JP2010208986A - Water-repellent and oil-repellent pigment and cosmetic containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a surface-treated pigment exhibiting water- and oil-repellency by virtue of a fluorine compound free of perfluorooctanoic acid (PFOA); and a cosmetic containing the pigment. <P>SOLUTION: This pigment is obtained by surface-treating a pigment powder with a fluorine compound expressed by chemical formula (1), which is a fluorine compound phosphoric acid or a salt thereof containing 100 ppb or less amount of perfluorooctanoic acid as an impurity in the compound, where in the formula, n and m are each an integer of 1 or more provided that n+m=3; and M is a hydrogen atom or a monovalent metal ion, ammonium salt or diethanolamine salt. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a water- and oil-repellent pigment suitable for blending in makeup cosmetics or sunscreen cosmetics represented by foundations, eye shadows, cheeks, lipsticks, and the like and cosmetics containing the same.

  Conventionally, in order to impart water repellency and oil repellency to makeup cosmetics or sunscreen cosmetics represented by foundations, eye shadows, cheeks, lipsticks, etc., perfluoroalkyl phosphorus represented by the following general chemical formula (2) A water- and oil-repellent pigment formed by surface-treating pigment powder with an acid ester compound is used (see Patent Documents 1 to 3).

  In the fluorine compound represented by the general chemical formula (2), when it is generally produced in an industrialization process (generally referred to as a telomer method), 1H, 1H, It contains perfluorooctanoic acid derived from 2H, 2H-perfluorodecanol (hereinafter abbreviated as “PFOA”). Generally, the content of PFOA is at a level of tens of thousands of ppb or more. For this reason, the pigment powder surface-treated with this fluorine compound contained PFOA at a concentration of several hundred ppb or more. It has been reported by the US Department of the Environment (hereinafter abbreviated as “EPA”) that PFOA is extremely persistent in the natural environment. Can see. In various government agencies, universities, etc., the concentration of PFOA in rivers and the concentration in human blood have been measured and reported. According to these reports, the concentration ranges from tens of ppb to hundreds of ppb. Currently, no examples of health damage due to PFOA have been reported, but the EPA is currently investigating.

  On the other hand, EPA has declared that the content of PFOA will be zero by 2015 for products using 1H, 1H, 2H, 2H-perfluorodecanol as a raw material by the telomer method. Thus, the pigment powder surface-treated with the perfluoroalkyl phosphoric acid represented by the chemical formula (2) or a salt thereof contains PFOA at a higher level than that detected in nature. For this reason, development in order to obtain a surface-treated pigment exhibiting water and oil repellency with a fluorine compound not containing PFOA is strongly demanded in the cosmetic field.

Japanese Patent Publication No. 5-86984 JP-A-3-246210 JP-A-4-330007

Journal of Occupational Health, 46 (1), 49-59 (2004).

  The present invention has been made in view of the above-mentioned problems, and provides a surface-treated pigment that exhibits water and oil repellency by a fluorine compound that does not contain PFOA (perfluorooctanoic acid), and also contains the pigment. The purpose is to provide cosmetics to be used.

The present inventor defines the number of carbon atoms of the perfluoroalkyl group in the fluorine compound as 6, and thereby, a compound not using 1H, 1H, 2H, 2H-perfluorodecanol as a raw material, that is, represented by the following chemical formula (1) The above-mentioned problems have been solved by limiting to fluorine compound phosphoric acid or a salt thereof.
In short, the water- and oil-repellent pigment according to the first invention is
It is a fluorine compound represented by the following chemical formula (1), and is obtained by surface-treating a pigment powder with a fluorine compound phosphoric acid or a salt thereof, in which the content of perfluorooctanoic acid as an impurity is 100 ppb or less. It is characterized by this.

  In the present invention, the content of perfluorooctanoic acid as the impurity is preferably 20 ppb or less (second invention).

  A cosmetic according to the third invention is characterized by containing the water / oil repellent pigment of the first invention or the second invention.

