JP3492386B2 - Hydrophobic powders and cosmetics - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrophobic powder obtained by surface treatment of powder, and a cosmetic characterized by blending the hydrophobic powder. More specifically, it is obtained by reacting a fluorine-modified organohydrogenpolysiloxane having at least one Si—H group and at least one perfluoroalkyl group in the molecule on the surface of powder, and is hydrophobic and oleophobic. The present invention relates to an excellent hydrophobic powder, and a cosmetic composition containing the hydrophobic powder, which has excellent water resistance, sebum resistance, and oil resistance, and has excellent makeup retention and usability. is there.

[0002]

2. Description of the Related Art Conventionally, there are many known methods for hydrophobizing hydrophilic powders, and it is already well known to utilize the hydrophobic property of silicone oil. For example, in Japanese Examined Patent Publication No. 9890/41, the surface of animals and plants and mineral powder is coated with a silicone resin coating material and dried and baked to impart lubricity to the powder. Japanese Patent Office Sho 45
In -2915, to a mineral powder such as talc, a silicone having hydrogen directly bonded to silicon in the molecular chain is simply attached by blender mixing or the like, and then heated and baked to impart water repellency to the powder. There is. In Japanese Examined Japanese Patent Publication 45-18999,
Dissolve dimethylpolysiloxane or methylhydrogenpolysiloxane in talc in an organic solvent and contact it, and then add a substance such as zinc octoate as a cross-linking polymerization catalyst for methylhydrogenpolysiloxane and bake it to free the powder. Liquidity is added. In Japanese Examined Patent Publication No. 49-1769, titanium dioxide is directly coated with various alkylpolysiloxanes, emulsion coating or solvent solution coating, and if necessary, an ester compound having a total carbon number of 6 or more is used in combination and dried and baked to obtain dust of the powder. Properties and dispersibility are modified. In Japanese Examined Patent Publication No. 56-43264, methylhydrogenpolysiloxane is mechanochemically crosslinked and polymerized on the powder surface to produce a hydrophobic powder. In addition, as a technique for powder modification using fluorine-modified silicone
In -93605, the metal oxide fine powder is surface-treated with a silicon compound containing a perfluoroalkyl group to improve the fluidity of the powder.

[0003]

[Problems to be Solved by the Invention] The aforementioned Japanese Patent Publication No. 41-9890
, JP-B-45-2915, JP-B-45-18999, JP-B-49-1769
And the hydrophobic powder produced by the method of JP-B-56-43264 is not sufficient as the hydrophobicity desired for cosmetics, etc. There is a problem that makeup is broken by oil contained in sebum and other cosmetics. JP-A-3-93605 exemplifies a silane coupling agent containing a perfluoroalkyl group as a silicon compound containing a perfluoroalkyl group, and a cyclic polysiloxane and a chain polysiloxane having a perfluoroalkyl group. When a silane coupling agent containing a perfluoroalkyl group is used, the silane coupling agent reacts with the functional group on the surface of the powder, and therefore the reactivity may differ depending on the type of powder, and insufficient treatment may be possible. When a cyclic polysiloxane having a perfluoroalkyl group or a chain polysiloxane is used, since these polysiloxanes do not have a reactive functional group, they drop off from the powder surface over time and the hydrophobicity deteriorates. Had the problem.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above technical problems, the inventors of the present invention have selected one or more powders selected from inorganic powders and organic powders. , A hydrophobic powder having high hydrophobicity and excellent oleophobicity when surface-treated with a fluorine-modified organohydrogenpolysiloxane having at least one Si-H group and at least one perfluoroalkyl group in the molecule Based on this finding, it was found that when this powder was blended into a cosmetic, a cosmetic having good water resistance, sebum resistance and oil resistance, and long lasting makeup and usability was obtained. As a result, the present invention has been completed.

