JP2003055142A - O/w-type cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare an O/W-type cosmetic free from tackiness, giving smooth and refreshing feeling and having excellent adhesiveness to the skin, water and oil repellency and aging stability. SOLUTION: A powdery water and oil repellent surface-treated with a phosphoric acid ester having a perfluoroalkyl group and an acrylic copolymer having a molecular weight of 30,000-300,000 and holding a dimethylpolysiloxane as a side chain is formulated together with an ionic surfactant to a cosmetic.

Description

Description: TECHNICAL FIELD [0001] The present invention relates to an oil-in-water cosmetic. [0002] Conventionally, oil-in-water type cosmetics have a fresh and refreshing feeling of use since the continuous phase is composed of an aqueous component, and are known as emulsions, creams, foundations and sunscreens. Widely used for cosmetics and the like. However, this oil-in-water type cosmetic has a drawback that a cosmetic film formed by being applied to the skin is easily adapted to water. Especially, in cosmetics such as foundations and sunscreen cosmetics, cosmetics are formed by sweat secreted from the skin. It was remarkable in that it caused collapse. [0003] In order to cope with such drawbacks, a technique of imparting water and oil repellency by blending a perfluoropolyether compound with an oil-in-water type cosmetic (Japanese Unexamined Patent Publication (Kokai) No. Sho 6).
JP-A 1-234928 and JP-A-63-10791
No. 1) and a technique of blending a water- and oil-repellent powder surface-treated with a fluorine compound into an oil-in-water cosmetic. [0004] However, JP-A-61-234928 and JP-A-6-234928 in which a perfluoropolyether compound is blended into an oil-in-water cosmetic.
In the conventional technique disclosed in Japanese Patent Application Laid-Open No. 3-107911, the perfluoropolyether compound is incompatible with other additives commonly used in cosmetics, so that only the perfluoropolyether compound is emulsified as an oil agent. There is a problem that it is difficult to obtain a stable cosmetic when it is blended in a large amount in the cosmetic. On the other hand, the conventional technique of mixing a water- and oil-repellent powder surface-treated with a fluorine compound into an oil-in-water type cosmetic cannot provide a cosmetic that is sufficiently satisfactory in emulsifying properties and feeling of use. There are points. The present invention has been made to solve such problems, and has a non-greasy, smooth and refreshing feeling of use, adhesion to skin, water and oil repellency, and stability over time. It is an object of the present invention to provide an oil-in-water cosmetic excellent in quality. [0006] In order to achieve the above object, an oil-in-water cosmetic according to the present invention comprises:
General formula: (In the formula, Rf represents a perfluoroalkyl group or a perfluorooxyalkyl group having 3 to 21 carbon atoms, is linear or branched, and has a single chain length, even if it has a complex chain length. N represents an integer of 1 to 12, y represents a number of 1 to 3, and M represents hydrogen, an alkali metal, ammonium or substituted ammonium.) A phosphoric acid ester having the general formula: (Wherein, n is an integer, a, b, c, d are the respective molar ratios in the copolymer, which are not 0, and d is 40
It is not less than mol% and not more than 60 mol%. A) a water- and oil-repellent powder which is simultaneously surface-treated with a high molecular weight acrylic copolymer having dimethylpolysiloxane having a molecular weight of 30,000 to 300,000 as a side chain, and an ionic surfactant. It is characterized by becoming. According to the present invention, a phosphoric acid ester having a perfluoroalkyl group represented by the general formula (1) and a molecular weight of 30,000 to 300 represented by the general formula (2)
Water- and oil-repellent powders, which are simultaneously surface-treated with an acrylic copolymer high molecular weight product having dimethylpolysiloxane in the side chain of 000, and an ionic surfactant contained in the cosmetic, To obtain oil-in-water cosmetics with excellent makeup lasting, non-greasy, smooth and refreshing feel, and excellent adhesion to skin and stability over time, as they exhibit water and oil repellency Can be. Next, specific embodiments of the oil-in-water cosmetic according to the present invention will be described. The water- and oil-repellent treating agent used in the present invention has a general formula: (In the formula, Rf represents a perfluoroalkyl group or a perfluorooxyalkyl group having 3 to 21 carbon atoms, is linear or branched, and has a single chain length, even if it has a complex chain length. N represents an integer of 1 to 12, y represents a number of 1 to 3, and M represents hydrogen, an alkali metal, ammonium or substituted ammonium.) Or perfluoroalkyl phosphate ester diethanolamine salt which is a solid content of an aqueous dispersion emulsion commercially available from Asahi Glass Co., Ltd. under the name of AG-530. Sodium perfluoroalkyl phosphate ester with the same molecular structure but different salt forms, potassium perfluoroalkyl phosphate ester Unsalted, ammonium perfluoroalkyl phosphoric acid salts, and the like. On the other hand, the molecular weight used in the present invention is 3000
General formula having 0 to 300,000 dimethylpolysiloxane in the side chain: (Wherein, n is an integer, a, b, c, d are the respective molar ratios in the copolymer, which are not 0, and d is 40
It is not less than mol% and not more than 60 mol%. ) (Hereinafter referred to as “acrylic silicon copolymer”)
As KP-54 from Shin-Etsu Chemical Co., Ltd.
