JP2000136115A - Powder treated with silicon compound and cosmetic containing the powder - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain powder for cosmetic use giving a moisture-retention feeling preferable as cosmetics and free from the lowering of the potency to give moisture-retention feeling by the moisture evaporated from human body by treating a powdery material with a specific silicon compound. SOLUTION: A powdery material (preferably titanium oxide, etc.), is treated with (A) a silicon compound (preferably having hydroxyl group) produced by bonding (i) a polysiloxane or a silane to (ii) a natural hydrophilic substance and preferably further with (B) a silicon compound producing a silanol hydroxy group by hydrolysis (concretely, methyltriethoxysilane, etc.). Preferably, the powder is treated with a polycondensation product produced by the polycondensation of the component A and the component B, the component (ii) is a polyamino acid, a polysaccharide or a hydrolyzed protein and the component A is a silylated peptide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a powder treated with a silicon compound and a cosmetic containing the same.
More specifically, the present invention relates to a powder treated with a silicon compound in which a natural hydrophilic substance and polysiloxane or silane are combined, and a cosmetic containing the powder.

[0002]

2. Description of the Related Art Conventionally, foundations, white powder,
Cosmetics containing powder, such as makeup cosmetics such as blusher, eyeshadow and eyebrow, and body cosmetics such as body powder and baby powder (hereinafter referred to as powder cosmetics. Liquid cosmetics containing powder are also included in the powder cosmetics referred to herein.)) Are commercially available. However, regarding these powder cosmetics, various problems such as elongation on the skin, smoothness, lack of moist feeling and moisturizing feeling, and makeup collapse have been pointed out.
The solution is desired, and various solutions have been considered. Powder cosmetics include inorganic pigments such as titanium oxide, iron oxide, ultramarine, zinc oxide, magnesium oxide, talc, kaolin, sericite, silica, mica, chromium hydroxide, carbon black, nylon powder, and polymethyl methacrylate. , A styrene-divinylbenzene copolymer, a polyethylene powder, an organic powder such as a fish scale foil, an organic dye, and a polymethyl sesquisyl osane powder. However, these powders do not themselves have a moisturizing feeling. Therefore, when these are blended into cosmetics, it is necessary to blend them with other materials that impart a moisturizing feeling in order to give a moisturizing feeling.

[0003] As a method of blending another material for imparting a moisturizing feeling, the surface of the powder is usually treated with a material for imparting a moisturizing feeling, that is, the powder is treated with a water-soluble substance or a hydrophilic substance. A method of covering the surface is generally used. However, simply covering the powder surface with a water-soluble substance or a hydrophilic substance will wash away the water-soluble substance or the hydrophilic substance due to moisture radiating from the human body, and these substances will be separated from the powder itself. Thus, there is a problem that a sufficient moisturizing feeling cannot be provided.

Therefore, a method of treating the above powder with a silicon compound in which a synthetic hydrophilic substance such as polyether-modified polysiloxane or polyether-modified silane is combined with polysiloxane or silane has been proposed. However, it was not satisfactory as to the favorable feel of the product. Titanium oxide and zinc oxide have a catalytic activity of decomposing organic substances in contact with light when irradiated with light in the presence of oxygen. This catalytic activity is particularly great when used in powders due to the increased surface area. Due to this catalytic activity, titanium oxide and zinc oxide mixed in powder cosmetics have a problem of destroying and coloring vitamin C, which is often used in cosmetics, and a solution to this problem is also desired.

[0005]

PROBLEM TO BE SOLVED BY THE INVENTION A powder for a powdery cosmetic which gives a moisturizing sensation with a favorable feel as a cosmetic and which does not reduce the ability to give a moisturizing sensation due to moisture radiated from the human body It is an object of the present invention to provide a powder cosmetic composition containing the same. Further, when a powder of titanium oxide or zinc oxide is used as the powder, it is possible to provide a powder which reduces the catalytic activity and does not cause a problem such as coloring, and a cosmetic containing the powder. It is an issue.

As a result of intensive studies, the present inventors have found that these problems can be solved by treating powders for powder cosmetics with a silicon compound in which a natural hydrophilic substance and polysiloxane or silane are combined. The present invention has been completed.

