JP3229396B2 - Water repellent cosmetic - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-repellent cosmetic , particularly a water-repellent cosmetic containing an organopolysiloxane derivative.

[0002]

2. Description of the Related Art In recent years, silicone oils are excellent in physical properties such as heat resistance, weather resistance and low surface tension. In particular, in the field of external preparations for skin, the water repellency of silicone oil is used to protect the skin from water or detergents, and it is urgently necessary to develop a wider use of the silicone oil. However, the use of silicone oil is limited because it has no affinity for water and is hardly emulsified in water. Therefore, in addition to a general emulsifier for emulsifying the silicone oil, a modified silicone oil having a hydrophilic group introduced into the silicone oil has been developed as an emulsifier having a high affinity for the silicone oil. As this example, a polyether-modified silicone into which a polyoxyalkylene group has been introduced, and a silicone into which an ionic group has been introduced are known.

[0003]

However, although the above-mentioned conventional modified silicone oils all have the emulsifying ability of silicone oil, the adjusted emulsified composition has poor stability over time. In particular, when the silicone oil accounts for 50% by weight or more of the total oil component, the stability over time tends to be remarkably deteriorated, which hinders the use of the silicone oil.
Among the modified silicone oils, polyether-modified silicone is widely used as an external preparation for skin from the viewpoint of safety.
If left for a long time at a high temperature of about ℃, the polyoxyethylene group undergoes oxidative deterioration and is decomposed, giving off odor,
H may decrease. For this reason, when the cosmetics are displayed in the store for a long time, there is a possibility that the quality may change. The present invention has been made in view of the problems of the prior art, and its purpose is to sufficiently exhibit excellent usability and water repellency.
So while, to provide a good water repellency cosmetic stability with time.

[0004]

Means for Solving the Problems As a result of intensive studies by the present inventors to achieve the above object, excellent usability and repellency can be obtained by using an organopolysiloxane derivative having a specific sugar residue as an emulsifier. Let's make full use of water
One, found that excellent water repellency cosmetic aging stability can be obtained, and have completed the present invention. That is, the water-repellent cosmetic according to claim 1 of the present invention has the following general formula 3.

Embedded image [Among the chemical formula 3, R and R ^a each show the same or different hydrocarbon group having 1 to 8 carbon atoms. R ^{1 to} R ⁶ are the same or different, and at least one of them is represented by general formula 4

Embedded image in -R ⁷ -O-G (Formula 4, R ⁷ is - _{(CH 2) 2-20} - represents a group, G
Represents a glycosyl group derived from a monosaccharide . ), And the remainder represents a hydrocarbon group having 1 to 8 carbon atoms or a hydroxy group. The average value of m and n indicates the same or different 0 or a positive number, and 1 ≦ m + n ≦ 1000. And one or more kinds of organopolysiloxanes derivative having a sugar residue represented by, blended, and one or two or more silicone oils, and the silicone oil is full
It is characterized by being at least 50% by weight of the oily component .

[0005] The water-repellent cosmetic according to claim 2 is characterized in that the silicone oil comprises one or more of cyclic dimethylpolysiloxane oil, dimethylpolysiloxane oil and methylphenylpolysiloxane oil . Less than,
The configuration of the present invention will be described in more detail. In the sugar residue-containing organopolysiloxane derivative represented by Chemical Formula 3, R
And _Ra are the same or different and represent a hydrocarbon group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a butyl group or a phenyl group. R ⁷ is-(CH ₂ )
_2-20- is shown.