That is, in the present invention, one or more powders selected from inorganic powders and organic powders have at least one Si—H group and at least one perfluoroalkyl group in the molecule, More specifically, general formula (1):

[Chemical formula 2] [Wherein R 1 s may be the same or different and represent a methyl group or a phenyl group, and R 2 s may be the same or different as each other, a methyl group, a phenyl group, hydrogen, a hydroxyl group or R
R3 represents the same group as 3; -R4 -Rf (wherein R4 represents a divalent alkylene group having 2 to 6 carbon atoms, and Rf represents a perfluoroalkyl group having 1 to 12 carbon atoms). Represents an organic group represented by, and 1 and m and n are an average number of 1 = 0 to
The numbers are 50, m = 10 to 100, and n = 1 to 100. ] A hydrophobic powder obtained by surface-treating with a fluorine-modified organohydrogenpolysiloxane represented by the following, and a cosmetic characterized by containing the hydrophobic powder.

The present invention will be described in detail below. The powder used in the present invention is silicon, anhydrous silicic acid, magnesium silicate, talc, kaolin, mica, bentonite, titanium-coated mica, bismuth oxychloride, zirconium oxide,
Magnesium oxide, zinc oxide, titanium dioxide, fine particle titanium oxide, aluminum oxide, calcium sulfate, barium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, iron oxide, ultramarine blue, dark blue, chromium oxide, chromium hydroxide, calamine and carbon black, And inorganic powders such as composites thereof, polyamide powders such as nylon powder,
Polyolefin powder such as polyethylene powder, polyester powder, polystyrene powder, polyacrylate powder such as polymethylmethacrylate, silicone resin powder, fluororesin powder such as Teflon powder, divinylbenzene, styrene copolymer powder, polyurethane powder, polyepoxy powder, Celluloid, acetyl cellulose, cellulose, chitin, chitosan, polysaccharides, protein powder, CI pigment yellow, CI pigment orange, CI pigment red, CI pigment violet, CI pigment blue,
Examples include organic powders such as CI pigment green and CI pigment brown, and composite powders of these inorganic powders and organic powders. Further, the shape of these powders is not particularly limited, and may be any shape such as plate-like, lump-like, scale-like, and spherical,
Both perforated and non-perforated can be used.

More specifically exemplifying the fluorine-modified organohydrogenpolysiloxane of the present invention, general formula (1):

[Chemical formula 3] In the above, R1 is a methyl group or a phenyl group, and the more methyl groups, the higher the hydrophobicity. R3 is a group having a perfluoroalkyl group represented by --R4 --Rf,
Examples of the divalent alkylene group having 2 to 6 carbon atoms represented by

[Chemical formula 4] ,

[Chemical formula 5] ,

[Chemical formula 6] ,

[Chemical formula 7] ,

[Chemical formula 8] ,

[Chemical formula 9] ,

[Chemical formula 10] Etc. can be mentioned. 1 to 1 carbon atoms represented by Rf
Examples of the perfluoroalkyl group of 2 include:

[Chemical formula 11] ,

[Chemical formula 12] ,

[Chemical formula 13] ,

[Chemical formula 14] ,

[Chemical formula 15] ,

[Chemical Formula 16] Groups and the like. Further, 1 and m and n are average numbers of 1 = 0 to 50, m = 1 to 100 and n = 1 to 100, and m is related to the number of Si—H groups in the molecule, and The degree of cross-linking polymerization of the fluorine-modified organohydrogenpolysiloxane when the surface treatment is performed is determined. m is small and Si-
When the amount of H groups is small, the degree of crosslinking is low, and conversely, when m is large and the amount of Si—H groups is large, the degree of crosslinking is high, and the range of 10 to 100 is selected depending on the physical properties required for the hydrophobic powder. N is related to the number of perfluoroalkyl groups in the molecule,
The larger the value of n and the more perfluoroalkyl group, the higher the hydrophobicity and oleophobicity, but the dispersibility and usability of the powder change, and therefore the hydrophobic powder has a physical property of 1 to 10 depending on the physical properties required.
It is selected in the range of 0.

The amount of fluorine-modified organohydrogenpolysiloxane added to the powder may be 0.1 to 20% by weight, and is preferably determined by the specific surface area of the raw material powder. Although it cannot be said that the powder surface characteristics differ from one powder to another, it is generally impossible to say that it is 10 mg of fluorine-modified organohydrogenpolysiloxane per gram. The content of the hydrophobic powder thus obtained in the cosmetic is usually 1 to 99% by weight.