  In the present invention, the content of PFOA after the surface treatment is reduced to a natural level by regulating the carbon number of the perfluoroalkyl group to 6 like the fluorine-based phosphoric acid of the above chemical formula (1) or a salt thereof. Can be suppressed. In addition, according to the present compound, the perfluoroalkyl phosphate compound represented by the general formula (2) has a carbon chain number of a perfluoro group sufficient to have water and oil repellency due to the present structure. It is possible to provide a cosmetic having the same performance as that of the pigment powder surface-treated with.

  Next, specific embodiments of the water / oil repellent pigment and the cosmetics containing the same according to the present invention will be described.

  Examples of the surface treatment method for the pigment powder of the fluorine compound represented by the chemical formula (1) used in the present invention include the following methods.

  The phosphoric acid represented by the chemical formula (1) is dissolved in a suitable organic solvent having a polarity such as alcohol at a suitable concentration, and mixed with the pigment powder by dropping or adding in a mixer. The pigment powder surface-treated with the fluorine-type compound shown by Chemical formula (1) can be obtained by evaporating and removing, heat-treating, and crushing as needed.

  In addition, when the phosphate of the fluorine compound represented by the chemical formula (1) is used, since the fluorine compound is often a water emulsion, the pigment powder is made into a water slurry and has an appropriate concentration. A pigment powder surface-treated with the fluorine compound represented by the chemical formula (1) is obtained by adding the fluorine compound in the form of an aqueous emulsion, heating (may be acidified), washing with water, drying and crushing. Obtainable.

  With respect to the fluorine compound represented by the chemical formula (1) in the present invention, 2- (perfluorohexyl) ethyl phosphoric acid or a salt thereof is particularly preferable. In particular, the surface treatment with 2- (perfluorohexyl) ethyl phosphoric acid is a process material. The method used is preferable because it is simple.

  Further, the content of PFOA in the fluorine compound represented by the chemical formula (1) in the present invention is 100 ppb or less, preferably 50 ppb or less, more preferably 10 ppb or less, which is almost the same as the natural world. Further, the amount of PFOA contained in the pigment powder after the surface treatment with the fluorine compound represented by the chemical formula (1) of the present invention is 20 ppb or less, preferably 10 ppb or less, more preferably 5 ppb or less. .

  Regarding the measurement of the content of PFOA, it is best to measure by the mass spectrometry method by liquid chromatography according to the method disclosed in Analytical Biochemistry, 118, 336-343 (1981), but the current detection limit is several ppb. is there.

  The treatment amount of the fluorine compound represented by the chemical formula (1) in the present invention varies depending on the pigment powder, but is in the range of 0.05 to 30% by mass, preferably 0.1 to 20% by mass with respect to the pigment powder mass. % Range. When the treatment amount is less than 0.05% by mass with respect to the mass of the pigment powder, water repellency or oil repellency or both are hardly exhibited. When the treatment amount exceeds 30% by mass with respect to the mass of the pigment powder, the excess of the compound represented by the chemical formula (1) remains as a single unit without being surface-treated, and there is a problem with the feel and fluidity of the treated pigment powder. Will occur.

  In the present invention, examples of the pigment surface-treated with the fluorine compound represented by the chemical formula (1) include inorganic pigments, organic pigments, and plastic powder pigments. Among these, examples of the inorganic pigment include titanium oxide, zinc oxide, iron oxide, magnesium oxide, mica, sericite, talc, silica, aluminum oxide, barium sulfate, titanium-coated mica, boron nitride, and barium sulfate. Examples of organic pigments include Risol Rubin B, Lake Red C, Risol Red, Rhodamine B, Herringdon Pink CN, Benzine Orange G, and Flocitannin Blue. Examples of the plastic powder pigment include nylon powder, acrylic powder, silicon powder, urethane powder, and polytetrafluoroethylene powder.

  In cosmetics containing the water- and oil-repellent pigments of the present invention, in addition to the surface-treated pigments, oil agents, powders (pigments, dyes, resins), fluorine compounds, resins, surface active agents used in ordinary cosmetics Components such as an agent, a sticking agent, a preservative, a fragrance, a moisturizing agent, a physiologically active component, a salt, a solvent, a chelating agent, a neutralizing agent, and a pH adjusting agent can be blended simultaneously.

  Here, as the powder, for example, red 104, red 201, yellow 4, blue 1, black 401 and other dyes, yellow 4 aluminum lake, yellow 203 barium lake and other lake dyes, Nylon powder, silk powder, urethane powder, Teflon (registered trademark) powder, silicon powder, cellulose powder, silicone elastomer and other polymers, yellow iron oxide, red iron oxide, black iron oxide, chromium oxide, carbon black, ultramarine, bitumen Colored pigments such as titanium oxide, cerium oxide, white pigments, talc, mica, sericite, body pigments such as kaolin, pearl pigments such as titanium mica, barium sulfate, calcium carbonate, magnesium carbonate, aluminum silicate, silica Metal powder such as magnesium acid, inorganic powder such as silica, alumina, boron nitride , Particulate titanium oxide, particulate iron oxide, alumina-treated fine titanium oxide particles, silica treated ultrafine titanium dioxide, bentonite, smectite, and the like. There are no particular restrictions on the shape and size of these powders. These powders may or may not be subjected to various conventionally known surface treatments. Examples of surface treatments include, for example, acrylic silicone treatment, methyl hydrogen polysiloxane treatment, silicone resin treatment, octyltriethoxysilane treatment, one-end reactive silicone treatment, N-acylated lysine treatment, organic titanate treatment, silica treatment, Various treatments such as alumina treatment, cellulose treatment, perfluoropolyether treatment, and fluorinated silicone resin treatment such as hydrophilic treatment, lipophilic treatment, and water repellency treatment can be used.

  When this surface-treated pigment powder is used as a cosmetic, it feels good when blended with a slippery plate-like powder such as barium sulfate or boron nitride, or a resin or inorganic spherical powder. It becomes a cosmetic with excellent slipperiness. Among these, in particular, the spherical powder is blended in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the powder obtained by coating the fluorine compound polymer on the pigment surface in an amount of 2 to 6% by mass. By doing, a feeling of application improves and the skin feel after application can also be improved. If the blending amount of the spherical powder is less than 0.1 parts by mass, the feeling of application is not improved, and if it exceeds 5 parts by mass, the cosmetic may not adhere well to the skin depending on the dosage form of the preparation, and the makeup may become dirty , You may need to familiarize the skin with the skin over and over again.

  Examples of the spherical powder in the present invention include, for example, resin powder such as silicone resin, silicone elastomer, urethane, polystyrene, polypropylene, alginate, nylon, and acrylic resin, and inorganic powder such as silica, alumina, and zirconia. Can be mentioned. The term “spherical” as used herein refers to a shape having a true spherical shape to a substantially spherical shape, and is characterized by excellent slipperiness. Moreover, as a magnitude | size of spherical powder, the powder which exists in the range of 1-20 micrometers in the maximum diameter is mentioned, Especially preferably, the powder which exists in the range of 1-10 micrometers is mentioned.

  Examples of the oil include higher alcohols such as cetyl alcohol, isostearyl alcohol, lauryl alcohol, hexadecyl alcohol, octyldodecanol, fatty acids such as isostearic acid, undecylenic acid, oleic acid, glycerin, sorbitol, ethylene glycol, propylene glycol, Polyhydric alcohols such as polyethylene glycol, myristic myristate, hexyl laurate, decyl oleate, isopropyl myristate, hexyl decyl dimethyloctanoate, glyceryl monostearate, diethyl phthalate, ethylene glycol monostearate, octyl oxystearate, etc. Esters, hydrocarbons such as liquid paraffin, petrolatum, squalane, lanolin, reduced lanolin, wax such as carnauba wax, mink , Cacao oil, coconut oil, balm kernel oil, camellia oil, sesame oil, castor oil, oils such as olive, ethylene-alpha-olefin co-oligomer, and the like. In addition, methyl hydrogen polysiloxane, dimethyl polysiloxane, methyl phenyl polysiloxane, polyether-modified organopolysiloxane, fluoroalkyl / polyoxyalkylene co-modified organopolysiloxane, alkyl-modified organopolysiloxane, fluorine-modified organopolysiloxane, amodimethicone And silicone compounds such as amino-modified organopolysiloxane, silicone gel, acrylic silicone, trimethylsiloxysilicic acid, and silicone RTV rubber, and fluorine compounds such as perfluoropolyether, fluorinated pitch, fluorocarbon, fluoroalcohol, and fluorinated silicone resin. It is done.

  Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and a betaine surfactant.

  Examples of the solvent include purified water, ethanol, light liquid isoparaffin, lower alcohol, ethers, LPG, fluorocarbon, N-methylpyrrolidone, fluoroalcohol, perfluoropolyether, alternative chlorofluorocarbon, and volatile silicone.

  Specific examples of the cosmetic of the present invention include, for example, foundations, white powder, concealer, face powder, blusher, eye shadow, eyeliner, teak, lipstick, nail color and other makeup cosmetics, emulsions, creams, lotions, Calamine lotion, sunscreen agent, suntan agent, after shave lotion, pre-shave lotion, pack, cleansing agent, facial cleanser, acne anti-cosmetic basic cosmetics, hair color, body powder, deodorant, soap, body shampoo, bath preparation , Perfume and the like.

  The blending amount of the water / oil repellent pigment blended in the cosmetic of the present invention is preferably from 0.1 to 80% by mass, more preferably from 1 to 60% by mass, based on the total amount of the cosmetic. In addition, as a compounding quantity of an antioxidant, 0.001-10 mass% is preferable.

  As the dosage form of the cosmetic of the present invention, conventionally known dosage forms such as a bilayer, a water-in-oil emulsion, an oil-in-water emulsion, a gel, a spray, a mousse, an oil, and a solid can be used. it can. In particular, for use as a sunscreen agent, a two-layered, water-in-oil emulsion, gel, oil-in-water emulsion, oily, mousse or the like is preferable.

  Next, specific examples of the water / oil repellent pigment and the cosmetics containing the same according to the present invention will be described. In addition, this invention is not limited to the Example described below.

(Production Example 1)
2- (perfluorohexyl) ethyl phosphoric acid having a PFOA content of 35 ppb was dissolved in isopropyl alcohol so as to be 5%. Place 1 kg of titanium oxide in a Henschel mixer, and then add a 5% isopropyl alcohol solution of 2- (perfluorohexyl) ethyl phosphate to 5% of 2- (perfluorohexyl) ethyl phosphate with respect to titanium oxide. Put in and mix well with titanium oxide. Thereafter, the Henschel mixer was heated, and if necessary, the inside of the Henschel mixer was decompressed to remove isopropyl alcohol. The pigment powder was taken out of the Henschel mixer, heated at 130 ° C. for 6 hours, and then crushed to obtain titanium oxide treated with 5% by mass of 2- (perfluorohexyl) ethyl phosphoric acid.

(Production Example 2)
In the same manner as in Production Example 1, each surface-treated pigment powder was obtained in which 5- (perfluorohexyl) ethyl phosphoric acid was treated with sericite, talc, and mica instead of titanium oxide.

(Production Example 3)
Tridecafluorooctyl trichloride using Bengala, yellow iron oxide and black iron oxide instead of titanium oxide in the same manner except that the heating temperature after removal from the Henschel mixer of Production Example 1 was changed from 130 ° C to 110 ° C. Each of bengara, yellow iron oxide and black iron oxide treated with 3% by mass of ethoxysilane was obtained.

(Production Comparative Example 1)
A perfluoroalkyl phosphate compound having a number average of 13 carbon atoms and a PFOA content of 12000 ppb as a solid content per kg of titanium oxide as a perfluoroalkyl phosphate ester compound represented by the above general chemical formula (2) is 50 g. The ammonium salt solution was mixed with 200 g of isopropyl alcohol, and the mixture and 1 kg of titanium oxide were mixed with a Henschel mixer. Thereafter, the Henschel mixer was heated, and if necessary, the inside of the Henschel mixer was decompressed to remove isopropyl alcohol. Thereafter, the pigment powder is taken out of the Henschel mixer, heated at 130 ° C. for 6 hours, and then crushed to obtain titanium oxide treated with 5% by mass of a perfluoroalkyl phosphate ammonium salt having a number average of 13 carbon atoms. It was.