1, copolymers dissolved in isopropanol, butyl acetate, volatile silicon and the like, which are commercially available under the names of KP-543, KP-545 and the like. As a method for simultaneously coating the surface of the powder with the perfluoroalkyl phosphate compound and the acrylic silicone copolymer, Japanese Patent Application No. 2000-120.
809. That is, the concentration of the predetermined amount of perfluoroalkylphosphoric acid or the perfluoroalkylphosphate ester compound and the acrylic silicon copolymer to be coated on the surface as solids is about 0.5 to 20 wt%, respectively. Then, simultaneously dissolve or disperse in an appropriate solvent to form an emulsion, add the powder during heating and stirring, stir for a certain period of time, and then heat (under reduced pressure if necessary) to remove the solvent. It is preferable to heat at 110 ° C. for 6 hours and then pulverize to obtain the desired water- and oil-repellent powder. As a suitable solvent used here, an organic solvent such as isopropyl alcohol, butyl acetate, volatile silicon, and acetone is preferable. The amount of the perfluoroalkylphosphoric acid represented by the general formula (1) or the phosphoric ester having a perfluoroalkyl group to be coated on the powder is not particularly limited, but is not limited to sufficient water repellency. The minimum required amount of oil repellency is sufficient, and the amount of coating is 30% by weight.
In view of the fact that the compound represented by the general formula (2) itself may be precipitated out of the formula (2) above and adversely affect the feel of the cosmetic, the particle size of the raw material powder may vary slightly. Preferably, the amount of the acrylic silicon copolymer represented by the general formula (2) is not limited to 30% by weight. A coverage of generally 0.1 to 10% by weight is suitable. In addition, the coating amount is 0.1% by weight.
When the amount is less than the above, it is not preferable because the cosmetic is inferior in emulsifiability and adhesion to the skin. When the coating amount exceeds 10% by weight, the coating of the powder with the compound represented by the general formula (1) is applied. The oil-repellency brought about by the above is not sufficiently exhibited, or the acrylic silicone copolymer represented by the general formula (2) serves as a binder to attach the powder particles to each other to form a powder having a poor touch, resulting in a rough feeling and stickiness. It is not preferable because it becomes a cosmetic that gives a feeling. In the present invention, the powder to be surface-coated includes inorganic pigments, organic pigments and resin powder pigments. Here, as the inorganic pigment, for example, titanium oxide, red iron oxide, yellow iron oxide, black iron oxide, ultramarine, zinc white, magnesium oxide, zirconium oxide, mica, sericite, talc, silica, kaolin, calcium carbonate, chromium hydroxide , Magnesium silicate, aluminum oxide, barium sulfate, titanium-coated mica and the like. As the organic pigment, for example, Lisor Rubin B, Lake Red C,
Lysole Red, Rhodamine B, Herringdon Pink C
N, permanent red, benzidine orange G, phthalocyanine blue and the like. Examples of the resin powder pigment include nylon powder, acrylic powder, and silicon powder. In the present invention, the compounding amount of the water- and oil-repellent powder is preferably from 0.1 to 80% by weight, more preferably from 1 to 60% by weight, based on the total amount of the cosmetic. The ionic surfactants used in the oil-in-water cosmetics of the present invention are those generally used in cosmetics, and include, for example, fatty acid soaps, acyl glutamates, alkyl phosphates and polyphosphates. Anionic surfactants such as oxyalkylene-added alkyl phosphates and cationic surfactants such as alkylamine salts and alkyl quaternary ammonium salts can be used.
