JPH01182368A - Hydrophobic powder and cosmetic product containing same - Google Patents

Abstract

PURPOSE:To provide the title cosmetic product outstanding in water repellency, good in cosmetic retentivity and skin fitness, giving moderate humectant feel, thus favorable in usability, consisting mainly of hydrophobic powder prepared by surface treatment with a high-molucular weight silicone of specific formula. CONSTITUTION:The objective cosmetic product consisting mainly of hydrophobic powder prepared by surface treatment with a high-molecular weight silicone of the formula [R1 is CH3 or partially C6H5; R2 is CH3, OH or alkoxy; n is 3,000 to 20,000]. Optimally, the amount of said high-molecular weight silicone to be used be 1-10wt.% based on the powder.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a hydrophobic powder that can be used in cosmetics, paints, printing inks, etc., and cosmetics containing the same. More specifically, we will discuss powders with excellent hydrophobicity characterized by having the powder surface treated with high molecular weight silicone, and cosmetics containing the hydrophobic powders that have excellent makeup retention and usability. .

[Prior Art] There have been many known methods for making hydrophilic powders hydrophobic, and in particular, it is already well known to utilize the hydrophobic properties of silicone oil. For example, in Japanese Patent Publication No. 41-9890, lubricity is imparted to the powder by coating the surface of animal, plant, or mineral powder with a silicone resin paint and drying it by baking. In Japanese Patent Publication No. 45-2915, silicone, which has hydrogen that directly bonds with silicon in its molecular chain, is simply attached to mineral powder such as talc by mixing in a blender, etc., and then heated and baked to make the powder water repellent. is granted. In Japanese Patent Publication No. 45-18999, dimethylpolysiloxane or methylhydrodiene polysiloxane is dissolved in an organic solvent and then contacted and adhered to talc.
Thereafter, if necessary, zinc octoate or the like is added as a crosslinking polymerization catalyst for methylhydrodienepolysiloxane and baked, thereby imparting free-flowing properties to the powder. In Japanese Patent Publication No. 49-1769, titanium dioxide was coated directly with various alkylpolysiloxanes, an ester compound having a total carbon number of 6 or more was used as needed, and dry baking was performed to improve the dustability and dispersibility of the powder. quality. In Japanese Patent Publication No. 56-43264, a hydrophobic powder is produced by mechanochemically cross-linking and polymerizing methylhydrodiene poly and siloxane on the powder surface.

[Problems to be solved by the invention] The method using dimethylpolysiloxane found in the above patent does not have sufficient hydrophobicity, and the method using methylhydrodiene polysiloxane may cause reactions on the powder in some cases. The reaction progressed further over time, resulting in a change in hydrophobicity.

[Means for Solving the Problems] As a result of intensive research in order to solve these problems, the present inventors have found that by treating the surface of powder with high molecular weight silicone, it has excellent hydrophobicity, and that the hydrophobicity with time increases. It was discovered that a hydrophobic powder with little change in .

That is, the present invention is based on the following general formula (R1 represents a methyl group or a part of phenyl group, R2
represents a methyl group, a hydroxyl group or an alkoxy group. Also,
n is a number calculated from the number average molecular weight determined by gel permeation chromatography using polystyrene as a standard sample, and represents a number from 3,000 to 20,000. ) This is a hydrophobic powder characterized by surface treatment with high molecular weight silicone, and when this hydrophobic powder is blended into cosmetics, it has excellent water repellency, and its hydrophobicity (water repellency) increases over time. It has been found that a cosmetic can be obtained that has no problems such as the above, has little makeup smearing, has good adhesion to the skin, and has a moderately moist feeling.

The silicone used in the present invention has a high molecular weight and exhibits a soft rubber-like shape, such as high molecular weight dimethylpolysiloxane, methylphenylpolysiloxane, dimethylpolysiloxane containing a terminal hydroxyl group, methylphenylpolysiloxane containing a terminal hydroxyl group, and alkoxy-terminated silicone. Examples include dimethylpolysiloxane containing dimethylpolysiloxane and methylphenylpolysiloxane containing a terminal alkoxy group. Conventionally, silicone oil used for surface treatment of powder has a degree of polymerization of 3 to 2.000.
However, there are no examples of using high molecular weight silicone as in the present invention for surface treatment of powder.

