JPS62201807A - Cosmetic - Google Patents

Abstract

PURPOSE:A cosmetic which requires no blending of water-soluble high polymer, causes no molds, etc., is storable for a long period and shows improves effects on feeling in use such as smoothness, etc., containing an oily agent for cosmetic and partially methylated cyclodextrin. CONSTITUTION:A cosmetic containing an oily agent for cosmetic and partially methylated cyclodextrin as active ingredients. In order to prepare the cosmetic, aqueous solutions or aqueous dispersions of the oily agent and the partially methylated cyclodextrin (partially methylated CD for short) are previously made, blended with a cosmetic base, kneaded and dissolved by a well-known method of cosmetic production. The blending ratio of the oil agent and the partially methylated CD is preferably 3-10wt% based on the total amounts of water and the oily agent. The partially methylated CD is a compound wherein hydrogen of each hydroxyl group at the 2, 3 or 6 position of cyclodextrin is partially replaced with methyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a cosmetic oil-based agent and a cosmetic containing a partially methylated cyclodextrin.

° (Prior art) Cosmetics are generally divided into oils, surfactants, fragrances,
Although prepared from a base such as water, surfactants are known to have drawbacks such as their toxicity, skin irritation, or reducing the effectiveness of preservatives commonly added to cosmetics.

Therefore, it is necessary to improve these problems (various interfaces).

Active agents or their alternatives have been proposed (e.g.
(See Japanese Patent Application Laid-open Nos. 59-1403 and 55-11527, etc.). In particular, the latter is derived from oil-based raw materials for cosmetics, aqueous raw materials, water-soluble polymers, and cyclodextrins, and is interesting because a certain level of emulsion stability can be expected without using commonly used surfactants. It is an invention.

(Problems to be Solved by the Invention) However, as is clear from the composition, in order to achieve the intended purpose, the formulation of water-soluble polymers is essential. Furthermore, although cyclodextrin itself can be expected to have a certain degree of microbial stability, it is degraded by α-amylase produced by certain spore-forming bacteria or molds, making it unsuitable for long-term storage. There were problems such as:

Therefore, the present inventors searched for a substance that can be used as a cosmetic base material or in combination with other base materials as a substitute for surfactants, and found that partially methylated cyclodextrin (partially methylated cyclodextrin)
Compared to the case of using cyclodextrin mentioned above, if IJ is used in combination with oil-based ingredients, it is not a foolproof method that does not necessarily require the combination of water-soluble polymers, and it is smoother when used in general cosmetics. The present invention was completed based on the discovery that the present invention has an excellent effect on the feeling of use when using the product.

(Means for Solving the Problems) Accordingly, the present invention provides a cosmetic containing an oily agent for cosmetics and a partially methylated cyclodextrin.

The cosmetics referred to in the present invention may be any type of cosmetics as long as they contain oily ingredients. Specifically, so-called creams such as cold creams and vanishing creams; hand lotion creams such as hand lotion cream, liquid nokter base s/') skin creams, etc.: white powder, lipstick, Eye shadow and other products; liquids, etc.; hair loaf, 7, hair tonic, and other hair products;
Includes cosmetic soaps, etc.

Therefore, oily agents for cosmetics include all oily components used in the above-mentioned cosmetics, regardless of their type or origin. For example, hydrocarbons, natural vegetable oils, fatty acids,
Or these and lower alcohol esters S, Xa alcohol, wax, steric acid, fat-soluble vitamins,
Examples include fragrances and the like. More specifically, the hydrocarbons include liquid paraffin, squa2, premethane, octene-1 polymerized oil, dodecene-1 polymerized oil, 2,6,10
゜15.19,23-hexamethyltetracosane, liquid polyisobutylene, liquid polyisobutyne, etc.; natural vegetable oils include olive oil, soybean oil, rice bran oil, palm oil, castor oil, cottonseed oil rings; fatty acids include carbon atoms of 10 ~
20 saturated or unsaturated fatty acids, such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, linoleic acid, lylunic acid, stearolic acid, etc.; esters of these and lower alcohols include! Tylstearate, hexyl laurate, butyl palmitate,
Butyl myristate, hexyl stearate, hexyl myristate, etc.; higher alcohols have 10 carbon atoms
~20 Alcohols obtained by high-pressure reduction of animal and vegetable oils such as cetyl alcohol, stearyl alcohol, and oleic alcohol; Waxes include esters of fatty acids and higher-hydric alcohols that are insoluble in water, and dihydric alcohols. , beeswax, spermaceti wax, carnauba wax, wool wax, etc. Examples of sterins include lanosterin, cholesterin, etc.; examples of fat-soluble vitamins include vitamins A and D.