A species or two or more species may be selected and used. In addition,
Particularly preferred among these are fatty acid soaps. Here, the fatty acid used in the fatty acid soap preferably has an alkyl group or an alkenyl group having 12 or more carbon atoms, and more preferably has 14 to 22 carbon atoms. In particular,
For example, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, 12-hydroxyoutearic acid, undecylenic acid, tallic acid, isostearic acid, linoleic acid, linoleic acid, eicosapentaenoic acid (EPA), docosahexaene In addition to a single fatty acid such as acid (DHA), complex fatty acids such as coconut oil fatty acid, palm fatty acid, and bovine fatty acid are exemplified. Among them, stearic acid and isostearic acid are preferred from the viewpoint of stability. One or more of these fatty acids are used. In addition, as a counter ion of the fatty acid soap, sodium, potassium, triethanolamine salt and the like can be mentioned. The fatty acid soap in the present invention is a soap obtained by neutralizing a part or all of the fatty acid with a base. However, in the present invention, free fatty acids that remain unreacted without neutralization may be present. In the present invention, the fatty acid soap can also be obtained by, for example, a method in which a fatty acid and an aqueous alkali solution containing the counter ion are mixed together with other components to produce a fatty acid soap in the system. In the present invention, the amount of the ionic surfactant is 0.1 to 20 with respect to the total amount of the cosmetic.
% By weight. In the present invention, a surfactant other than the ionic surfactant may be included. Such surfactants include imidazoline-based amphoteric surfactants, amphoteric surfactants such as betaine-based amphoteric surfactants, sorbitan fatty acid esters, glycerin or polyglycerin fatty acids, propylene glycol fatty acid esters, hydrogenated castor oil derivatives, Glycerin alkyl ethers, POE sorbitan fatty acid esters, POE sorbitol fatty acid esters, POE glycerin fatty acid esters, POE fatty acid esters, POE alkyl ethers, POE alkyl phenyl ethers, POE-P
OP alkyl ethers, tetra POE-tetra POP
Ethylenediamine condensates, POE castor oil or hydrogenated castor oil derivatives, POE beeswax-lanolin derivatives, alkanolamides, POE propylene glycol fatty acid ester, POE alkylamine, POE fatty acid amide, sucrose fatty acid ester, POE nonylphenylformaldehyde condensate, Nonionic surfactants such as rukyethoxydimethylamine oxide and trioleyl phosphate, and surfactants such as modified silicone can be used. One or more of these may be selected and used. In the oil-in-water type cosmetic of the present invention, in addition to the above-mentioned components, components which can be generally used in cosmetics can be used as long as the desired effects of the present invention are not hindered.
Examples include fats, waxes, hydrocarbons, higher alcohols,
Oils such as esters, metal soaps, silicone oils, fluorine oils, lower alcohols, polyhydric alcohols, dyes, dyes such as natural dyes, film forming agents, humectants, fragrances, preservatives And ultraviolet absorbers, antioxidants, bactericides, plant extracts, animal extracts, enzymes, drugs, and special components such as acids and alkalis. The oil-in-water cosmetic of the present invention can be applied to any cosmetics such as skin care cosmetics, makeup cosmetics, and hair cosmetics. Among these cosmetics, cosmetics that particularly easily exhibit effects include make-up cosmetics. Among these make-up cosmetics, foundations, white powder, makeup base, blush, lipstick, concealer, eye shadow, eye Liners and mascaras are specific examples. The form of the oil-in-water cosmetic of the present invention may be cream, gel, emulsion, liquid, or solid. EXAMPLES Next, specific examples of the oil-in-water type cosmetic according to the present invention will be described. Note that the present invention is not limited to the embodiments described below. Examples 1 and 2 and Comparative Example 4 described below
The surface-treated powder used and blended in the Japanese Patent Application No. 2000
Prepared by the method described in US Pat. That is, a perfluoroalkyl phosphate ammonium salt having 13 carbon atoms on average has a solid content of 3.5 w.
t%, acrylic silicon copolymer (Shin-Etsu Chemical: K
A solution in which both are dissolved in isopropyl alcohol so that the solid content of P-541) is 1 wt% is produced. At this time, the perfluoroalkyl phosphate ammonium salt is not completely dissolved in isopropyl alcohol but exists as an emulsion, and the solution is cloudy. Then, while injecting 5 kg of titanium oxide into a high-speed stirring mixer, 10 kg of the solution was added dropwise during mixing and stirring.