The powder used in the present invention includes silicic acid, silicic anhydride, 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, navy blue, chromium oxide,
Inorganic powders such as chromium hydroxide, calamine and carbon black, and composites thereof, polyamide, polyester, polyethylene, polypropylene, polystyrene,
Polyurethane, vinyl resin, urea resin, phenol resin, fluororesin, silicone resin, acrylic resin, melamine resin, epoxy resin, polycarbonate resin, divinylbenzene-styrene copolymer, copolymer consisting of two or more monomers of the above compounds. Polymer, celluloid, acetyl cellulose, cellulose, chitin, chitosan, polysaccharide, protein, hard protein, CI pigment yellow, CI picment orange, CI picment red, CI pigment violet, CI pigment blue, CI pigment green and CI These include organic powders such as pigment brown, and composite powders of these inorganic powders and organic powders, and one or more of these may be selected and used.

Further, the shape of the above powder is not particularly limited, and may be plate-like, lump-like,
Any shape can be used, such as scaly, spherical, porous spherical, etc. Moreover, both porous and non-porous materials can be used.

The high molecular weight silicone of the present invention is used in an amount of 0.1 to 20% by weight, particularly preferably 1 to 10% by weight, based on one or more of the powders. If it is less than 0.1% by weight, water repellency tends to be poor, and if it exceeds 20% by weight, usability tends to be poor. Further, in this case, it is more preferable that the entire surface of the powder is coated with the polymer silicone, but water repellency can be obtained even if the powder is only partially coated.

Various commonly used processes can be employed for producing the hydrophobized powder. When adding high molecular weight silicone to powder, it is added by dissolving it in a suitable volatile solvent (e.g. volatile silicone, volatile isoparaffin, hexane, trichlorotrifluoroethane, chloroform, dichloromethane, etc.). It may be prepared by removing the volatile solvent by stirring or adding, mixing and leaving at room temperature or heating and drying, or it may be added directly without being dissolved in the solvent.

Furthermore, when it comes to mixing high molecular weight silicone and powder, commonly used methods can be used, and no special equipment is required, and stirring and mixing using mechanochemical methods can also be used, such as ball mills, hodgersite ball mills, vibration mixing, etc. The high molecular weight silicone and the powder can be mixed using a ball mill, vibratory rod mill, vibratory mill, attritor, bot mill, rod mill, pan mill, dryer, etc.

The amount of the hydrophobic powder thus obtained to be applied to the cosmetic composition of the present invention is usually about 1 to 99% by weight.

[Effects of the Invention] The present invention relates to a hydrophobic powder whose surface is treated with a high molecular weight silicone and a cosmetic containing the hydrophobic powder. It is a cosmetic that is easy to use because it is highly water-based and has little change in water repellency over time, and has good makeup retention as it does not cause makeup smearing, has good adhesion to the skin, and has a moderately moisturizing feel. .

In addition to cosmetics, the hydrophobic powder of the present invention can also be used as an inorganic additive for paints, printing inks, plastics (reinforcing materials, colorants, etc.),
Inorganic additives for rubber (mainly adhesives): Can be widely used for magnetic tapes (magnetic iron oxide), lubricants, etc.

[Example] The present invention will be explained in more detail below by way of examples.

Example 1 Dimethylpolysiloxane (R1 and R2 are methyl groups,
n = 7,000) was dissolved in 200 parts of trichlorotrifluoroethane at room temperature to prepare a treatment solution. Fifty parts of talc were mixed and stirred in a Henschel mixer at room temperature while gradually adding the above treated solution. After the addition of the treatment liquid was completed, a temperature control was applied to the jacket part of the Henschel mixer, and the temperature was raised to about 60° C. While mixing for 30 minutes, trichlorotrifluoroethane was removed and recovered to obtain hydrophobized talc.

Example 2 Dimethylpolysiloxane (R1 and R2 are methyl groups,
n = 5,000) was dissolved in 100 parts of volatile isoparaffin at room temperature to prepare a treatment solution. Kaolin 5
0 parts were mixed in a ball mill at room temperature while gradually adding the above treated solution. After the addition of the treatment liquid was completed, the kaolin was taken out and left at room temperature for 3 days to remove volatile isoparaffins to obtain hydrophobized kaolin.