Various processes can be adopted as a method of surface-treating the powder with a fluorine-modified organohydrogenpolysiloxane. For example, fluorine-modified organohydrogenpolysiloxane is not diluted in the raw material powder, or is used as it is, or in a suitable solvent (eg, methanol, ethanol, chloroform, dichloromethane, petroleum ether, hexane, volatile silicone, etc.).
After diluting and adding by spraying or dropping to uniformly disperse, it may be dried at room temperature or by heating, and then baked by heating, or by a mechanochemical method in which the reaction is carried out by mixing and stirring using a ball mill or the like. Good. At this time, an alkaline substance, an organic acid salt of various metals, an acidic substance or the like may be used as a reaction accelerator for the fluorine-modified organohydrogenpolysiloxane.

In addition to cosmetics, the hydrophobic powder of the present invention is for dry toner for electrophotographic copying machines, additives for plastics (reinforcing agents, colorants, etc.), additives for rubber (adhesives, etc.), magnetic tapes. It can be used as a magnetic material, a pigment for paints and inks, a lubricant, a powder for extinguishing agents, and the like.

[0011]

The present invention will be described in more detail with reference to the following examples. The present invention is not limited to these.

Example 1 Mica 24.2% by weight, talc 22.6% by weight, titanium dioxide
0.6% by weight, zinc oxide 2.1% by weight, spherical nylon 1.1% by weight and pigment were mixed in an appropriate amount, mixed with a Henschel mixer, and then fluorine-modified organohydrogenpolysiloxane (Note 1) 2.1% by weight was dissolved in ethanol 47.3% by weight. After spraying and stirring the substance, the ethanol is distilled off at 70 ° C. After that, it is baked at 100 ° C. for 3 hours. (Note 1)

[Chemical 17]

Comparative Example 1 Mica 24.2% by weight, talc 22.6% by weight, titanium dioxide
An appropriate amount of 0.6% by weight, zinc oxide 2.1% by weight, spherical nylon 1.1% by weight and pigment were mixed and mixed with a Henschel mixer.

Comparative Example 2 Mica 24.2% by weight, talc 22.6% by weight, titanium dioxide
0.6% by weight, zinc oxide 2.1% by weight, spherical nylon 1.1% by weight and pigment were mixed in an appropriate amount, mixed in a Henschel mixer, and then dissolved in ethanol 47.3% by weight, methylhydrogenpolysiloxane (molecular weight 2600) 2.1% by weight. After spraying and stirring, ethanol is distilled off at 70 ° C. After that, it is baked at 100 ° C. for 3 hours.

Example 2 Mica 27.5% by weight, talc 44.4% by weight, titanium dioxide 1
A mixture of 1.7% by weight, iron oxide (red, yellow, black) 8.2% by weight, citric acid 1% by weight, fluorine-modified organohydrogenpolysiloxane (Note 2) 2% by weight, and dichloromethane 5.2% by weight under stirring at 50 ° C. After heating under reflux for 30 minutes, heat and stir at 100 ° C for 2 hours to distill off dichloromethane, and further at 120 ° C for 1 hour.
A time baking process was performed. (Note 2)

[Chemical 18]

Comparative Example 3 Mica 27.5% by weight, talc 44.4% by weight, titanium dioxide 1
1.7% by weight and 8.2% by weight of iron oxide (red, yellow, black) are mixed with a Henschel mixer.

Comparative Example 4 Mica 27.5% by weight, talc 44.4% by weight, titanium dioxide 1
A mixture of 1.7% by weight, iron oxide (red, yellow, black) 8.2% by weight, citric acid 1% by weight, methylhydrogenpolysiloxane (molecular weight 1000) 2% by weight, dichloromethane 5.2% by weight under stirring at 50 ° C. After heating under reflux for a minute, the mixture was heated and stirred at 100 ° C. for 2 hours to distill off dichloromethane, and further baked at 120 ° C. for 1 hour.