And stir for 30 minutes. Thereafter, the mixture is heated to 120 ° C. and the pressure in the stirrer is reduced to about 2 hours to completely remove isopropyl alcohol as a solvent. afterwards,
Heated at 110 ° C for 6 hours and finished 2m
pulverized with a hammer mill with a screen of
% Perfluoroalkyl phosphate (C 1
Titanium oxide surface-coated with 3) and 2 wt% of an acrylic silicon copolymer was obtained. In addition, surface-treated powders having the same surface coverage were obtained in the same manner for yellow iron oxide, red iron oxide and black iron oxide. Here,
The surface-treated powder (water- and oil-repellent powder) thus obtained is
In the following, the composite coated titanium oxide, the composite coated yellow iron oxide, the composite coated red iron oxide, and the composite coated black iron oxide will be referred to respectively. On the other hand, each fluorine compound-treated powder (each pigment) used in Comparative Example 1 was prepared by the method described in Japanese Patent Publication No. 5-86984, and was 5 wt% of a C13 perfluoroalkyl phosphoric acid. Each powder (titanium oxide, yellow iron oxide, red iron oxide, black iron oxide) is obtained by coating the surface of each powder with an ester diethanolamine salt. On the other hand, each siliconized powder (each pigment) used in Comparative Example 2 was prepared by a well-known method, and
Each powder (titanium oxide, yellow iron oxide, red iron oxide, black iron oxide) was surface-coated with t% silicon to obtain a powder. The pigments obtained by the above surface treatment methods (composite coating treatment, perfluoroalkyl phosphate ester diethanolamine salt treatment, silicon treatment) indicate the water and oil repellency of each pigment. Table 1 shows the measurement results of the angles. Here, the contact angle was measured using a goniometer-type contact angle measuring device manufactured by Elmer. [Table 1] Subsequently, Examples 1 and 2 and Comparative Examples 1 to 4
Will be described step by step. (Examples 1, 2 and Comparative Examples 1 to 4) Oil-in-water emulsified foundation The oil-in-water emulsified foundation having the formulation shown in Table 2 was prepared by the following production method, and was evaluated for "emulsifiability" and "stickiness". The following evaluation methods were used to evaluate each of the following items: "Nasa", "Refreshing feeling", "Adhesion to skin", "Water and oil repellency", and "Stability over time". The results are also shown in Table 2. Indicated. [Table 2] (Production method) (1) to (6) are dissolved by heating (oil phase). The mixed and pulverized (14) to (29) are added thereto and uniformly dispersed by a homomixer. Furthermore, separately (7) to (13)
Was uniformly mixed by heating (aqueous phase), the aqueous phase was added to the oil phase, mixed and emulsified by a homomixer, and then filled in a container to obtain an oil-in-water foundation. (Evaluation method and evaluation criteria) (Evaluation of "emulsifiability"): Each of the oil-in-water foundations of Examples 1 and 2 and Comparative Examples 1 to 4 was filled into a glass bottle containing 50 ml, and the appearance was visually observed. The judgment was made based on the standard. ：: Good ：: Slight oil film on the surface △: Slight separation ×: Separation (evaluation of “no stickiness”, “freshness”, “skin adhesion”) Examples 1 and 2, Comparative Example 1 About 10 oil-in-water foundations were used by 10 specialized panelists, and were judged according to the following criteria. ◎: 9 or more panelists evaluated as good ○: 7 or more panelers evaluated as good Δ: 4 to 6 panelists evaluated as good ×: 3 or less evaluated as good (“water repellency” Evaluation of "Oiliness") The oil-in-water foundations of Examples 1 and 2 and Comparative Examples 1 to 4 were applied on artificial skin, and the contact angle of water or liquid paraffin to the cosmetic film after evaporation of volatile components such as moisture. Was measured by the method described above and evaluated according to the following criteria. ：: contact angle of 90 degrees or more ：: contact angle of 60 to less than 90 degrees △: contact angle of 40 to less than 60 degrees x: contact angle of less than 40 degrees (evaluation of “temporal stability”) After storing the oil-in-water foundations of Comparative Examples 1 to 4 at 50 ° C. for one month, the state was visually evaluated according to the following criteria. ◎: No change in the state was observed. ：: A slight change was observed in the state. 