JPH06145023A - Emulsified composition - Google Patents

Abstract

PURPOSE:To obtain an emulsified composition, capable of sufficiently manifesting excellent usability and water repellency and excellent in stability with time by blending an organopolysiloxane derivative having a saccharide residue with a silicone oil. CONSTITUTION:This emulsified composition is obtained by blending (A) one or two or more organopolysiloxanes, expressed by the formula [R and R<a> are 1-8C hydrocarbon group; at least one of R<1> to R<6> is organic group expressed by the formula R<7>-O-G (R<7> is 2-20C organic group; G is glycosyl derived from monosaccharides, oligosaccharides or polysaccharides) and the rest are 1-8C hydrocarbon group or OH; the average values of m and n denote 0 or positive numbers; m+n is 1-1000] with (B) one or two or more of silicone oils, e.g. a cyclic dimethylpolysiloxane oil, a dimethylpolysiloxane oil and a methylphenylpolysiloxane oil. The ingredient (A) is blended in an amount of >=0.01wt.%, especially preferably >=0.1wt.% and this composition is especially effective when the ingredient (B) accounts for >=50wt.% of the oily ingredient.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an emulsion composition, particularly an emulsion composition containing an organopolysiloxane derivative.

[0002]

2. Description of the Related Art Silicone oil has been widely used in cosmetics, pharmaceuticals, foods, sundries, etc. in recent years because of its excellent heat resistance, weather resistance and low surface tension. Particularly in the field of external preparations for skin, the water repellency of silicone oil is used to protect the skin from water, detergents, etc., and there is an urgent need to develop a wider range of methods for using this silicone oil. However, silicone oil has no affinity for water and is difficult to be emulsified in water, so that its usage is limited. Therefore, in addition to general emulsifiers for emulsifying silicone oil, modified silicone oils having a hydrophilic group introduced into silicone oil have been developed as emulsifiers having a high affinity for silicone oil. Known examples of this include polyether-modified silicones having a polyoxyalkylene group introduced therein and those having an ionic group introduced therein.

[0003]

However, all of the above-mentioned conventional modified silicone oils have the emulsifying ability of silicone oil, but the prepared emulsion composition is inferior in stability over time. In particular, when the silicone oil accounts for 50% by weight or more of all the oily components, the stability over time tends to be significantly deteriorated, which hinders the use of the silicone oil.
Among the above-mentioned modified silicone oils, polyether-modified silicone is widely used as an external preparation for skin from the viewpoint of safety.
When left at a high temperature of about ℃ for a long time, the polyoxyethylene group undergoes oxidative degradation and decomposes, giving off a strange odor,
H may decrease. For this reason, when the cosmetics are displayed in the store for a long time, there is a risk of deterioration. The present invention has been made in view of the above problems of the prior art, and an object thereof is to provide a silicone-based emulsion composition having excellent stability over time.

[0004]

[Means for Solving the Problems] As a result of intensive investigations by the present inventors in order to achieve the above object, the use of an organopolysiloxane derivative having a specific sugar residue as an emulsifier resulted in excellent stability over time. The inventors have found that a silicone-based emulsion composition can be obtained, and completed the present invention.
That is, the emulsion composition according to claim 1 of the present invention has the following general formula 3

[Chemical 3] [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 is represented by the general formula 4

Embedded image -R ⁷ -O-G (in Formula 4, R ⁷ represents an organic group having 2 to 20 carbon atoms, G is a monosaccharide, shows a glycosyl group derived from an oligosaccharide or polysaccharide.) In The represented organic group is shown, and the rest is a hydrocarbon group having 1 to 8 carbon atoms or a hydroxy group. m and n
Mean the same or different 0 or a positive number, and 1
≦ m + n ≦ 1000. ] One or more kinds of organopolysiloxane derivatives having a sugar residue represented by the above and one or more kinds of cyclic dimethylpolysiloxane oil, dimethylpolysiloxane oil, methylphenylpolysiloxane oil are blended. Characterize.

The emulsified composition according to claim 2 is
Corn oil is cyclic dimethyl polysiloxane oil, dimethyl
Of polysiloxane oil and methylphenylpolysiloxane oil
One or two or more and the silicone oil is a whole oil
It is characterized by being 50% by weight or more in the sex ingredient. Since
The configuration of the present invention will be described in more detail below. In the above chemical formula 3
Odors containing organopolysiloxane derivatives
, R and R^aAre the same or different carbon numbers 1 to 8
Indicates a hydrogen group, methyl group, ethyl group, butyl group or fluorine
Examples thereof include a phenyl group. Also, R⁷Carbon indicated by
Examples of the organic group of 2 to 20 include-(CH₂)₂-,-(C
H₂)₃-,-CH₂CH (CH₃) CH₂-,-(CH₂)
_Four-,-(CH₂)_Five-,-(CH₂)₆-,-(CH₂)₇
-,-(CH₂)₈-,-(CH₂)₂-CH (CH₂CH₂
CH₃)-,-CH₂-CH (CH₂CH₃)-,-(CH
₂)₃-O- (CH₂)₂-,-(CH₂)₃-O- (C
H₂)₂-O- (CH₂)₂-,-(CH₂) 3-O-CH₂
CH (CH₃)-,-CH₂-CH (CH₃) -COO
(CH₂)₂-, Etc. can be illustrated.

