearate 4.0
Carnauba 1.0
Surface treated fine particle zinc oxide (Product 64 of the present invention) 10.0
Surface-treated fine particle titanium oxide (Invention product 65) 2.0
Surface treatment talc (Invention product 51) 2.0
Surface-treated sericite (Invention product 53) 2.0
Cyclomethicone 3.0
Octyl methoxycinnamate 5.0
Mineral oil 1.0
Vaseline 1.0
B Dipropylene glycol 2.0
Sodium hyaluronate 0.2
The remainder of the water (preparation method) A component was heated to 70 ° C., and everything other than the powder of the present invention was uniformly dissolved, and then B was gradually added to A while slowly stirring with a homomixer or a dispermixer. Stir and emulsify.
(Results) A W / O type UV protective cosmetic product having excellent water and oil repellency and good usability was obtained. Moreover, the dispersibility of the treated powder of the present invention was high, and high UV protection ability was exhibited. SPF35, PA ++

Foundation with UV protection (Surface treatment powder production method 9)
In a Henschel mixer, 94 g of synthetic phlogopite was added, and 5 g of the surface treatment agent represented by the chemical formula (2) synthesized by the surface treatment agent production method 1 dispersed in 45 g of 3 wt% methanol phosphate solution was added and stirred. After stirring, 1 g of amino-modified silicone was added and further stirred. What was dried at 110 ° C. for 4 hours after stirring was designated as Product 66 of the present invention.

(Prescription) (mass%)
Surface treated talc (Invention product 51) Remaining surface treated synthetic phlogopite (Invention product 66) 10.0
Surface-treated fine particle zinc oxide (Product 64 of the present invention) 5.0
Octyl methoxycinnamate 6.0
Mineral oil 5.0
Fine silica 3.0
Phytosteryl isosterate 3.0
Dimethicone 3.0
Nylon powder 3.0
Triethylhexanoin 3.0
Water 3.0
Polyglyceryl-2 triisostearate 1.0
Color material 1.0
(Preparation method) All components were mixed with a Henschel mixer until uniform, and filled into a container to obtain a product.
(Results) A foundation having excellent elongation, smoothness and adhesion to the skin, excellent dispersibility in oil, and no color unevenness was obtained. SPF25, PA ++

Lipstick (Surface treatment powder production method 10)
In a beaker, 95.0 g of Bengala was weighed, 100 g of purified water was added and stirred well. The acid shown in the following Table 3 was added to adjust the pH to 3, and 5.0 g of the surface treatment agent shown in the chemical formula (2) synthesized by the surface treatment agent production method 1 was added, mixed for 30 minutes, and filtered. The surface-treated powder obtained by taking it out and drying it at 110 ° C. for 4 hours in a dryer and pulverizing it with an atomizer was designated as Product 67 of the present invention.

(Prescription) (mass%)
Polybutene 60.0
Isostearyl malate 10.0
Trioctanoin 10.0
Dextrin palmitate 3.0
Diglycerin triisostearate 3.0
Pentaerythrityl tetraisostearate3.0
(Dimethicone / Methicone) Copolymer 2.0
Dimethicone 2.0
Calcium carbonate 1.0
Dextrin myristate 1.0
Surface-treated titanium oxide (present product 48) 1.0
Surface treatment Bengala (Invention product 67) 1.0
Surface-treated mica (Invention product 52) 1.0
Other coloring material, fragrance The balance (preparation method) All ingredients were weighed out and uniformly mixed using a roll mill.
(Result) A lipstick having a vivid color tone with excellent dispersibility of the pigment was obtained. A product having excellent adhesion and difficult to transfer color to a container or the like was obtained.

Film-type eyeliner (prescription) (mass%)
A Surface-treated iron oxide (black) (Product 57 of the present invention) 14.0
Glycerin 5.0
Polyoxyethylene sorbitan monooleate 1.0
Preservative appropriate amount Water 19.0
B Vinyl acetate resin emulsion 45.0
Carboxymethylcellulose (10% aqueous solution) 15.0
Acetyltributyl citrate 5.0
Fragrance Appropriate amount (Preparation method) Add glycerin and polyoxyethylene sorbitan monooleate to purified water, heat and melt, add surface-treated iron oxide (black), and prepare A in a colloid mill. B heated to 70 ° C. was mixed with A, dispersed uniformly with a homomixer, and filled into a container to obtain a product.
(Results) An eyeliner with good makeup and water / oil repellency and excellent adhesion was obtained.

Felt-tip type eyeliner (prescription) (mass%)
A Surface treated carbon black (Invention product 63) 5.0
Polyoxyethylene (10) dodecyl ether 2.0
Purified water 80.0
B Glycerin 10.0
Preservative Appropriate amount Perfume Appropriate amount Water Remainder (Preparation method) After dissolving polyoxyethylene (10) dodecyl ether in water, surface-treated carbon black was added and uniformly pulverized with a ball mill to prepare A. B was added to A and dispersed uniformly, and then filled into a container to obtain a product.
(Results) A pen-type eyeliner with no makeup dullness and excellent water color and oil repellency was obtained.