大 き な: A large change was observed in the state. X: Separation was observed. It has almost the same non-stickiness, freshness, and water and oil repellency as those of Nos. 1 and 2, but has problems with emulsification, adhesion to skin, and stability over time. Comparative Example 2 has almost the same non-stickiness, freshness, and water repellency as those of Examples 1 and 2, but has insufficient emulsifying properties, and has poor adhesion to skin, oil repellency, and aging. There is a problem with stability. Comparative Example 3, in which the untreated powder was blended, had insufficient tackiness and refreshing feeling, and had problems in emulsifying properties, adhesion to skin, and water / oil repellency. In Comparative Example 4 in which only the nonionic surfactant was emulsified, the emulsifying properties, the adhesion to the skin, the water and oil repellency, and the stability over time were insufficient. In contrast, Example 1 and Example 2 were excellent in all items. Next, Embodiments 3 and 4 will be described. (Example 3) Solid foundation (1) Stearic acid 2.5 (2) Glyceryl stearate 2.0 (3) Microcrystalline wax 1.0 (4) Preservative proper amount (5) 1,3-butylene Glycol 10.0 (6) Agar 1.0 (7) Carboxyvinyl polymer 0.2 (8) Triethanolamine 1.0 (9) Remaining purified water (10) Composite coated titanium oxide 7.0 (11) Complex coating treatment yellow iron oxide 1.0 (12) Composite coating treatment red iron oxide 0.3 (13) Composite coating treatment black iron oxide 0.1 100.0 In Example 3, (1) to (3) were dissolved by heating. (Oil phase), and mixed and pulverized (10) to (13) are added thereto and uniformly dispersed. Further, (4) to (9) were separately heated and mixed uniformly (aqueous phase), and the aqueous phase was added to the oil phase and filled in a container to obtain a solid foundation. The solid foundation of the present example thus obtained is excellent in all the items of emulsifying property, lack of stickiness, refreshing feeling, adhesion to skin, makeup persistence, water and oil repellency, and stability over time. there were. (Example 4) Mascara (1) Stearic acid 4.0 (2) Beeswax 5.0 (3) Carnauba wax 30.0 (4) Paraffin wax 3.0 (5) Sorbitan sesquioleate 2. 0 (6) Preservative appropriate amount (7) Propylene glycol 10.0 (8) Triethanolamine 3.5 (9) Purified water Remaining (10) Composite coated black iron oxide 10.0 100.0 In Example 4 Is obtained by heating and dissolving (1) to (5) (oil phase), adding (10) to this, and uniformly dispersing with a homomixer. Furthermore, (6) to (9) were uniformly mixed by heating (aqueous phase), the aqueous phase was added to the oil phase, mixed and emulsified by a homomixer, and then filled in a container to obtain a mascara. The mascara of this example thus obtained was excellent in all of the items of emulsifiability, lack of stickiness, freshness, adhesion, water and oil repellency, and stability over time. As described in detail above, the oil-in-water cosmetic of the present invention has a non-greasy, smooth, refreshing feeling, adhesion to skin, water and oil repellency, and stability over time. It had excellent quality.

   ────────────────────────────────────────────────── ─── Continuation of front page    F term (reference) 4C083 AA122 AB232 AB242 AB432                       AC012 AC022 AC072 AC122                       AC242 AC422 AC442 AC482                       AC542 AD092 AD212 AD352                       BB05 BB06 BB25 CC01 CC12                       CC14 DD33 EE03 EE06 EE11

Claims (1)

[Claim 1] A general formula: (In the formula, Rf represents a perfluoroalkyl group or a perfluorooxyalkyl group having 3 to 21 carbon atoms, is linear or branched, and has a single chain length even if it has a complex chain length. N represents an integer of 1 to 12, y represents a number of 1 to 3, and M represents hydrogen, an alkali metal, ammonium or substituted ammonium.) A phosphoric ester having the general formula: (Wherein, n is an integer, a, b, c, d are the respective molar ratios in the copolymer, which are not 0, and d is 40
It is not less than mol% and not more than 60 mol%. A) a water- and oil-repellent powder which is simultaneously surface-treated with an acrylic copolymer high molecular weight product having a molecular weight of 30,000 to 300,000 and having a side chain of dimethylpolysiloxane, and an ionic surfactant. An oil-in-water cosmetic which is characterized in that: