JPH03213137A - Emulsifiers and emulsified cosmetics containing them - Google Patents

Abstract

PURPOSE:To obtain a W/O type emulsifier having high emulsion stability by adding fatty acid to carbohydrate selected from glucosamine, N- acetylglucosamine and a homopolymer or copolymer with a polymerization degree of 10 or less thereof. CONSTITUTION:An emulsifier is obtained by adding fatty acid to carbohydrate selected from glucosamine, N-acetylglucosamine and a homopolymer or copolymer with a polymerization degree of 10 or less. The range of the carbon chain of fatty acid used in addition is different according to the mean polymerization degree of carbohydrate and the addition amount of fatty acid but pref. about 10-22 in the number of carbon atoms. Fatty acid can be easily added through an ester bond or an amide bond by a known method. The pref. addition amount of fatty acid is within the range of about 1.0-3.5 per the monosaccharide of carbohydrate. This emulsifier can be adapted to the emulsion of a large amount of an oil component and water used in cosmetics, medicines or food and has high emulsion stability and an excellent use feeling and especially useful in obtaining a W/O type emulsified composition.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to an emulsifier suitable for blending in chemical products, pharmaceutical products, foods, etc., and cosmetics containing the emulsifier. (Prior Art) Conventionally, emulsifiers have been used for emulsifying and dispersing pharmaceuticals, foods, and cosmetics such as creams and emulsions, solubilizing fragrances and vitamins, and improving quality such as controlling foaming properties. Glycerin fatty acid esters such as diglycerin diisostearate, propylene glycol monostearate,
Propylene glycol fatty acid esters such as propylene glycol monolaurate, sucrose fatty acid esters, sorbitan monooleate, sorbitan sesquiolate. Sorbitan fatty acid esters such as sorbitan monostearate, their polyoxyethylene ethers, lecithin, etc. have been used. In the emulsified composition obtained by blending a conventionally known emulsifier, the dispersed phase is oil, and 3! ! There are two types: oil-in-water type (referred to as 0/W type), which has water as its successor phase, and water-in-oil type (hereinafter referred to as W2O type), which has the opposite phase, but in the cosmetics and pharmaceutical fields, normal human Recently, emulsifiers suitable for W10 type emulsified compositions have been developed from the viewpoints that the skin is in a W2O type emulsified state and that they have superior moisturizing and water repellent properties compared to O/W type dairy emulsified compositions. Development is desired.

[Problem to be solved by the invention]

The W10 type emulsion composition obtained in the above-mentioned prior art has the disadvantage that it is difficult to obtain emulsion stability and usability compared to the 0/W type dairy emulsion. In other words, due to the decrease in viscosity due to the slight temperature during storage,
It easily causes drainage and impregnation, causing flaking and film formation, and because the outer phase is oily, it has the disadvantage of giving a strong stickiness and sliminess when used in cosmetics. Ta. Therefore, it has been desired to develop an emulsifier for producing a W10 type emulsion composition with excellent emulsion stability and a cosmetic composition with excellent usability. The object of this invention is to provide an emulsifier with excellent emulsion stability and a dairy cosmetic containing the emulsifier with excellent usability.

[Means to solve the problem]