(Production Comparative Example 2)
In the same manner as in Production Comparative Example 1, sericite, talc and talc were treated with 5% by mass of a perfluoroalkyl phosphate ammonium salt having a number average of 13 carbon atoms using sericite, talc and mica instead of titanium oxide. Got each of mica.

(Production Comparative Example 3)
The number of carbons in terms of number average using Bengala, yellow iron oxide and black iron oxide instead of titanium oxide in the same manner except that the heating temperature after taking out from the Henschel mixer of Production Comparative Example 1 was changed from 130 ° C to 110 ° C. Each of Bengala, yellow iron oxide and black iron oxide treated with 5 mass% of perfluoroalkyl phosphate ammonium salt of No. 13 was obtained.

  Table 1 shows the contact angles and the content of PFOA of the surface-treated pigments obtained in Production Examples 1 to 3 and Production Comparative Examples 1 to 3 with water and liquid paraffin. From these results, the pigment powder surface-treated with the fluorine-based phosphoric acid represented by the chemical formula (1) or a salt thereof has water repellency and oil repellency similar to those of conventional perfluoroalkyl phosphate compounds. Moreover, it can be seen that the surface-treated pigment powder has a very low content of PFOA compared to the fluorine-based compound represented by the chemical formula (2).

  Here, the measurement method of PFOA uses the measurement method according to the above-mentioned literature, but it is simply measured by the following method. That is, a certain amount of sample (fluorine compound itself or surface-treated powder) is extracted and concentrated in methanol, and then measured by liquid chromatography / mass spectrometry.

  Next, a powder foundation was prepared using the surface-treated pigment according to the present invention.

Example 1
Using the surface-treated powder obtained in Production Example 1 and Production Example 2, a powder foundation was prepared with the following composition.
First, a powder base was prepared with the following composition.
<Powder base formulation>
Surface treatment sericite 60.0
Surface treatment talc 27.0
Surface treated titanium oxide 10.0
Surface-treated yellow iron oxide 2.0
Surface treatment Bengala 0.7
Surface-treated black iron oxide 0.2
Methylparaben 0.1
Total 100.0

Next, a binder base was prepared with the following formulation.
<Binder base formulation>
Dimethylpolysiloxane (20CS) 70.00
Dimethylpolysiloxane trimethylsiloxysilicate 29.85
Phenoxyethanol 0.10
Tocophenol 0.05
Total 100.00

The powder base and binder base were mixed with a mixer so as to be 90% and 10%, respectively, to obtain a powder foundation.

(Comparative Example 1)
A powder foundation was prepared in the same manner as in Example 1 using the surface-treated powder obtained in Production Comparative Example 1 and Production Comparative Example 2.

  The powder foundation evaluation and PFOA content of Example 1 and Comparative Example 1 are shown in Table 2. From Table 2, the pigment powder surface-treated with 2- (perfluorohexyl) ethyl phosphoric acid of the chemical formula (1) and the pigment powder surface-treated with the conventional perfluoroalkyl phosphate compound represented by the chemical formula (2) A powder foundation with the same performance with no difference in finish and stability from the body was obtained.

  The water- and oil-repellent pigments of the present invention are suitable for use in makeup cosmetics or sunscreen cosmetics represented by foundations, eye shadows, cheeks, lipsticks and the like.

Claims (3)

It is a fluorine compound represented by the following chemical formula (1), and is obtained by surface-treating a pigment powder with a fluorine compound phosphoric acid or a salt thereof, in which the content of perfluorooctanoic acid as an impurity is 100 ppb or less. A water- and oil-repellent pigment characterized by that.

  The water / oil repellent pigment according to claim 1, wherein the content of perfluorooctanoic acid as the impurity is 20 ppb or less.   A cosmetic comprising the water- and oil-repellent pigment according to claim 1.