The water repellency and oil repellency of Examples 1 and 2 and Comparative Examples 1 to 4 were examined by the following methods, and the results are shown in Table 1. (Water repellency) 5 ml of deionized water in a 10 ml sample tube
Then, 0.1 g of the powders of the examples and comparative examples were added and shaken. The judgment was performed as follows. X: Dispersed in water. B: Water-repellent, but partly dispersed in water. ◯: There is water repellency and it floated on the surface of water. (Oil repellency) 5m liquid paraffin in 10ml sample tube
Then, 0.1 g of the powder of Examples and Comparative Examples was added, and the mixture was shaken. The judgment was performed as follows. X: Dispersed in oil. Δ: Oil-repellent, but partly dispersed in oil. ◯: It has oil repellency and floated on the oil surface.

[0019]

[Table 1]

Example 3 Mica 29.2% by weight, Talc 63.6% by weight, Red No. 226 2.2
% By weight, 1.6% by weight of iron oxide (red, yellow, black) and 1.2% by weight of ultramarine blue powder in a vibrating ball mill (Central Kako I type,
After mixing and grinding for 10 minutes in 1.5 horsepower), 2.2% by weight of fluorine-modified organohydrogenpolysiloxane (Note 3) was added, and mixed and ground for 70 minutes with a vibrating ball mill. The powder of Example 3 was a hydrophobic powder having excellent water repellency and oil repellency. (Note 3)

[Chemical 19]

Example 4 Mica 6.6% by weight, talc 4.1% by weight, kaolin 4.1% by weight, titanium coated mica 0.8% by weight, titanium dioxide
1.2% by weight and 1.7% by weight of iron oxide (red, yellow, black) were mixed in a Henschel mixer, and then 77.7% by weight of hexane and 3.8% by weight of fluorine-modified organohydrogenpolysiloxane (Note 4).
Is dissolved and sprayed to disperse it uniformly, and then hexane is distilled off while stirring and baking is carried out at 150 ° C. for 2 hours. The powder of Example 4 was a hydrophobic powder having excellent water repellency and oil repellency. (Note 4)

[Chemical 20]

Example 5 Mica 13.0% by weight, talc 18.6% by weight, titanium-coated mica 2.6% by weight, iron oxide (red, yellow, black) 1.1% by weight, ultramarine blue
After mixing 5.2% by weight and 7.7% by weight of navy blue and blue with a Henschel mixer, 2.6% by weight of fluorine-modified organohydrogenpolysiloxane (Note 5) dissolved in 49.2% by weight of petroleum ether was added dropwise and the petroleum ether was distilled off while stirring and mixing. Leave.
Then, the mixture was placed in a rotary ball mill and mixed and ground for 2 hours. The powder of Example 5 was a hydrophobic powder having excellent water repellency and oil repellency. (Note 5)

[Chemical 21]

Example 6 Talc 29.3% by weight, titanium dioxide 11.7% by weight, kaolin
After mixing 8.2% by weight and an appropriate amount of pigment with a Henschel mixer, a solution prepared by dissolving 9.7% by weight of fluorine-modified organohydrogenpolysiloxane (Note 6) in 40.6% by weight of methanol is added dropwise and 0.5% by weight of tartaric acid is added and stirred. Then 70
Methanol was distilled off at ℃, put into a pot mill and mixed and ground for 5 hours. The powder of Example 6 was a hydrophobic powder having excellent water repellency and oil repellency. (Note 6)

[Chemical formula 22]

Example 7 Titanium dioxide 17.9% by weight, talc 17.9% by weight, kaolin
After mixing 8.9% by weight and an appropriate amount of pigment with a Henschel mixer, 5.3% by weight of fluorine-modified organohydrogenpolysiloxane (Note 7) dissolved in 50.0% by weight of dichloromethane was added, and the dichloromethane was distilled at 70 ° C with stirring. Leave. After that, it is baked at 100 ° C for 2 hours. The powder of Example 7 was a hydrophobic powder having excellent water repellency and oil repellency. (Note 7)

[Chemical formula 23]

Example 8 A solution prepared by dissolving 8.0% by weight of fluorine-modified organohydrogenpolysiloxane (Note 8) in 52.0% by weight of methanol in 40.0% by weight of silicic acid anhydride was added and stirred, and methanol was distilled off at 70 ° C., then 180 Bake at 3 ° C for 3 hours. The powder of Example 8 was a hydrophobic powder having excellent water repellency and oil repellency. (Note 8)

[Chemical formula 24]

Example 9 White powder (1) Hydrophobic powder of Example 1 99.0% by weight (2) Squalane 1.0% by weight (3) Preservative proper amount (4) Perfume proper amount (production method) Hydrophobic powder of (1) Dissolved in the body at 80 ℃ (2) (3)
(4) was added, mixed with a Henschel mixer, and ground with a grinder to obtain a white powder.