[0007]

That is, the present invention provides a powder treated with a silicon compound in which a natural hydrophilic substance and polysiloxane or silane are bonded. The present invention further provides a powder cosmetic containing a powder treated with a silicon compound in which a natural hydrophilic substance and polysiloxane or silane are combined.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION As a natural hydrophilic substance used in the present invention, that is, a natural hydrophilic substance which binds to polysiloxane or silane, polyamino acids, polysaccharides and hydrolyzed proteins are exemplified. In particular, hydrolysable proteins such as hydrolysable collagen, hydrolysable keratin, hydrolysable silk protein, hydrolysable casein, hydrolysable soybean protein, and hydrolysable wheat protein are typical examples. That is, as a silicon compound in which a natural hydrophilic substance and polysiloxane or silane are bonded, a silylated polypeptide is a typical example. As silylated polypeptides, JP-A-8
And Japanese Patent Application Laid-Open No. Hei 8-67608.

The polysiloxane or silane that forms a silicon compound by combining with a natural hydrophilic substance includes 3-chloropropyltrimethoxysilane, 3-triethoxysilylpropylsuccinic anhydride and epoxy-modified silane such as β- (3 4,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane and the like.

[0010] Methods for producing a silicon compound for treating a powder by combining a natural hydrophilic substance with polysiloxane or silane are described in JP-A-8-59424 and JP-A-8-67608. The methods that are being illustrated

The powder to be treated with a silicon compound in which a natural hydrophilic substance and polysiloxane or silane are bonded is not particularly limited as long as it is a substance substantially insoluble in water and oil. , Iron oxide, ultramarine, zinc oxide, magnesium oxide, talc, kaolin,
Inorganic pigments such as sericite, silica, mica, chromium hydroxide, and carbon black; nylon powder; polyacryl such as polymethyl methacrylate; styrene-divinylbenzene copolymer; polyethylene powder; Dyes and methyl siloxane are exemplified. The particle size of the powder is not particularly limited, but in order to obtain an excellent feel as a cosmetic, 0.01 to 80 μm
m, particularly preferably 0.05 to 20 μm.

[0012] The treatment of the powder is performed by using a natural hydrophilic substance and a policy.
A silicon compound with loxane or silane alone
However, hydrolysis with this silicon compound
Perform with silicon compounds that generate lanolic hydroxyl groups.
Both are possible. In this case, the natural hydrophilic compound binds
The ratio of the silicon compound to the total silicon compound
The number of moles of the compound is 0.3% or more, preferably 0.5% or more.
〜１０10%. Hydrolysis of silanolic hydroxyl groups
As a silicon compound to be generated, methyltriethoxysila
, Methyltrimethoxysilane, methyltrichlorosila
Dimethyldiethoxysilane, dimethyldimethoxysilane
Orchid, dimethyldichlorosilane, phenyltriethoxy
Silane, phenyltrimethoxysilane, phenyltric
Lorosilane, hexyltriethoxysilane, hexylt
Limethoxysilane, hexyltrichlorosilane, Octi
Rutriethoxysilane, octyltrimethoxysilane,
Octyltrichlorosilane, decyltriethoxysila
, Decyltrimethoxysilane, decyltrichlorosila
, Tetraethoxysilane, trimethylchlorosilane,
Hexamethyldisilazane, hexamethyldisiloxane and
And perfluoroalkyltrimethoxysilane
A run is exemplified.

When the treatment of the powder is carried out using a silicon compound in which a natural hydrophilic substance and a polysiloxane or silane are combined with a silicon compound which forms a silanol hydroxyl group by hydrolysis, the natural hydrophilic substance is used in advance. A method is also possible in which a silicon compound in which a substance is bonded to polysiloxane or silane and a silicon compound that generates a silanol hydroxyl group by hydrolysis are polycondensed, and a powder is treated with the obtained polycondensate. In this case, the silicon compound in which a natural hydrophilic substance and polysiloxane or silane are bonded must have a silanol type hydroxyl group. Also in this case, the ratio of the silicon compound to which the natural hydrophilic compound is bonded to the total silicon compound is 0.3% or more, preferably 0.5 to 10%, in moles of the silicon compound. Examples of the silicon compound which generates a silanol hydroxyl group by hydrolysis are the same as those described above.