In the present invention, the glycosyl group derived from a monosaccharide, oligosaccharide or polysaccharide represented by G is
For example, glycosyl group, mannosyl group, galactosyl group,
Ribosyl group, arabinosyl group, xylosyl group, monosaccharide groups such as fructosyl group, maltosyl group, cellobiosyl group,
Oligosaccharide groups such as lactosyl group and maltotriosyl group,
Examples of the polysaccharide group include cellulose and starch, and preferable groups include a monosaccharide group and an oligosaccharide group. Also,
The average value of m and n represents the same or different 0 or a positive number, and 1 ≦ m + n ≦ 1000, preferably 1 ≦ m + n
≦ 500, more preferably 1 ≦ m + n ≦ 150. The method for producing the compound of general formula 3 is not particularly limited,
It can be produced by a generally known hydrosilylation reaction between an organohydrogenpolysiloxane and a sugar derivative having a double bond at the terminal. That is, the general formula 5

[Chemical 5] [In Chemical Formula 5, R and ^Ra represent the same or different hydrocarbon groups having 1 to 8 carbon atoms. R ¹ a to R ^6a is different each the same or at least one is a hydrogen atom, the number of remaining carbon 1
~ 8 hydrocarbon groups are shown. The average value of m and n shows the same or different 0 or a positive number, and 1 ≦ m + n ≦ 100.
An organohydrogenpolysiloxane represented by the formula

Embedded image R ⁸ —O—G [In the formula, R ⁸ has 2 to ⁸ carbon atoms having a double bond in the molecule.
20 represents an organic group, and G represents a glycosyl group derived from a monosaccharide, an oligosaccharide or a polysaccharide. ] It can manufacture by making it react with the sugar derivative represented by these in the presence of a platinum-type catalyst.

When unreacted hydrogen atoms bonded to Si remain after the completion of the reaction, it is preferable to add an olefin compound after the completion of the reaction so that the unreacted hydrogen atoms are reacted as much as possible. Particularly, among the sugar residue-containing organopolysiloxane derivatives represented by the following chemical formulas 7 to 8,
A sugar residue represented by G ^a 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 versatile and is suitable for obtaining a water-in-oil emulsion composition among the emulsion compositions according to the present invention.

[Chemical 7]

[Chemical 8] Further, in the sugar residue-containing organopolysiloxane derivative represented by the following chemical formula 9, the sugar residue represented by G ^b is a glucosyl group, the hydrocarbon group represented by R ¹¹ is a methyl group, and R ¹² is-. (CH ₂ ) ₃ — group and m is 20 to 7
Those having a value of 0 and n of 1 to 10 have general versatility and are suitable for obtaining a water-in-oil emulsion composition among the emulsion compositions according to the present invention.

[Chemical 9]Further, a sugar residue-containing organopolysiloxane represented by Chemical formula 9
G among the sun derivatives The sugar residue shown by b is glucosyl
Group, R¹¹The hydrocarbon group represented by is a methyl group, and R
¹²Is-(CH₂)₃A group, and m is 0 to 50, and n
The milk of 20 to 50 has general versatility and is the milk according to the present invention.
Suitable for obtaining an oil-in-water emulsion composition among the emulsion compositions
It

The amount of the sugar residue-containing organopolysiloxane compounded in the emulsion composition according to the present invention is not particularly limited, but is preferably 0.01% by weight or more, more preferably 0.1% by weight or more. is there. If it is less than 0.01% by weight, poor emulsification may occur. The upper limit of the compounding amount is not particularly limited, but when the amount is extremely large, the ratio of other components constituting the emulsified composition inevitably becomes low, so that it is preferably up to about 10% by weight. On the other hand, as the silicone oil to be emulsified in the present invention,
The following is exemplified. Dimethylpolysiloxane oil has a viscosity of 0.65 to 5000 CSt at 25 ° C, and methylphenylpolysiloxane oil has a viscosity of 25 ° C.
Examples of the cyclic dimethylpolysiloxane oil having a viscosity of 10 to 1000 CSt are octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. The blending amount is not particularly limited, but is an amount capable of producing an emulsion composition, and is preferably 0.1 to 70% by weight. The emulsion composition of the present invention can be used for creams and emulsions as skin cosmetics, emulsion foundations as makeup cosmetics, makeup bases, hair creams as hair cosmetics, and hair treatments.