Example 3 A treatment solution was prepared by dissolving 3 parts of dimethylpolysiloxane containing a terminal hydroxyl group (R1 is a methyl group, R2 is a hydroxyl group, n = 10,000) in 200 parts of trichlorotrifluoroethane at room temperature. 50 parts of titanium oxide were mixed in a Henschel mixer at room temperature while gradually adding the above treatment solution. After adding the treatment liquid, take out the powder and store it at room temperature.
Trichlorotrifluoroethane was removed by leaving the mixture for days to obtain hydrophobized titanium oxide.

Next, in order to show the superiority of the method of the present invention, the results of comparing the hydrophobized powder obtained by the method of the present invention and the raw material powder without treatment are shown in Table 1. [Sample] (Treatment powder) Hydrophobized talc (Example 1) Hydrophobized kaolin (Example 2) Hydrophobization titanium oxide (Example 3) (Untreated powder) Untreated talc (Comparative amount 1) Untreated kaolin (Comparative amount 2) Untreated titanium oxide (Comparative amount 3) [Method] Weighed 0.5 g of the above sample powder, placed it in a test tube containing 10 ml of water, and after shaking. , and allowed to stand for 1 hour. Next, the powder floating in the upper layer and the untreated powder settling in the lower layer were separated, dried, and their weights were measured to calculate the ratio.

Table 1 As is clear from the results in Table 1, the hydrophobized powder obtained by the method of the present invention is superior in water repellency to untreated powder.

Example 4 Methylphenylpolysiloxane (10% of Rt is phenyl group, the rest is methyl group, R2 is methyl group, n -15,
000) was dissolved in 50 parts of volatile silicone at room temperature to prepare a treatment solution. After adding the treatment liquid to 50 parts of red red iron, the mixture was mixed and stirred in a bot mill for 1 hour. Thereafter, the powder was heated to about 80° C. to remove volatile silicone to obtain hydrophobized red iron oxide.

Example 5 Methylphenylpolysiloxane containing a terminal hydroxyl group (5% of R1 is a phenyl group, the rest is a methyl group, R2 is a hydroxyl group, n
-20,000) was dissolved in 30 parts of dichloromethane to prepare a treatment liquid. To a composite powder obtained by mixing 40 parts of nylon and 10 parts of titanium oxide in a vibration mill, the above treatment liquid was gradually added and mixed and stirred in a vibration mill for 1 hour. Thereafter, the powder was taken out and left at room temperature for 2 days to remove the solvent and obtain a hydrophobized composite powder.

Example 6 Dimethylpolysiloxane (R1 and R2 are methyl groups,
n = 3,000) was dissolved in 100 parts of trichlorotrifluoroethane to prepare a treatment solution. Fifty parts of zinc oxide were mixed and stirred in a Henschel mixer while gradually adding the above treated solution. After adding the processing liquid, the temperature is controlled in the jacket part of the Henschel mixer to approximately 60℃.
Trichlorotrifluoroethane was removed and recovered while stirring for 30 minutes to obtain hydrophobized zinc oxide.

Example 7 White powder (1) Hydrophobized talc of Example 1 93.0%
(2) Squalane 1.5 (
3) Sorbitan sesquiolate 0.5 (4) Carboxymethyl cellulose (1% aqueous solution) 5.0 (5) Pigment appropriate amount (6)
Method for making 1 amount of fragrance: Mix (1) and (5) well in a blender, and add (3)
) Dissolve (6) in (2) and add it evenly to this, and then add (4) evenly thereto, then process with a pulverizer and compression mold.

Comparative Example 4 Comparative Example 4 was obtained in the same manner as in Example 7, except that the hydrophobized talc in Example 7 was replaced with untreated talc that was not treated with polymeric silicone.

The white powder of Example 7 was superior to the white powder of Comparative Example 4 in terms of adhesion and moisturizing properties, and had good makeup retention.