[0006] At a present invention, as the glycosyl group derived from a monosaccharide represented by G, for example glycosyl groups, mannosyl, galactosyl, ribosyl group, arabinosyl group, xylosyl, Tantomoto such fructosyl group Is an example
Is shown. Further, the average values of m and n represent the same or different 0 or positive numbers, and 1 ≦ m + n ≦ 1000, preferably 1 ≦ m + n ≦ 500, more preferably 1 ≦ m + n
≦ 150. The method for producing the compound of the general formula 3 is not particularly limited, but it can be produced by a generally well-known hydrosilylation reaction between an organohydrogenpolysiloxane and a sugar derivative having a double bond at a terminal. That is, general formula 5

Embedded image [In formula 5, R and ^Ra represent the same or different hydrocarbon groups having 1 to 8 carbon atoms. R ^{1a to} R ^6a are the same or different, at least one of them represents a hydrogen atom, and the rest has 1 carbon atom.
To 8 hydrocarbon groups. The average value of m and n represents the same or different 0 or a positive number, and 1 ≦ m + n ≦ 100
0] and an organohydrogenpolysiloxane represented by general formula 6

Embedded image R ⁸ -O-G [wherein, CH having a double bond in R ⁸ is not molecular ₂ = C
H (CH ₂ ) _0-18 represents a group , and G is derived from a monosaccharide.
Represents a glycosyl group . And the sugar derivative represented by the formula (1) in the presence of a platinum-based catalyst.

If unreacted hydrogen atoms bonded to Si remain after the reaction, it is preferable to add an olefinic compound after the reaction and react the unreacted hydrogen atoms as much as possible. In particular, among the sugar residue-containing organopolysiloxane derivatives represented by the following chemical formulas (7) to (8),
A sugar residue represented by Ga is a glucosyl group, a hydrocarbon group represented by R ⁹ is a methyl group, R ¹⁰ is a — (CH ₂ ) ₃ — group, and m is 5 to 70. It is suitable for obtaining a water-in-oil type water repellent cosmetic among the water repellent cosmetics according to the present invention.

Embedded image

Embedded image Also, of the sugar residue-containing organopolysiloxane derivative represented by the following formula 9, a sugar residue is glucosyl group represented by Gb, the hydrocarbon group represented by R11 methyl group, R ₁₂ is - (CH ₂ ) a _3- group and m is from 20 to 7
Those having 0 and n of 1 to 10 have versatility and are suitable for obtaining a water-in-oil type water- repellent cosmetic among the water- repellent cosmetics according to the present invention.

Embedded image Also, among the sugar residue-containing organopolysiloxane derivatives represented by Chemical Formula 9, the sugar residue represented by Gb is a glucosyl group, the hydrocarbon group represented by R ¹¹ is a methyl group,
¹² is a — (CH ₂ ) ₃ — group, and m is 0 to 50;
There are those 20 to 50 is versatile, repellent according to the present invention
It is suitable for obtaining an oil-in- water type water-repellent cosmetic among aqueous cosmetics .

[0008] The amount of the organopolysiloxane containing a sugar residue to be incorporated into the water-repellent cosmetic according to the present invention is not particularly limited, but is preferably at least 0.01% by weight, more preferably at least 0.1% by weight. It is. If the amount is less than 0.01% by weight, poor emulsification may occur. There is no particular upper limit on the blending, but if the amount is extremely large, the proportion of other components constituting the water-repellent cosmetic is inevitably reduced, so that it is preferably up to about 10% by weight. on the other hand,
The following are examples of the silicone oil to be emulsified in the present invention. As a dimethylpolysiloxane oil, the viscosity at 25 ° C is 0.65 to 5000 CS.
t, methylphenylpolysiloxane oil 2
Those having a viscosity at 5 ° C. of 10 to 1000 CSt, and cyclic dimethylpolysiloxane oils such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane,
Dodecamethylcyclohexasiloxane and the like can be mentioned. The amount is not particularly limited, but is an amount capable of producing a water-repellent cosmetic, and is preferably 0.1 to 70% by weight. The water-repellent cosmetic of the present invention can be used in creams and emulsions as skin cosmetics, emulsified foundations as makeup cosmetics, makeup bases, hair creams as hair cosmetics, hair treatments, and the like.

[0009]

The present invention will be described in more detail with reference to the following examples. The present invention is not limited to the embodiments. Unless otherwise specified, the compounding amount is shown in% by weight. First, the creams shown in the following Table 1 were produced, and the stability over time and the water repellency of the skin after application were evaluated.

[Table 1] Comparative Example Example 1 2 3 1 2 Dimethylpolysiloxane oil (6CSt / 25 ℃) 10 10 -10 5 Cyclic Dimethylpolysiloxane oil (pentamer) 10 10 -10 10 Liquid paraffin --10 -10 Isopropyl myristate 55 55 55 cetyl alcohol 33 33 33 Oracanopolysiloxane containing sugar residue (Chemical Formula 10)--- 53 3 Sodium stearate-55-2 POE (25) cetyl ether 5-----Purified water Residue Residue Residue Residue ──────────────────────乳化 Emulsified particle size immediately after preparation 5 ~ 20 1 ~ 5 1 ~ 3 1 ~ 3 1 ~ 5 50 ℃ 1 Emulsion particle size after month −3 to 20 1 to 3 1 to 3 1 to 10 Stability over time × (separation) △ ○ ○ ○ Water repellency of skin after application ○ ○ × ○ ○ ────────ク リ ー ム In the creams according to Examples 1 and 2, the water repellency of silicone oil is exerted on the skin, and The composition itself is excellent in stability over time.

However, when no organopolysiloxane containing a saccharide residue is used as in Comparative Examples 1 and 2, although water repellency is good, stability over time is poor, and sodium stearate which is a general emulsifier, POE (25) cetyl ether or the like is insufficient. Furthermore, when liquid paraffin is used without using silicone oil,
It is understood that while sufficient emulsification is possible even with sodium stearate or the like, excellent water repellency cannot be obtained. Formula 10 has the following structure.

Embedded image <Production method> 32.3 g of methyl hydrogen polysiloxane represented by the following formula 11 and 78.4 allyl glucoside
g, 64.5 g of dioxane, and 5.0 g of chloroplatinic acid (0.2% dioxane solution), and reacted at 80 to 90 ° C. for about 3 hours. The reaction mixture was concentrated, partitioned with an ethyl acetate / water system, the aqueous layer was concentrated, and dialysis was performed for 3 days using a dialysis tube to remove unreacted allylglucoside, and the solution in the dialysis tube was distilled off. A sugar residue-containing organopolysiloxane represented by Chemical formula 10 was obtained.

Embedded image Next, the relationship between the mixing ratio of the silicone oil in the oil phase and the emulsion stability was examined using the following basic recipe. Basic formula A: Dimethyl polysiloxane oil (6CSt / 25 ° C) Table 2 B: Liquid paraffin Table 2 Isopropyl myristate 5% Cetyl alcohol 3% C: Sugar residue-containing organopolysiloxane (Chemical Formula 10) Table 2 D: POE ( 25) Silicone Table 2 E: Sodium stearate Table 2 Purified water residue ────────────────────────────── 100%

[Table 2] A 20% 15% 10% 5% 0 % B 0% 5% 10% 15% 20% ──────────────────────────────────── C 5 %--5%--5%--5%--5%--D-5%--5%--5%--5%--5%-E--5%--5%- − 5% − − 5% − − 5% 乳化 Emulsifying ○ ○ × ○ ○ × ○ ○ × ○ ○ △ ○ ○ ○ Stability ○ △ × ○ △ × ○ △ × ○ △ △ ○ ○ ○ Water repellency ○ ○ ○ ○ ○ ○ ○ ○ ○ △ △ △ × × × ──な Clear from Table 2 above As described above, when A / B is 1 or more, water repellency is good, but when a general emulsifier is used, emulsifying property is poor, and POE (25) silicone which is a conventional modified silicone is used. In this case, emulsification is possible, but emulsification stability is poor, and denaturation and off-flavor may occur depending on storage conditions.

On the other hand, a sugar residue-containing organopolysilo
The water-repellent cosmetic according to the present invention containing xanth has an emulsion stability while maintaining excellent water repellency when the proportion of the silicone oil in the oily component is 50% or more.
It has been confirmed that it has been improved. Hereinafter, specific mixing examples of the water-repellent cosmetic according to the present invention will be described. Example 3 Emollient oil glycerin 10.0 1,3-butanediol 40.0 Sugar residue-containing organopolysiloxane (Formula 12) 10.0 Cyclic dimethylpolysiloxane (tetramer) 34.75 Glyceryl trioctanoate 5 0.0 Vitamin E acetate 0.2 Vitamin D2 0.05 The emollient oil of Example 3 is excellent in emollient effect and also excellent in stability over time. Incidentally, Chemical formula 12 has the following structure.

Embedded image <Production method> 12.9 g of methyl hydrogen polysiloxane represented by the following formula (13), 49.0 g of allyl glucoside, 200 g of isopropyl alcohol, and 3.0 g of chloroplatinic acid (0.2% isopropyl alcohol solution) were charged, respectively. Was reacted in the same manner as described above.

Embedded image Example 4 Hand Cream Dimethylpolysiloxane (5000CSt / 25 ° C) 5.0 Cyclic dimethylpolysiloxane (tetramer) 15.0 Cyclic dimethylpolysiloxane (pentamer) 10.0 Organically modified bentonite 3.0 Sugar residue Contained organopolysiloxane (Chemical formula 14) 3.0 Purified water Residual preservative Appropriate amount The hand cream of Example 4 has excellent usability, and is also excellent in water repellency and stability over time.

Example 4 Hand cream dimethylpolysiloxane (5000 CSt / 25 ° C.) 5.0 Cyclic dimethylpolysiloxane (tetramer) 15.0 Cyclic dimethylpolysiloxane (pentamer) 10.0 Organically modified bentonite 3.0 Sugar residue-containing organopolysiloxane (Chemical formula 14) 3.0 Purified water Residual preservative Appropriate amount The hand cream of Example 4 has excellent usability, and is also excellent in water repellency and stability over time.

The organopolysiloxane containing a saccharide residue represented by Chemical formula 14 has the following structure.

Embedded image <Production method> 16.3 g of methyl hydrogen polysiloxane, 49.0 g of allyl glucoside, 100 g of dioxane, and 5.0 g of chloroplatinic acid (0.2% dioxane solution) shown in the following formula 15 were each charged, and the mixture was heated at about 80 to 90 ° C. The reaction was performed for 3 hours. The reaction mixture was concentrated and partitioned with an ethyl acetate / water system, and the solvent in the organic layer was distilled off to obtain Compound 15.

Embedded image Example 5 Hair cream dimethylpolysiloxane (1000 CSt / 25 ° C.) 12.0 Carnauba wax 5.0 Microcrystalline wax 8.0 Isopropyl myristate 10.0 Methylphenylpolysiloxane 20.0 Sugar residue-containing organopolysiloxane (Chemical Formula 16) 15.0) Sugar residue-containing organopolysiloxane (Formula 17) 15.0 Purified water Residual preservative Appropriate amount Perfume Appropriate amount The hair cream of Example 5 has excellent water repellency and excellent stability over time. Was.

The organopolysiloxane containing a saccharide residue shown in Chemical formulas 16 and 17 has the following structures, respectively.

Embedded image

Embedded image Example 6 Sunscreen lotion sugar residue-containing organopolysiloxane (Formula 18) 0.1 glycerin 3.0 1,3-butanediol 2.0 dimethylpolysiloxane (5 CSt / 25 ° C.) 10.0 methylphenylpolysiloxane ( 5CSt / 25 ° C) 3.0 Octyl paramethoxycinnamate 5.0 Carboxyvinyl polymer 0.4 Caustic potash 0.08 Preservatives Appropriate amount Disodium edetate 0.02 Purified water residue The sunscreen lotion of Example 6 was excellent. Have a feeling of use,
And it is excellent in stability.

The organopolysiloxane containing a saccharide residue shown in Chemical formula 18 has the following structure.

Embedded image Example 7 Emulsion Foundation Purified Water 38.2 Glycerin 15.0 Sodium L-Glutamate 2.0 Sodium Hyaluronate 0.1 Preservative 0.3 Glycerin Triisooctanoate 5.0 Decamethylcyclopentasiloxane 10.0 Dimethyl Poly Siloxane (6CSt / 25 ° C) 5.0 Sugar residue-containing organopolysiloxane (Chemical formula 19) 2.0 Sugar residue-containing organopolysiloxane (Chemical formula 20) 2.0 Antioxidant 0.1 Fragrance 0.3 Hydrophobization Treated sericite 7.4 Hydrophobized talc 1.0 Hydrophobized zinc oxide 2.0 Hydrophobized titanium oxide 8.0 Hydrophobized iron oxide (yellow) 1.0 Hydrophobized iron oxide (red) 4 Hydrophobized iron oxide (black) 0.2 The emulsified foundation according to Example 7 has excellent usability, water repellency and excellent stability over time. .

The sugar residue-containing organopolysiloxane represented by Chemical Formulas 19 and 20 has the following structure.

Embedded image

Embedded image Example 8 Cream Glycerin 7.5 Purified Water 46.125 Sodium L-Glutamate 1.25 Methylparaben 0.125 Sugar Residue-Containing Organopolysiloxane (Formula 21) 5.0 Decamethylcyclopentasiloxane 15.0 Dimethylpolysiloxane ( 6CSt / 25 ° C) 15.0 Liquid paraffin 10.0 The sugar residue-containing organopolysiloxane of Chemical formula 21 is
It has the following structure.

Embedded image Example 9 Shampoo composition Lauryl ether sulfate 20.0 Dimethyl polysiloxane (6CS / 25 ° C) 3.0 Laurylamine oxide 1.0 Cationized cellulose 0.5 Organopolysiloxane containing sugar residue (Formula 10 ) 2 Ethylene glycol distearate 2.0 Butylhydroxytoluene 0.2 Dye Appropriate amount Perfume Appropriate amount Purified water 71.1 The shampoo composition of Example 9 has excellent usability and excellent stability over time. is there.

Example 10 Hair rinse composition Distearyl dimethyl ammonium chloride 1.0 Dimethyl polysiloxane (20 CS / 25 ° C.) 2.0 Cationized cellulose 0.5 Cetanol 1.5 Stearyl alcohol 1.5 Liquid paraffin 0 Sugar residue-containing organopolysiloxane (Chemical Formula 10 ) 1.0 Glycerin 5.0 Methylparaben 0.1 Perfume Appropriate amount Purified water 86.4 The hair rinse composition of Example 10 has excellent usability and is stable over time. It is also excellent in nature.

[0017]

The water-repellent cosmetic according to the present invention is silicone
By adding 50% by weight or more of the base oil to the total oil component, and blending a sugar residue-containing organopolysiloxane and silicone oil, excellent usability and water repellency are sufficiently exhibited, and stability over time is obtained. be able to.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Keisuke Kinomura 5-1-1 Umei, Takasago-shi, Hyogo Prefecture Japan Seika Co., Ltd. (72) Inventor Masaki Kojima 5-1-1 Umei, Takasago-shi, Hyogo Prefecture No. Nippon Seika Co., Ltd. (56) References JP-A-5-186596 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) A61K ^7/ 00-7/50

Claims (2)

(57) [Claims] (1) The following general formula (1): [Wherein R and ^Ra are the same or different and each have 1 carbon atom
To 8 hydrocarbon groups. R ^{1 to} R ⁶ are the same or different, and at least one is a group represented by the general formula 2 —R ⁷ —OG (wherein R ⁷ represents a — (CH ₂ ) _2-20 — group ; G
Represents a glycosyl group derived from a monosaccharide . ), And the remainder represents a hydrocarbon group or a hydroxy group having 1 to 8 carbon atoms. The average value of m and n is
Same or different 0 or positive number, and 1 ≦ m + n ≦ 1
000. And one or more kinds of organopolysiloxanes derivative having a sugar residue represented by, blended, and one or two or more silicone oils, and the silicone oil is 50-fold of the total oil component
Water-repellent cosmetic , characterized in that the amount is not less than% . 2. A emulsion composition of claim 1 wherein the silicone oil is cyclic dimethylpolysiloxane oils, dimethylpolysiloxane oil, water-repellent, characterized in that consists of one or more kinds of methylphenyl polysiloxane oil make up
Fees .