The present invention provides glucosamine, N-acedelglucosamine,
and an emulsifier characterized in that a fatty acid is not added to a carbohydrate selected from homopolymers or copolymers having a degree of polymerization of 10 or less, and an emulsified cosmetic containing the emulsifier. Related. The carbohydrate selected from glucosamine, N-acetylglucosamine, and homopolymers or copolymers thereof with a degree of polymerization of 10 or less used in the present invention is a natural polymer contained in large amounts in crustaceans, pentapods, etc. Chitin can be treated with conventionally known methods 1, such as neutralizing and desalting after treatment with concentrated hydrochloric acid,
It can be easily obtained by carrying out a hydrolysis reaction using an enzyme or the like and, if necessary, a deacetylation reaction by treatment with a concentrated alkali. At this time, if a polymer having a degree of polymerization higher than 10 is used, the solubility during emulsification will decrease, so it is preferable that the degree of polymerization is 10 or less. Furthermore, the degree of deacetylation, which indicates the proportion of glucosamine residues in the polymer of glucosamine and N-acetylglucosamine, is not particularly limited. In addition, the range of the carbon chain of the fatty acid used in this light varies depending on the average degree of polymerization of the sugar and the E1 loading of the fatty acid,
The preferred range is 10 to 22 carbon atoms, and lauric acid. Myristic acid, palmidic acid, stearic acid, oleic acid, isomyristic acid, isopalmitic acid. Isostearic acid, isooleic acid, etc. are preferred. In the present invention, fatty acids can be added to the yIs selected from glucosamine, N-acetylglucosamine, and homopolymers or copolymers thereof with a degree of polymerization of 10 or less by a conventionally known method via an ester bond or an amide bond. This allows for easy addition. - For example, a carbohydrate selected from glucosamine, N-acetylglucosamine, and homopolymers or copolymers thereof with a degree of polymerization of 10 or less is dispersed in pyridine, and a fatty acid halide or fatty acid anhydride is added to the dispersion in pyridine. In addition, there is a method of reacting at around 85°C for 2 to 8 hours. Addition amount of fatty acid halide or fatty acid anhydride at this time 1
The amount of fatty acid added can be easily controlled by appropriately adjusting the reaction time and temperature. In the present invention, the amount of fatty acids added is 3.
When the number is 5 or more, the hydrophilicity decreases, resulting in poor dispersibility in the aqueous phase during emulsification.If the number is 1.0 or less, the lipophilicity decreases, resulting in poor dispersibility in the oil phase during emulsification. 1. From getting worse.
0~3.5f! It is preferable to fall within the range of i. Emulsifiers in which fatty acids are added to carbohydrates selected from glucosamine, N-acetylglucosamine, and their homopolymers or copolymers with a degree of polymerization of 10 or less obtained by these methods have a weight difference depending on the reaction conditions, etc. The color becomes liquid or paste with a brown hue. If necessary, the colored material at this time can be removed using conventional decolorization methods such as activated carbon,
It can be easily decolorized and purified by treatment with Celite, etc. The emulsifier of the present invention can be applied to the emulsification of many oils and water used in cosmetics, pharmaceuticals, foods, etc. In cosmetics, liquid paraffin, which is the oil used in the shell, hydrocarbon oils such as sorghum, isoparaffin, and petrolatum, ester oils such as isopropyl myristate, isocetyl stearate, and glycerin trioctanoate, and dimethyl Silicone oils such as polysiloxane and methylcyclopentasiloxane, fatty acids, and higher alcohols. Olive oil, coconut oil, safflower oil, castor oil. It can be applied to emulsify water with oilworms such as cottonseed oil, lanolin, waxes such as carnauba wax, etc. For producing an emulsified composition using the emulsifier of the present invention, conventionally known methods such as a phase inversion method, a paste method, a self-emulsification method, etc. can be applied. The emulsion composition obtained at this time has extremely excellent emulsion stability, good water retention and water repellency, and when used as a cosmetic, it has a "sticky feeling" and "
A product with less slimy feeling can be obtained. In addition, the emulsifier of the present invention has excellent emulsion stability and usability as a cosmetic.
Although it is suitable for making a ZO type emulsion type composition, it is also possible to easily make an O/W type emulsion type composition by using it in combination with other emulsifiers. Even when the emulsifier of the present invention is applied to pharmaceuticals, foods, etc. other than cosmetics, emulsified compositions with excellent stability can be obtained. K Examples The present invention will be described in detail with reference to Examples below, but the present invention is not limited to these scopes. Note that the degree of fat H substitution in the following description represents the amount of fatty acid added per monosaccharide unit of carbohydrate, and its measurement was performed according to elemental analysis. The elemental analyzer is HT-3 from Yanagimoto Seisakusho.