[0009]

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

[Table 1] ─────────────────────────────────── Comparative Examples Example 1 2 3 1 2 2 ─ ────────────────────────────────── Dimethylpolysiloxane Oil (6CSt / 25 ℃) 10 10 -10 5 Cyclic Dimethylpolysiloxane oil (pentamer) 10 10 -10 10 Liquid paraffin--10 -10 Isopropyl myristate 5 5 5 5 5 Cetyl alcohol 3 3 3 3 3 Sugar residue-containing organopolysiloxane (Chemical 10) --- 5 3 Sodium stearate − 5 5 − 2 POE (25) cetyl ether 5 − − − − Purified water Residual Residual Residual Residual Residual ─────────────────────── ───────────── Emulsion particle size immediately after preparation 5 to 20 1 to 5 1 to 3 1 to 3 1 to 5 50 ℃ 1 Emulsified particle size after months −3 to 20 1 to 3 1 to 3 1 to 10 Stability over time × (separation) △ ○ ○ ○ Water repellency of skin after application ○ ○ × ○ ○ ───────── ──────────────────────────── In the creams of Examples 1 and 2, the water repellency of the silicone oil is exerted on the skin, and The composition itself has excellent stability over time.

However, when the sugar residue-containing organopolysiloxane is not used as in Comparative Examples 1 and 2, the water repellency is good, but the stability over time is poor, and sodium stearate, which is a general emulsifier, POE (25) cetyl ether or the like is not sufficient. Furthermore, when liquid paraffin or the like 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. Chemical formula 10 has the following structure.

[Chemical 10] <Production Method> 32.3 g of methyl hydrogen polysiloxane represented by the following chemical formula 11 and allyl glucoside 78.4
g, 64.5 g of dioxane and 5.0 g of chloroplatinic acid (0.2% dioxane solution) were charged, and the reaction was carried out 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 dialyzed for 3 days using a dialysis tube to remove unreacted allyl glucoside, and the solution in the dialysis tube was distilled off. A sugar residue-containing organopolysiloxane of Chemical formula 10 was obtained.

[Chemical 11] Next, using the following basic formulation, the relationship between the blending ratio of the silicone oil in the oil phase and the emulsion stability was investigated. Basic formulation 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% ──────────────────────────────────── Emulsification ○ ○ × ○ ○ × ○ ○ × ○ ○ △ ○ ○ ○ Stability ○ △ × ○ △ × ○ △ × ○ △ △ ○ ○ ○ Water repellent ○ ○ ○ ○ ○ ○ ○ ○ ○ △ △ △ × × × ── ────────────────────────────────── Clear from Table 2 above As described above, when A / B is 1 or more, the water repellency is good, but on the other hand, the emulsification property is poor when a general emulsifier is used, and POE (25) silicone which is a conventional modified silicone is used. In this case, emulsification was possible, but the emulsion stability was poor and, in some cases, denaturation and generation of off-flavor occurred depending on storage conditions.

Therefore, it is understood that the emulsion composition according to the present invention is particularly effective when the ratio of the silicone oil in the oil component is 50% or more. Below, the specific compounding example of the emulsion composition concerning this invention is shown. Example 3 Emollient oil glycerin 10.0 1,3-butanediol 40.0 Sugar residue-containing organopolysiloxane (Chemical formula 12) 10.0 Cyclic dimethylpolysiloxane (tetramer) 34.75 Glyceryl trioctanoate 5 0.0 Vitamin E acetate 0.2 Vitamin D ₂ 0.05 The emollient oil of Example 3 has an excellent emollient effect and also excellent stability over time. Chemical formula 12 has the following structure.

[Chemical 12] <Production Method> 12.9 g of methylhydrogenpolysiloxane represented by the following chemical formula 13 and 49.0 of allyl glucoside.
g, 200 g of isopropyl alcohol, and 3.0 g of chloroplatinic acid (0.2% isopropyl alcohol solution) were charged and reacted in the same manner as the sugar residue-containing organopolysiloxane of Chemical formula 10 above.

[ Example 13] Hand cream dimethyl polysiloxane (5000 CSt / 25 ° C) 5.0 Cyclic dimethyl polysiloxane (tetramer) 15.0 Cyclic dimethyl polysiloxane (pentamer) 10.0 Organic 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, water repellency, and stability over time.

The sugar residue-containing organopolysiloxane of Chemical formula 14 has the following structure.