Comparative Example 5 Comparative Example 5 was obtained in the same manner as in Example 9 except that the untreated mixed powder of Comparative Example 1 was used. The white powder of Example 9 was superior to the white powder of Comparative Example 5 in terms of adhesion and moisturization, and was a white powder with good makeup retention even when sweating, without losing makeup.

Example 10 Solid Foundation (1) Hydrophobic powder of Example 2 84.7% by weight (2) Lanolin 5.3% by weight (3) Liquid paraffin 5.3% by weight (4) Sorbitan sesquioleate 2.1% by weight (5) Stearin Acid 1.6 wt% (6) Triethanolamine 1.0 wt% (7) Preservative Appropriate amount (8) Perfume Appropriate amount (Production method) Add (6) to 50% of purified water and keep at 70 ° C to make water phase part. Mix (2) to (5) and (7), heat and dissolve to 70
Keep at ℃ and use as oil phase. Add the oil phase to the water phase and homogenize it with a homomixer. Add this to (1) and knead with a kneader, then evaporate the water and treat with a crusher. While stirring well (8) Was uniformly sprayed and compression molded to obtain a solid foundation.

Comparative Example 6 Comparative Example 6 was obtained in the same manner as in Example 10 except that the untreated mixed powder of Comparative Example 3 was used. The solid foundation of Example 10 is superior to the solid foundation of Comparative Example 6 in adhesion and moistness,
It was a solid foundation with good makeup retention even when sweating.

Example 11 Blusher (1) Hydrophobic powder of Example 3 93.6% by weight (2) Lanolin 2.9% by weight (3) Liquid paraffin 2.9% by weight (4) Sorbitan sesquioleate 0.6% by weight (5) Preservative Appropriate amount (6) Perfume Add appropriate amount (production method) (1) to (2) to (6) heated and dissolved at 80 ° C.,
The mixture was mixed with a Henschel mixer and ground with a grinder. A blusher was obtained by molding in a medium plate by compression molding.

Example 12 Oily foundation stick (1) Hydrophobic powder of Example 4 54.7% by weight (2) Squalane 32.3% by weight (3) Solid paraffin 5.0% by weight (4) Carnauba wax 3.0% by weight (5) Isopropylmillimeter State 5.0% by weight (6) Preservative Amount (7) Perfume Amount (manufacturing method) 5 parts of squalane is added to hydrophobic powder of (1) and uniformly dispersed with a homomixer, and further (1) to (2) and squalane. Heat and dissolve 6 parts, add to this, and add (7) and stir well. This was poured and cooled to obtain an oily foundation stick.

Example 13 Solid Eye Shadow (1) Hydrophobic powder of Example 5 93.3% by weight (2) Dimethylpolysiloxane (5000CS) 1.9% by weight (3) Squalane 1.9% by weight (4) Vaseline 1.9% by weight ( 5) Sorbitan trioleate 1.0% by weight (6) Preservative proper amount (7) Perfume proper amount (production method) Add (2) to the hydrophobic powder of (1) and mix for 70 minutes.
(3) to (6) are added to this, and (7) is further added, and they are mixed well with a blender. This was crushed with a crusher and compression molded to obtain a solid eye shadow.

Example 14 Cream (1) Hydrophobic powder of Example 6 38.5% by weight (2) Solid paraffin 4.6% by weight (3) Lanolin 9.4% by weight (4) Liquid paraffin 25.2% by weight (5) Sorbitan sesquioleate 4.6% by weight (6) Purified water 17.7% by weight (7) Perfume proper amount (8) Preservative proper amount (production method) Part of (4) and (5) were added to (1), and dispersed evenly with a mixer, ( The rest of (2), (3) and (4) and (7) and (8) were dissolved by heating and added to this, and the temperature was maintained at 70 ° C (oil phase).
(6) was heated to 70 ° C., added to the oil phase, uniformly emulsified and dispersed with a homomixer, and after emulsification, cooled to 40 ° C. with stirring to obtain a cream.