Waterproof mascara (prescription) (mass%)
A Surface-treated iron oxide (black) (Invention 57) 5.0
Ammonium acrylate copolymer 30.0
Preservative appropriate amount water 10.0
B Light isoparaffin 30.0
Solid paraffin 8.0
Lanolin wax 8.0
Sorbitan sesquioleate 4.0
Fragrance Appropriate amount (Preparation method) A surface-treated iron oxide (black) was added to water and dispersed with a homomixer. Then, ammonium alkyl acrylate copolymer was added and heated to prepare A. B was added and uniformly emulsified and dispersed with a homomixer, and then filled into a container to obtain a product.
(Results) A mascara with excellent water and oil repellency and a long lasting makeup was obtained.

Loose type eye shadow (prescription) (mass%)
Surface-treated mica (Product 52 of the present invention) 28.0
Bismuth oxychloride 40.0
Silica 10.0
Surface-treated titanium oxide (Invention product 1) 5.0
Surface treatment bengara (product 55 of the present invention) 6.0
Surface-treated iron oxide (yellow) (Invention product 56) 5.0
Surface-treated carbon black (Product 63 of the present invention) 1.0
Surface-treated fine particle titanium oxide (Invention product 65) 5.0
(Preparation method) All raw materials were weighed, uniformly dispersed with a mixer, and filled into a container to obtain a product.
(Results) An excellent eye shadow having good skin feel, excellent adhesion, no dullness, and water and oil repellency was obtained.

Emulsification type eye shadow (prescription) (mass%)
A Surface treatment talc (Product 51 of the present invention) 10.0
Surface treatment kaolin (Invention 54) 2.0
Surface treated ultramarine (Product 58 of the present invention) 4.0
Surface treatment chrome green (Invention product 59) 1.0
B Isopropyl myristate 8.0
Liquid paraffin 5.0
Stearic acid 3.0
Propylene glycol monolaurate 3.0
C Butylene glycol 5.0
Glycerin 1.0
Triethanolamine 1.2
Preservative appropriate amount Water The remainder (preparation method) A was mixed uniformly with a blender. After C was dissolved by heating, A was added and mixed with stirring. B was heated and melted, added to the mixed A and C with stirring, and emulsified and dispersed with a homomixer. The solution was stirred and cooled to room temperature and filled into a container to obtain a product.
(Results) A liquid eye shadow excellent in color development, water resistance and oil resistance, in which elution of metal ions was suppressed by the surface treatment was obtained.

Pencil type eyebrow ink (prescription) (mass%)
A Surface-treated iron oxide (black) (Product 57 of the present invention) 20.0
Surface-treated kaolin oxide (Product 54 of the present invention) 15.0
Surface treatment talc (Invention product 51) 10.0
Surface-treated titanium oxide (Invention product 1) 5.0
B (myristic acid / palmitic acid / stearic acid /
Ricinoleic acid / eicosanedioic acid) Glyceriz 20.0
Stearic acid 10.0
Beeswax 5.0
Hardened castor oil 5.0
Vaseline 4.0
Lanolin 3.0
Liquid paraffin 3.0
(Preparation method) A was mixed uniformly with a blender. B was heated and melted, and A was added and kneaded. Molded into a core and made into a pencil shape with wood.
(Results) An excellent eyebrow ink having a smooth and good feeling on the skin and having water and oil repellency was obtained.

  Since the surface-treated powder of the present invention has water repellency, oil repellency, touch and adhesion, which have been difficult to combine with each other, the makeup and feel of makeup is good using this, and makeup with good makeup Provide a fee.

Claims (5)

A surface-treated powder characterized in that the surface of a base powder is treated with a perfluoropolyether compound having an amino group represented by the general formula (1).

(Where, m represents an integer of 0 to 5, n represents an integer of 1 to 20 in average, ^{R 1} represents an alkylene group having 2 to 6 carbon atoms, ^{R 2} is the sum of hydrogen atoms or carbon atoms Represents an alkyl group, an aralkyl group or an aryl group having 1 to 8; R ³ represents a hydrogen atom or an alkyl group, an aralkyl group or an aryl group having a total of 1 to 8 carbon atoms; and X represents a fluorine atom or a carbon number. 1 to 3 perfluoroalkyl groups, and Z represents NH or N—CH ₃ or an oxygen atom.) 2. The surface-treated powder according to claim 1, wherein X in the general formula (1) is a trifluoromethyl group. A surface-treated powder, wherein the perfluoropolyether compound having an amino group according to claim 1 or 2 is surface-treated with 1 to 50 mass% of the amount of the base powder. A method for producing the surface-treated powder according to any one of claims 1 to 3, wherein the perfluoropolyether compound having an amino group is neutralized with an acidic substance in the production process. To produce surface-treated powder. Cosmetics containing the surface-treated powder according to any one of claims 1 to 4.