Example 8 Solid white powder (1) Hydrophobized talc of Example 1 74. Oχ
(2) Hydrophobized kaolin of Example 2 10.0 (
3) Hydrophobized titanium oxide of Example 3 5.0 (4)
Liquid paraffin 3.0 (5) Sorbitan sesquiolate 2.0 (6) Lanolin
4.0(7) Propylene glycol 2.0(8) Pigment
Appropriate amount (9) Fragrance
How to make: (1), (2), (3), and (8) while stirring well in a blender. Then, add the IJ mixture to the mixture, process it in a crusher, and compression mold it.

Comparative Example 5 Comparative Example 5 was obtained in the same manner as in Example 8, except that the hydrophobized talc, hydrophobized kaolin, and hydrophobized titanium oxide in Example 8 were replaced with untreated talc, kaolin, and titanium oxide, respectively.

The solid white powder of Example 8 had better makeup retention than the solid white powder of Comparative Example 5, and had excellent adhesion and moisturizing properties.

Example. 9 is red (1) mica 9.0% (
2) Talc 19.8 (3
) Red No. 226 0.2 (4
) Iron oxide (red, yellow, black) 0.6 (5) Ultramarine 0.2 (6
) deca, methylcyclopentasiloxane 66.0 (7
) Dimethylpolysiloxane (Ih and R2 are methyl groups n = 7,000) 2.0 (
8) Lanolin 1.0 (9)
) Liquid paraffin 1.0 (10)
Sorbitan Sesquiolate 0.2 (11) Preservative
Appropriate amount (12) Incense N
3afi manufacturing method> After mixing (1) to (5) with a Henschel mixer, (
Add 7) dissolved in (6) and add (6) while stirring.
) is distilled off and heated at 180-200°C for 2 hours. (8)-(
12) was added, mixed with a Henschel mixer, crushed with a crusher, and then molded into a medium plate by compression molding.

Comparative Example 6 Comparative Example 6 was prepared in the same manner as Example 9 except that dimethylpolysiloxane was removed. The blusher of Example 9 had better makeup retention than the blusher of Comparative Example 6. It had excellent adhesion and firmness.

Example 10 Oil-based foundation stick (1) Mica 5.6% (2) Talc 3.5 (3) Kaolin 3.4 (4) Titanium coated mica 0.7 (5) Titanium dioxide
1.0 (6) Iron oxide (red, yellow, black) 1.4 (7) Dichloromethane 66.0 (
8) Methylphenylpolysiloxane (10% of R1 is phenyl group, the rest is methyl group, R2 is methyl group, n = 15,000) 3.0
(9) Squalane 11.0 (
10) Solid paraffin 1.7 (1
1) Carnauba Rou 1.0 (12
) Isopropyl myristate 1.7 (13) Preservative
Appropriate amount (14) Fragrance
Manufacturing method: Mix (1) to (6) in a Henschel mixer, then (
Add (8) into the dissolved (7) and add (7) while stirring.
is distilled off to create a hydrophobic powder. Add 5 parts of squalane to this hydrophobic powder, disperse it evenly with a homomixer, and then add (1 part of squalane).
0) to (13), 6 parts of squalane are heated and dissolved, and added to this, and (14) is added and stirred well. Pour this in and cool it.

Comparative Example 7 Comparative Example 7 was obtained in the same manner as in Example 10, except that methylphenylpolysiloxane was replaced with the same amount of dimethylpolysiloxane (100C3).

The oil-based foundation stick obtained in Example 10 had better makeup retention than the oil-based foundation stick of Comparative Example 7, and was excellent in adhesion and moisture.

Example 11 Solid eyeshadow (1) Mica 12.5%
(2) Talc 18.0 (
3) Titanium coated mica 2.5 (4
) Iron oxide (red, yellow, black) 1.0 (5) Ultramarine 5.0 (6
) Deep blue 7.5 (7) Dimethylpolysiloxane containing terminal hydroxyl groups (R1 is methyl group, R2 is hydroxyl group, n = 10,000) 2
．． 5(8) Hexane 47
．． 5(9) Dimethylpolysiloxane (toocs)
i.

(10) Squalane 1.0 (
11) Vaseline 1.0 (1
2) Sorbitantriolate 0.5 (13) Preservative
Appropriate amount (14) Fragrance
3! i Weighing method> After mixing (1) to (6) with a Henschel mixer, (
Add (7) to the dissolved (8) and add (8) while stirring.
is distilled off to create a hydrophobized powder. Add (9) to this powder,
Mix and grind for 70 minutes in a vibrating ball mill. To this (10
) to (13) are heated and dissolved, added, and mixed well with a blender. This is crushed using a crusher and compression molded.

Comparative Example 8 Comparative Example 8 was obtained in the same manner as in Example 11 except that the terminal hydroxyl group-containing dimethylpolysiloxane was removed.

The solid eyeshadow obtained in Example 11 had better makeup retention than the eyeshadow mill in Comparative Example 8, and was excellent in adhesion and moisture.

Example 12 Cream (1) Hydrophobized talc of Example 1 15.0%
(2) Hydrophobized kaolin 4.2 (
3) Hydrophobized titanium oxide of Example 3 6.0 (4)
Solid paraffin 5.7 (5) Lanolin 10.4 (6) Liquid paraffin 30.0 (7) Sorbitan sesquiolate 4.7 (8) Purified water
24.0(9) Pigment
Appropriate amount (10) fragrance
Appropriate amount (11) Preservatives
Appropriate amount (Production method) Add part of (6) and (7) to (1) to (3) and (9), and use a Henschel mixer to uniformly disperse 4), (5), (
The remainder of step 6), (10) and (11), were melted by heating and added to this, and kept at 70°C (oil phase). (8) was heated to 70°C, added to the oil phase, and uniformly emulsified and dispersed using a homomixer. After emulsification, the mixture was cooled to 40°C while stirring to obtain a cream.

Comparative Example 9 Comparative Example 9 was carried out in the same manner as in Example 12, except that the hydrophobized talc, hydrophobized kaolin, and hydrophobized titanium oxide in Example 12 were replaced with untreated talc, kaolin, and titanium oxide that were not treated with polymer silicone. I got it.

The cream of Example 12 had better adhesion and moisturizing properties than the cream of Comparative Example 9, and had good makeup retention.

Example 13 Emulsion (1) Hydrophobized talc of Example 1 5.2% (
2) Hydrophobized kaolin of Example 2 3.6 (3)
Hydrophobized titanium oxide of Example 3 5.2 (4) Stearic acid 1.7 (5) Cetyl alcohol 0.3 (6) Liquid paraffin 22.4 (7) Polyoxyethylene (10 mole addition) oleate ester
1.4 (8) Sorbitan triolate 1.4 (9) Propylene glycol 6.3 (1
0) Polyethylene glycol 4000 6.3 (
11)) Reethanolamine 0.9 (
12) Veegum 0.4 (1
3) Purified water 44.9 (14
) Pigment (appropriate amount) (15) Fragrance (appropriate amount) (16) Preservative (appropriate amount) Production method> (1) to (3) and (14) were mixed in a Henschel mixer, and then heated and dissolved in the mixture (4) to (8), ( 15)
, (16) was added, dispersed uniformly with a homomixer, and heated to 70°C.
(oil phase). Add (9) to (12) to (13), heat and stir, and maintain at 70°C (aqueous phase). The oil phase was added to the water phase and uniformly emulsified and dispersed using a homomixer. After emulsification, the mixture was cooled to 40° C. while stirring to obtain a milky lotion.

Comparative Example 10 The same procedure as in Example 13 was carried out except that the hydrophobized talc, hydrophobized kaolin, and hydrophobized titanium oxide in Example 13 were replaced with untreated talc, kaolin, and titanium oxide that had not been treated with polymer silicone. Comparative Example 10 was obtained.

The emulsion of Example 13 had better adhesion and moisturizing properties than the emulsion of Comparative Example 10.

Claims (1)

[Scope of Claims] 1) A hydrophobic powder characterized by being surface-treated with a high molecular weight silicone represented by the following general formula. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R_1 represents a methyl group or a part of it is a phenyl group, and R
_2 represents a methyl group, a hydroxyl group, or an alkoxy group. Further, n represents a number from 3,000 to 20,000. ) 2) A cosmetic comprising a hydrophobic powder obtained by surface treatment with a high molecular weight silicone represented by the following general formula. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R_1 represents a methyl group or a part of it is a phenyl group, and R
_2 represents a methyl group, a hydroxyl group, or an alkoxy group. Further, n represents a number from 3,000 to 20,000. ).