Example 15 Emulsion (1) 17.1 wt% hydrophobic powder of Example 7 (2) 2.0 wt% stearic acid (3) 0.4 wt% cetyl alcohol (4) 20.3 wt% liquid paraffin (5) Polyoxy Ethylene (10 mol) oleate 1.0 wt% (6) Sorbitan trioleate 1.0 wt% (7) Propylene glycol 5.0 wt% (8) Polyethylene glycol 5.0 wt% (9) Triethanolamine 1.0 wt% (10) Veegum 0.5 Weight% (11) Purified water 65.7% by weight (12) Pigment Suitable amount (13) Perfume Suitable amount (Production method) (1) Heat-dissolved (2) to (6) and (13) are added and uniformly dispersed with a homomixer. And keep it at 70 ° C (oil phase). Add (7) to (10) to (11) and heat and stir 70
Keep at ℃ (water phase). The oil phase was added to the aqueous phase, the mixture was uniformly emulsified and dispersed by a homomixer, and after emulsification, the mixture was cooled to 40 ° C. with stirring to obtain an emulsion.

Example 16 Cream (1) Hydrophobic powder of Example 8 1.6 wt% (2) Vaseline 4.3 wt% (3) Dimethylpolysiloxane (100CS) 3.1 wt% (4) Tri-2-ethylhexanoic acid Glyceryl 3.1 wt% (5) Liquid paraffin 10.9 wt% (6) Potassium stearate 2.1 wt% (7) POE (20) Cetyl alcohol 2.1 wt% (8) Glycerin 10.1 wt% (9) 1,3-Butylene glycol 5.1 % By weight (10) Purified water 56.6% by weight (11) Perfume Proper amount (production method) (2) to (5) and (11) are heated and dissolved to disperse (1) and maintain it at 70 ° C. to obtain an oil phase. (6) to (10) were melted by heating and kept at 70 ° C, an oil phase was added, and after emulsification, the mixture was stirred and cooled to 40 ° C to obtain a cream.

[0036]

The hydrophobic powder of the present invention has high hydrophobicity,
It is a powder that has no change in hydrophobicity over time and is highly oleophobic. In addition, cosmetics containing this hydrophobic powder are excellent in water resistance, sebum resistance and oil resistance, and have a long lasting makeup,
It is a cosmetic that has good adhesion to the skin and good usability.

─────────────────────────────────────────────────── --- Continuation of the front page (56) References JP-A-1-318070 (JP, A) JP-A-3-163172 (JP, A) JP-A-3-188012 (JP, A) JP-A-60- 163973 (JP, A) JP-A-2-295913 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) A61K ⁷ /00-7/50 C09C 3/00-3/12 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. One or more powders selected from inorganic powders and organic powders, containing at least one S in the molecule.
A hydrophobic powder which is characterized in that i-H group to a surface treatment with a fluorine-modified organohydrogenpolysiloxane having at least one perfluoroalkyl group, small in the molecule
At least one Si-H group and at least one perfluoro
Fluoro-modified organohydrogenpolysiloxane with alkyl group
Hexane is, the general formula (1): ## STR1 ## [Wherein R 1 represents a methyl group or a phenyl group, and
R 2 may be the same or different, R 2 is a methyl group or phenyl
Group, hydrogen, hydroxyl group or the same group as R 3 and the same as each other.
R 3 may be one or different, and R 3 is —R 4 —Rf (wherein R 3
4 represents a divalent alkylene group having 2 to 6 carbon atoms, and Rf is
It represents a perfluoroalkyl group having 1 to 12 carbon atoms . )
Represents an organic group represented by the formula, l and m and n are average numbers, and 1 =
0 to 50, m = 10 to 100, n = 1 to 100
It ] Hydrophobicity characterized by being a compound represented by
powder. 2. A cosmetic comprising the hydrophobic powder according to claim 1 incorporated therein.