[Chemical 14] <Production Method> 16.3 g of methylhydrogenpolysiloxane shown in Chemical formula 15 below, 49.0 g of allyl glucoside, 100 g of dioxane, and 5.0 g of chloroplatinic acid (0.2% dioxane solution) were charged respectively, and the mixture was heated at about 80 to 90 ° C. The reaction was carried out for 3 hours. The reaction mixture was concentrated, partitioned with an ethyl acetate / water system, and the solvent of the organic layer was distilled off to obtain Compound 15.

[Chemical 15] Example 5 Hair cream dimethyl polysiloxane (1000 C St / 25 ° C.) 12.0 Carnauba wax 5.0 Microcrystalline wax 8.0 Isopropyl myristate 10.0 Methylphenyl polysiloxane 20.0 Sugar residue-containing organopolysiloxane ) 15.0 Sugar residue-containing organopolysiloxane (Chemical formula 17) 15.0 Purified water Residual preservative Appropriate amount Fragrance Appropriate amount The hair cream of Example 5 is excellent in water repellency and stability over time. It was

The sugar residue-containing organopolysiloxanes shown in Chemical formulas 16 and 17 have the following structures, respectively.

[Chemical 16]

[Chemical 17] Example 6 Sunblock Lotion Sugar Residue-containing Organopolysiloxane (Chemical 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 potassium 0.08 Preservative Suitable amount disodium edetate 0.02 Purified water Residual Example 6 sunscreen lotion was excellent Have a feeling of use,
It also has excellent stability.

The sugar residue-containing organopolysiloxane shown in Chemical formula 18 has the following structure.

[Chemical 18] 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 Perfume 0.3 Hydrophobic 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 and water repellency, and is also excellent in stability over time. .

The sugar residue-containing organopolysiloxanes shown in Chemical formulas 19 and 20 have the following structures.

[Chemical 19]

[Chemical 20] Example 8 Cream glycerin 7.5 Purified water 46.125 Sodium L-glutamate 1.25 Methylparaben 0.125 Sugar residue-containing organopolysiloxane (Chemical formula 21) 5.0 Decamethylcyclopentasiloxane 15.0 Dimethylpolysiloxane ( 6CSt / 25 ° C) 15.0 Liquid paraffin 10.0 In addition, the sugar residue-containing organopolysiloxane of Chemical formula 21 is
It has the following structure:

[Chemical 21] Example 9 Shampoo composition Lauryl ether sulphate 20.0 Dimethylpolysiloxane (6CS / 25 ° C) 3.0 Laurylamine oxide 1.0 Cationized cellulose 0.5 Sugar residue-containing organopolysiloxane (Chemical formula 6) 2. 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 stability over time. is there.

Example 10 Hair rinse composition Distearyl dimethyl ammonium chloride 1.0 Dimethyl polysiloxane (20CS / 25 ° C.) 2.0 Cationized cellulose 0.5 Cetanol 1.5 Stearyl alcohol 1.5 Liquid paraffin 1. 0 Sugar residue-containing organopolysiloxane (Chemical formula 11) 1.0 Glycerin 5.0 Methylparaben 0.1 Perfume Suitable 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 sex.

[0017]

The emulsion composition according to the present invention, when blended with a sugar residue-containing organopolysiloxane and a silicone oil, is capable of exhibiting excellent usability and water repellency while achieving stability over time. You can

[Chemical 13]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Sumiyo Fukushima 5-1-1 Umei, Takasago-shi, Hyogo Nihon Seika Co., Ltd. (72) Inventor Keisuke Kinomura 5-1-1 Umei, Takasago-shi, Hyogo No. NIPPON SEIKI CO., LTD. Research Institute (72) Inventor Masaki Kojima 5-1-1 Umei, Takasago City, Hyogo Prefecture

Claims (2)

[Claims] 1. The following general formula 1 [In the above chemical formula 1, R and R ^a each have the same or different carbon number 1
~ 8 hydrocarbon groups are shown. R ^{1 to} R ⁶ are the same or different, and at least one is represented by the general formula 2 —R ⁷ —O—G (wherein, R ⁷ represents an organic group having 2 to 20 carbon atoms, and G is Represents a glycosyl group derived from a monosaccharide, an oligosaccharide or a polysaccharide), and the rest represents a hydrocarbon group having 1 to 8 carbon atoms or a hydroxy group. m and n
Mean the same or different 0 or a positive number, and 1
≦ m + n ≦ 1000. ] One or more kinds of organopolysiloxane derivatives having a sugar residue represented by the above and one or more kinds of silicone oil are blended, and an emulsified composition. 2. The emulsified composition according to claim 1, wherein the silicone oil comprises one or more of cyclic dimethylpolysiloxane oil, dimethylpolysiloxane oil and methylphenylpolysiloxane oil, and the silicone oil is wholly contained. 50% by weight or more of an oily component, an emulsified composition.