A method of treating powder with a silicon compound to which a natural hydrophilic substance is bound alone, a combination of a silicon compound to which a natural hydrophilic substance is bound and a silicon compound which forms a silanol hydroxyl group by hydrolysis. A method of treating powder, or a polycondensate obtained by polycondensation of a silicon compound having a hydroxyl group and a silicon compound having a hydroxyl group and a silanolous hydroxyl group formed by hydrolysis, which is bonded to a natural hydrophilic substance There is no particular limitation on the method of treating the powder by the method. For example, a method in which a silicon compound or a condensation polymer is dissolved in a solvent in which a powder to be treated is dispersed and heated to react the surface of the powder with the silicon compound or the condensation polymer is exemplified.

The powder cosmetic of the present invention is a cosmetic containing the powder treated as described above. The powder cosmetic of the present invention is obtained by subjecting the surface of a powder selected from an inorganic powder and an organic powder to hydrophobic treatment together with the treated powder of the present invention. Things can be blended.

As a method of hydrophobizing the surface of the powder to obtain the hydrophobized powder, for example, a method of adsorbing fats and oils on the surface of the powder, esterification or etherification using a functional group such as a hydroxyl group, etc. Fats and oils to make the powder lipophilic, metal soap treatment using zinc and magnesium salts of fatty acids, silicone treatment using dimethyl polysiloxane or methyl hydrogen polysiloxane, fluorine having a perfluoroalkyl group Examples of the method include treatment with a compound.

Here, the fluorine compound having a perfluoroalkyl group includes a perfluoroalkyl phosphate ester (described in US Pat. No. 3,632,744) and a resin having a perfluoroalkyl group (JP-A-55-16).
7209), perfluoroethylene resin, perfluoroalcohol, perfluoroepoxy compound, perfluorocarboxylic acid, perfluorosulfate, perfluoroalkylsilane (described in JP-A-2-218603) and the like. Can be

The powder to be treated to obtain the hydrophobized powder is not particularly limited as long as it is substantially insoluble in water and oil. For example, titanium oxide, iron oxide, ultramarine,
Inorganic pigments such as zinc oxide, magnesium oxide, mica, sericite, talc, silica, kaolin, chromium hydroxide, carbon black, nylon powder, polyacryl such as polymethyl methacrylate, styrene-divinylbenzene copolymer, polyethylene powder And organic powders such as fish scale foil, organic pigments, ultraviolet absorbers and the like.
These powders can be used alone or in combination of two or more. The particle size of the powder is not particularly limited, but in order to obtain an excellent feel as a cosmetic, 0.01 to 80 μm
m, particularly preferably 0.05 to 20 μm.

The cosmetic of the present invention further comprises other components which are usually incorporated in cosmetics, for example, vaseline, lanolin,
Ceresin, microcrystalline wax, carnauba wax, candelilla wax, higher fatty acids, solids such as higher alcohols, semi-solid oils, skrawan, liquid paraffin, ester oils, diglycerides, triglycerides,
Fluid oils such as silicone oils, fluorinated oils such as perfluoropolyether, perfluorodecalin and perfluorooctane, water-soluble and oil-soluble polymers, surfactants, inorganic and organic pigments, coloring agents such as organic dyes, pigments, Ethanol, preservatives, antioxidants, thickeners, pH adjusters, fragrances, UV absorbers, humectants, blood circulation promoters, cooling agents, antiperspirants, bactericides, skin activators, etc. It can be blended as long as the effect is not impaired.

The cosmetics of the present invention can be produced according to a usual method, and make-up cosmetics such as foundation, white powder, blusher, eyeshadow, eyebrow, body cosmetics such as body powder and baby powder, milky lotions and creams It can be applied to basic cosmetics and the like. The content of the treated powder of the present invention in the cosmetic is from 1 to 60 in the case of a press-up makeup cosmetic.
% By weight, and preferably 0.1 to 40% by weight in the case of a liquid makeup cosmetic.

[0021]

EFFECTS OF THE INVENTION The powder of the present invention and a cosmetic containing the same provide a moisturizing sensation that is preferable as a cosmetic, and the ability to give a moisturizing sensation due to moisture radiated from the human body is not reduced. . Furthermore, the powder of the present invention comprising titanium oxide or zinc oxide and cosmetics containing the same have reduced catalytic activity of titanium oxide and zinc oxide, and thus have problems such as coloring of vitamin C. Will not occur.

[0022]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but these examples are described only for explanation and do not limit the scope of the present invention. All percentages are by weight unless otherwise indicated.

Test 1 A solution of vitamin C saturated with 50% ethanol is prepared (hereinafter referred to as "test liquid C"). 10m of test liquid C
Approximately 1 mg of the powder to be tested is added to 1 and shaken, and then allowed to stand. The surface of the insoluble matter and the coloring of the solution are observed over time. (If it has catalytic activity, it will turn brown)

Example 1 Treatment of titanium oxide with N- [2-hydroxy-3- (3'-dihydroxymethylsilyl) propoxy] propyl hydrolyzed collagen Round bottom provided with a dropping funnel, reflux condenser and mechanical stirrer on the top lid Titanium oxide (average particle size 0.02 micron, manufactured by Nippon Aerosil Co., Ltd., P-2) was placed in a cylindrical glass reaction vessel.
5) 5 g and 300 ml of toluene were added, and the mixture was heated to reflux. There, N- [2-hydroxy-3- (3'-
Dihydroxymethylsilyl) propoxy] propyl hydrolyzed collagen (molecular weight of hydrolyzed collagen is about 2,000 in number average molecular weight) dissolved in 18 g of water was added from a dropping funnel, and the mixture was refluxed for 30 minutes.
10 ml of hydrochloric acid was added and the mixture was refluxed for 90 minutes. Replace the Dean-Stark dehydrator in which the equivalent amount of calcium carbonate sufficient to neutralize the used hydrochloric acid is placed in the drainage tank with a reflux condenser, add 50 ml of toluene, reflux for about 120 minutes, and remove from the Dean-Stark dehydrator. The water in the reaction system was removed. After cooling, the mixture was subjected to suction filtration, washed with a small amount of toluene, and collected by filtration. After drying under reduced pressure, 7 g of treated titanium oxide (sample T1
And). When Test 1 was performed on Sample T1, no coloration of the insoluble surface and the solution was observed even after 24 hours.

Example 2 Treatment of titanium oxide with N- [2-hydroxy-3- (3'-dihydroxymethylsilyl) propoxy] propyl hydrolyzed collagen and tetraethoxysilane A dropping funnel, a reflux condenser and a mechanical stirrer were placed on the upper lid. Titanium oxide (average particle size 0.02 micron, manufactured by Nippon Aerosil Co., Ltd., P-2)
5) 5 g, 9 g of tetraethoxysilane and 300 ml of ethanol were added, and the mixture was heated to reflux. There, N-
[2-Hydroxy-3- (3'-dihydroxymethylsilyl) propoxy] propyl hydrolyzed collagen (molecular weight of hydrolyzed collagen is about 2,000 in number average molecular weight)
A solution prepared by dissolving 0.5 g in 4.5 g of water was added from a dropping funnel and then refluxed for 30 minutes. Subsequently, 10 ml of 0.5N hydrochloric acid was added and the mixture was refluxed for 90 minutes. A Dean-Stark dehydrator, in which a sufficient amount of calcium carbonate is placed in a drainage basin to neutralize the used hydrochloric acid, is replaced with a reflux condenser, a water-ethanol azeotrope is distilled off, and water in the reaction system is removed. Removed. After cooling, the mixture was filtered by suction, washed with a small amount of ethanol, and collected by filtration. After drying under reduced pressure, 7 g of treated titanium oxide (sample T2
And). When Test 1 was performed on Sample T2, no coloration of the insoluble material surface or the solution was observed even after 24 hours.

Example 3 Treatment of titanium oxide with N- [2-hydroxy-3- (3'-dihydroxymethylsilyl) propoxy] propyl hydrolyzed collagen, tetraethoxysilane and methyltriethoxysilane 5 g of titanium oxide and tetraethoxysilane 9 g of treated titanium oxide (referred to as sample T3) was obtained in the same manner as in Example 2 except that 9 g of methyltriethoxysilane was further added when 9 g was added. Test 1 on sample T3
, The surface of the insoluble material and the coloring of the solution were not observed even after 24 hours.