was used. In addition, the 818 valence was calculated by the Atlas method. Example 1 5 g of glucosamine (manufactured by Sigma) was mixed with 30 d of pyridine.
In addition to this, the mixture was heated to 85° C. with stirring, and 18 g of A leicyl chloride was added dropwise, and the mixture was reacted for 3 hours. After finishing the reaction +45, pyridine was distilled off, and after washing with water at about 100 -, about 80
- extracted with chloroform, then about 250 d of water, and about 1
After washing with a 1:1 water:methanol solution of 50d, the washing liquid was distilled off to obtain a brown liquid emulsifier 1 with a degree of fat M substitution of 1.55.
2.2f? I got it. The valence of 11 [8] of this product was 4.3 (Sample 1). Example 2 The same procedure as in Example 1 was carried out using isostearic acid chloride instead of oleic acid chloride.
12.7 g of a brown liquid emulsifier with a degree of fatty acid substitution of 1.86 was removed. The 1118 valence of this product was 4.2 (Sample 2)
. Example 3: Exactly the same procedure as in Example 1, but using N- instead of glucosamine.
When acetylglucosamine was used and the amount of oleic acid chloride added was changed to 12g, fat Mfr conversion I
V1. 11.5 g of a brown liquid emulsifier was obtained. The 1118 value of this product was 6.1 (Sample 3). Example 4゜Exactly the same procedure as in Example 1, but using N- instead of glucosamine.
When acetyl glucosamine was used and 12 g of isostearic acid chloride was used instead of oleic acid chloride, fat i1@1 substitution, 54 brown liquid emulsifier 1
1.8g was obtained. )1[B@[i of this sample was 6.1 (Sample 4). Example 5 380 g of 6N hydrochloric acid was added to 20 g of chitin with a molecular size of about 180,000 and a degree of deacetylation of 80%, and a hydrolysis reaction was carried out with stirring at 70° C. for 6 hours. 400 minutes after completion of reaction
The filtrate was concentrated to dryness under reduced pressure using a rotary evaporator, the resulting powder was fractionated with methanol, and the soluble components were dried to obtain an average degree of polymerization. Obtained 2.5 carbohydrates 6.09. Next, 5 g of the '/Ilt'd was added to a mixed solvent of 20 dimethylformamide and 10 d of pyridine, heated to 95° C. with stirring, and 12 g of oleic acid chloride was added dropwise and reacted for 5 hours. After the reaction, the mixed solvent was distilled off and about 1
After washing with 00d water, about 80+d! Extracted with chloroform, then about 250 d of water, and about 150 d of 1.1 water:
After washing with a methanol solution, the washing liquid is distilled off to remove the fat
9.7 g of a brown liquid emulsifier with a degree of li substitution of 1.14 was obtained. The old B number of this product was 6.3 (Sample 5). Example 6 190 i of concentrated hydrochloric acid was added to 10 g of chitin having an average molecular weight of soo, ooo and a degree of deacetylation of 12%, and a hydrolysis reaction was carried out with stirring at 40° C. for 2 hours. After the reaction is completed, the filtrate is neutralized with 1N sodium hydroxide and filtered to remove insoluble matter. The filtrate is passed through an activated carbon-Celite column with an inner diameter of 4.4 Crn and a length of 100 IJ to adsorb the target substance. Wash the inside of the column with twice the amount of water, and add 200% of 30% ethanol solution.
- was passed through the solution to elute the target substance, and the cough solution was concentrated under reduced pressure at 50°C using a rotary evaporator and dried to obtain a saccharide of 3.09 with an average degree of polymerization of 2.5. Next, the carbohydrate 39 was added to a mixed solvent of 12 parts of dimethylformamide and 6 parts of pyridine, heated to 90° C. with stirring, and 6 g of oleic acid chloride was added dropwise and reacted for 5 hours. After the reaction, the mixed solvent was distilled off, washed with about 60 ml of water, extracted with about 50 d of chloroform, and further washed with about 150 ml of water.
water and about 100 d of a 1:1 water:methanol solution, and the cough wash was distilled off to obtain 5.3 g of a brown liquid emulsifier with a degree of fatty acid substitution of 1.03. This stuff! ! [The octavalent value was 7.9 (sample 6). Example 7 Average molecular weight 500,000 without hydrolysis reaction,
Example using chitin with a degree of deacetylation of 12%, chitin with an average molecular weight of about 180°000 and a degree of deacetylation of 80%, and chitin hydrolyzate with an average degree of polymerization of 10.2 and a degree of deacetylation of 80%. Oleic acid chloride was added to each sample using the h method similar to 1 (Sample 7, Sample 8, Sample 9). Samples 7 to 9 prepared here and Samples 1 to 6, which are emulsifiers of the present invention obtained in Examples 1 to 6, were mixed with liquid paraffin 1
Add 1g of each to 79 and dissolve by heating.
29 were added and the emulsifying ability of each was observed. The results are shown in Table 1. Table 1 [Evaluation details] (1) Solubility O: Completely dissolved, Δ: Difficult to dissolve, ×: Insoluble (2) Emulsifying ability ○: Completely emulsified, Δ: Slightly separated after several minutes. ×: Sample 7 obtained from chitin that was not emulsified and was not subjected to hydrolysis, as is clear from Table 1. Sample 8 was not dissolved at all in liquid paraffin, and Sample 9 obtained from a chitin hydrolyzate with a degree of polymerization of 10.2 was slightly dissolved but did not emulsify. On the other hand, samples n1 to 6 obtained according to the present invention had good or comparable solubility and emulsifying ability. Example 8゜The emulsifier of the present invention obtained in Examples 1 to 6 (Samples 1 to 6),