Example 4 Hydrolysis of titanium oxide with N- [2-hydroxy-3- (3'-dihydroxymethylsilyl) propoxy] propyl Hydrogen Collagen, treatment with tetraethoxysilane, methyltriethoxysilane and phenyltriethoxysilane Titanium oxide Example 2 except that when adding 5 g and 9 g of tetraethoxysilane, an additional 9 g of methyltriethoxysilane and 1.8 g of phenyltriethoxysilane were added.
10 g of treated titanium oxide (sample T4
And). When Test 1 was performed on Sample T4, the surface of the insoluble matter and the coloring of the solution were not observed even after 24 hours.

Example 5 Method of Preparing Polymer and Preparing Powder There was previously added 4.5 g of water to a round-bottom cylindrical glass reaction vessel equipped with a dropping funnel and a reflux condenser on the top lid and equipped with a mechanical stirrer. Add 0.5 g of N- [2-hydroxy-3- (3'-trihydroxysilyl) propoxy] propyl hydrolyzed collagen (the molecular weight of the hydrolyzed collagen is about 2000 in number average molecular weight) and 0.2 ml of 18% hydrochloric acid. Then, a mixture of 9 g of tetraethoxysilane, 9 g of methyltriethoxysilane and 1.8 g of phenyltriethoxysilane was dropped from the dropping funnel while stirring at 50 ° C. Further, after stirring at 50 ° C. for 6 hours, the mixture was cooled to 20 ° C. and about 0.1 g of a 25% aqueous sodium hydroxide solution was added dropwise while stirring to adjust the pH to 7.0. Then, 20
Stirred at C for 1 hour. Thereafter, 5 g of titanium oxide and 300 ml of toluene were added, stirred at 20 ° C. for 1 hour, and heated to reflux. Replace the Dean-Stark dehydrator in which the equivalent amount of calcium carbonate sufficient to neutralize the used hydrochloric acid is placed in the drainage tank with a reflux condenser, add 50 ml of toluene, reflux for about 120 minutes, and remove from the Dean-Stark dehydrator. The water in the reaction system was removed. After cooling, the mixture was subjected to suction filtration, washed with a small amount of toluene, and collected by filtration. After drying under reduced pressure,
10 g of a treated titanium oxide (sample T5) was obtained. When Test 1 was performed on Sample T5, the surface of the insoluble matter and the coloring of the solution were not observed even after 24 hours and 72 hours.

Example 6 In Example 5, N- [2-hydroxy-3- (3'-
N- [2-hydroxy-3] instead of trihydroxysilyl) propoxy] propyl hydrolyzed collagen (the molecular weight of the hydrolyzed collagen is about 2,000 in number average molecular weight)
-(3'-trihydroxysilyl) propoxy] propyl hydrolyzed sericin (the molecular weight of hydrolyzed sericin is about 2,000 in number average molecular weight) in the same manner as in Example 5, except that 10 g of the treated titanium oxide (sample T6). When Test 1 was performed on Sample T6,
Even after 24 hours and 72 hours, no coloration of the surface of the insoluble material or the solution was observed.

Example 7 In the same manner as in Example 5 except that 1.8 g of octyltriethoxysilane was used instead of 1.8 g of phenyltriethoxysilane, 10 g of treated titanium oxide (referred to as sample T7) was used. Obtained. When Test 1 was performed on Sample T7, the surface of the insoluble matter and the coloring of the solution were not observed even after 24 hours and 72 hours.

Example 8 10 g of treated zinc oxide (sample Z8) was prepared in the same manner as in Example 5 except that 5 g of zinc oxide (MZO-350, manufactured by Sumitomo Osaka Cement Co., Ltd.) was used instead of 5 g of titanium oxide.
And). When Test 1 was performed on Sample Z8, the surface of the insoluble matter and the coloring of the solution were not observed even after 24 hours and 72 hours.

COMPARATIVE EXAMPLE 1 When untreated titanium oxide was subjected to test 1, remarkable coloring was immediately observed.

COMPARATIVE EXAMPLE 2 When untreated zinc oxide was subjected to test 1, significant coloration was immediately observed.

Example 9 10 g of treated silica was prepared in the same manner as in Example 5, except that 5 g of silica powder (Silica Microbead P-1500, manufactured by Catalyst Chemical Industry Co., Ltd.) was used instead of 5 g of titanium oxide. A powder (referred to as sample S9) was obtained.

Example 10 Instead of 5 g of titanium oxide, 5 g of methylsiloxane powder
9 g of tetraethoxysilane, 9 g of methyltriethoxysilane, and 1.8 g of phenyltriethoxysilane using Tospearl 120A (manufactured by Toshiba Silicone Co., Ltd.).
Except that g was not used, in the same manner as in Example 5,
5.5 g of treated methylsiloxane powder (sample S10
And).

REFERENCE EXAMPLE 1 Samples T1 to T7 and untreated titanium oxide were compared for moisturizing feeling and moist feeling using 20 panelists. The processed samples, ie T1-T
7 shows the number of people who answered that the moisturizing feeling and moist feeling were excellent (the processing line in the table) and the number of people who answered that the untreated titanium oxide was better (the untreated line in the table). It is shown in the table below.

[Table 1]

REFERENCE EXAMPLE 2 Sample Z8 and untreated zinc oxide showed a moist feeling,
The moist feeling was compared using 20 panelists. Z8
The table below shows the number of respondents who answered that N was excellent (treated row in the table) and the number of those who answered that untreated zinc oxide was superior (untreated row in the table).

[Table 2]

REFERENCE EXAMPLE 3 Samples S9 and S10 were compared with untreated silica powder and methylsiloxane powder, respectively, for a moisturizing feeling and a moist feeling using 20 panelists. S9, S10
The table below shows the number of respondents who answered that the sample was excellent (processed row in the table) and the number of people who answered that the untreated sample was better (unprocessed row in the table).

[Table 3]

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4C083 AA021 AA072 AB171 AB172 AB211 AB212 AB241 AB242 AB431 AB441 AC911 AC912 AD071 AD091 AD151 AD152 AD211 AD212 AD411 AD432 BB60 CC01 DD17 EE01 EE06 FF01

Claims (8)

[Claims] 1. A powder treated with a silicon compound in which a natural hydrophilic substance and polysiloxane or silane are combined. 2. A powder treated with a silicon compound in which a natural hydrophilic substance and polysiloxane or silane are bonded, and a silicon compound which generates a silanol hydroxyl group by hydrolysis. 3. A silicon compound in which a natural hydrophilic substance and a polysiloxane or silane are bonded to each other, which is obtained by condensation polymerization of a silicon compound having a hydroxyl group and a silicon compound which produces a silanol hydroxyl group by hydrolysis. Powder treated with a condensation polymer. 4. The powder according to claim 1, wherein the natural hydrophilic substance is a polyamino acid, a polysaccharide or a hydrolyzed protein. 5. The powder according to claim 1, wherein the silicon compound in which a natural hydrophilic substance and polysiloxane or silane are bonded is a silylated peptide. 6. A silicon compound which produces a silanol hydroxyl group by hydrolysis is methyltriethoxysilane, methyltrimethoxysilane, methyltrichlorosilane, dimethyldiethoxysilane, dimethyldimethoxysilane, dimethyldichlorosilane, phenyltriethoxysilane,
Phenyltrimethoxysilane, phenyltrichlorosilane, hexyltriethoxysilane, hexyltrimethoxysilane, hexyltrichlorosilane, octyltriethoxysilane, octyltrimethoxysilane, octyltrichlorosilane, decyltriethoxysilane, decyltrimethoxysilane, decyltrichlorosilane 4. The powder according to claim 2, which is at least one silane selected from the group consisting of tetraethoxysilane, trimethylchlorosilane, hexamethyldisilazane, hexamethyldisiloxane, and perfluoroalkyltrimethoxysilane. body. 7. The powder to be treated is titanium oxide, zinc oxide, talc, kaolin, sericite, fish scale foil, silica,
The mica, nylon, polyacrylic and methyl siloxane are selected from the group consisting of,
6. Powder according to 6. 8. A cosmetic containing the powder according to claim 1.