Malto-oligosaccharide sesquiolate (sample 10) with an average degree of polymerization of 3.5, which is a fatty acid adduct of a carbohydrate with a structure similar to the carbohydrate used in the present invention, and diglycerine diisostearate, which is an existing emulsifier. (Trial, ! [1) and sorbitan sesquioleate (sample 12) were added in an amount of 0.3 g each to a test tube with an inner diameter of 18 rM1 containing 4.7 g of oil ~J shown in Table 2, and heated to about 70°C. After heating and melting at 5. Added 0g each. This was quickly stirred with a mixer for 30 seconds, capped, shaken up and down once, and further stirred with a mixer for 30 seconds to obtain an emulsified composition. This emulsion composition was left in a constant temperature room at 15°C,
One minute later, after the IR cycle, the emulsified state of 12jIfJ* was observed, and the emulsion stability was evaluated according to the following criteria. (Evaluation) [Contents] 5: Maintains stable emulsified state 4: Slightly separates, but maintains emulsified state (separation degree 1
3: Separation state is clear (separation degree 1-30%) 2: Separation almost in two layers (separation degree 30% or more) 1: Separation into 3 layers The results are shown in Table 2. As is clear from Table 2 in the margin below, Sample 1 is an emulsifier of the present invention.
For samples 10. to 6, the evaluation did not fall below "4", and the carbohydrate portion of the present invention was replaced with another carbohydrate. Sample 11, which is an existing emulsifier. It exhibited better emulsion stability than Sample 12 for each oil agent. Example 9゜The emulsifier of the present invention obtained in Examples 1 to 6 (Samples 1 to 6),
1 g of each of the emulsifiers (samples 10 to 12) used in Example 8
2g of N-acedel-0-stearoyl-glucosamine was added as a binder to each liquid paraffin, and 2g of N-acedel-0-stearoyl-glucosamine was added to each of these as a binder.After heating and dissolving, 809g of purified water was added to obtain an emulsified composition. Regarding the feel of this emulsified composition during use, 20 monitors evaluated "stickiness" and "slimy feeling J" based on the following criteria. (Review (Ii) (Contents) ○: "Stickiness @J" There is no "slimy feeling" and it is very light. Δ: "Slightly sticky" @1 "slimy feeling". ×: There is a "sticky feeling" and "slimy feeling". The results are shown in Table 3. *As is clear from Table 3, the degree in the table indicates the number of people.
The emulsified composition using Samples 1 to 6 had an excellent feel during use. Example 10 An emulsion was prepared using the emulsifier of the present invention according to the following formulation. (1) Sample 3 obtained in Example 3, 2.0
(1(2) Polyoxyethylene sorbitan monooleate (20E, 0) 1.0 a3)
Cetyl alcohol 0.594) Dipentaerythritol fatty acid ester 2,095) 1.3
-Butylene glycol 15. Og6) Liquid paraffin 14.5! ]7) Carboxyvinyl polymer 0.24Q8) Sodium hydroxide 0.06su9) Preservative 0.1910) Purified water 64.6! J above (
After dissolving 7) and (8) with a portion of (10) respectively. Mix these. Further, the remaining parts of (9) and (10) were added and dissolved by heating, and the mixture of (1) to (6) mixed and heated and dissolved was added and emulsified to obtain a milky lotion. The obtained emulsion had good emulsion stability, good ``compatibility with the skin'', no ``stickiness'' or ``sliminess'', and an excellent feel during use. Example 11 A cream was manufactured using the emulsifier of the present invention according to the following formulation. (1) Sample 5 with 8q in Example 5 3.0
g(2) Glyceryl monostearate 4.
0q(3) Polyethylene glycol monostearate (
40E, 0) 2. O. 4) Behenyl alcohol 2.0g5)
Cetyl alcohol 2.0g6) Dimethylpolysiloxane (100cSt) 0.5g7
) Squalane 3.098)
]・Glyceryl rioctanoate 8.0g9)
1.3-Butylene glycol 10. OQ
10) Preservative 0.2
gll) Purified water 65.
30 The above (9) to (11) were mixed, heated and dissolved, and the mixed, heated and dissolved mixture of (1) to (8) was added thereto to emulsify to obtain a cream. The resulting cream had good emulsion stability, good ``compatibility with the skin'', no ``stickiness'' or ``sliminess'', and an excellent feel during use. [Effect of the invention] The present invention provides glucosamine, N-7 cetylglucosamine,
Since it is an emulsifier that uses V4 material selected from homopolymers or copolymers with a polymerization degree of 10 or less as an Iji ingredient, it has an oil content that is not found in similar carbohydrates with a polymerization degree of 10 or more. It has solubility and emulsifying ability, and the cosmetics obtained by adding it have higher emulsion stability and better feel when used compared to those obtained with conventionally known emulsifiers. It is. It is particularly effective for obtaining a W10 type emulsion composition, so it is easy to impart water retention and water repellency.
It is a suitable emulsifier in cosmetics.

Claims (1)

[Scope of Claims] 1. An emulsifier characterized in that a fatty acid is added to a carbohydrate selected from glucosamine, N-acetylglucosamine, and homopolymers or copolymers thereof having a degree of polymerization of 10 or less. 2. An emulsified cosmetic comprising the emulsifier according to claim 1.