E, F or Ni, etc.; examples of fragrances include dalaniol, citronellol, tervineonol, linalool and the like.

In addition, the partially methylated cyclodextrin referred to in the present invention refers to a cyclodextrin (hereinafter sometimes abbreviated as r CD J) in which the hydrogen atoms of each hydroxyl group at the 2, 3, or 6 position are partially substituted with a methyl group. Heptakis-(2,6-di-0-methyl)β-CD, heptakis-(2,3,6-di-0-methyl) derived from β-CD, which is completely methylated at the 2 and 6 positions. -Methyl) excluding β-CD.

Specifically, compositions in which the average methylation rate of the hydroxyl group at each glucose unit position in the total glucose constituting the cyclodextrin exhibit different values and each have the following physical and chemical properties are preferably used. It can be mentioned as a thing.

(+) A) Average methylation rate 2nd position: 55-64th position 3rd position: 43th-51st position: 99-100th position B) Melting point (capillary method) 142-161°C C) Specific optical rotation [α 5: 158-162° (e = 1. water),
And silica gel thin layer chromatography (exhibition:
Rf value approximately 0 in chloroform/methanol = 9/1)
．． The main component is a composition that gives a single spot around 55 (hereinafter referred to as rPMCDi J).

(ii) A) Average methylation rate 2nd position: 55-66% 3rd position: 39-45th position 286-88th position B) Melting point (capillary method) 159-170°C C) Specific optical rotation [α 5: 156-159° (cxl, water) and silica) fpv thin layer chromatography (exhibition H
Solvent: Chloroform/methanol-9/1) K, Rf
The main component is a composition that gives a single spot at a value around 0.42 (hereinafter referred to as rPMCD-II J).

(in) A) Average methylation rate 2nd position: 53-61% 3rd position = 38-45th position: 70-77% B) Melting point (capillary method) 167-180°C C) Specific optical rotation [α] 25 : 167 to 180° (c=1, water), and gives a single spot at an Rf value of about 0.30 in silica gel thin layer chromatography (developing solvent: chloroform/methanol-9/1) composition (hereinafter referred to as rPMCD-III J).

1) V) A) Average methylation rate 2nd position: 52-55% 3rd position: 41-45th position 2 58-64% B) Melting point (capillary method) 178-195°C C) Specific optical rotation [α), 154-157° (c-1, water),
And, silica gel thin layer chromatography (development medium:
R4 value approximately 0 in chloroform/methanol-9/1)
．． 17 (hereinafter referred to as rPMCD-IV J).

Note that the above methylation rate was calculated as follows.

Preparation of sample for measuring methylation rate 1) Hydrolyzed methylated β-CD approximately 100 capes with water 4.251! Dissolve in tl, add 0.751 of trifluoroacetic acid and heat at 100'C.
Heat overnight. The reaction solution was concentrated under reduced pressure to remove trifluoroacetic acid. Add a small amount of water to the residue and concentrate again under reduced pressure.

2) Reduction The concentrated residue is dissolved in water 51117 and cooled in an ice-water bath.

After adding 0.56 F- of sodium borohydride little by little, the mixture was stirred at 0°C for 4 hours. After the reaction, excess sodium borohydride is decomposed with 30% acetic acid.

After stirring at 20°C for 1 hour, Amberlite
it・)IR-120B (H+form) 15 y
d and concentrated under reduced pressure.

Add a small amount of methanol to the residue and concentrate again under reduced pressure.

3) Add 1 or R1 of pyridine and 5 liters of acetic anhydride to the acetylation concentration residue, stir at 0°C overnight, and then distill off the reagent under reduced pressure.

Distillation under reduced pressure is carried out at a temperature below 40°C. Chloroform 6 to the residue
After adding Ogo and washing with saturated brine, drying with sodium sulfate and concentrating.

Add 1m of A7Ton to the residue and analyze the gas chromatoge 2 fee (
GC) sample.

CB) GC analysis conditions Column: 3% ECN55-M
(Shimadzu) 2frL)<3sutφ Support: Chromoaorb
W (AW-0MC8) 100-120m@ah Column temperature (Column tamp): 180
”C insertion part temperature (Inj@ction tamp):
260℃N2 flow rate: 2
2.5114/rnlnH2 pressure: 0.6 kg/d Calculation of methylation rate From f chromatography as shown in No. 1-1, calculate the proportion of acetylglucose methylated at each position, for example, at the 6th position. The methylation rate was calculated as the sum of the proportions of all 7 cetyl glucose containing 6-0-methyl.

The composition described above can be advantageously manufactured by the following method.

That is, dimethyl sulfate was mixed with β-CD in a sodium hydroxide aqueous solution with a concentration of β-CD and dimethyl sulfate of 10 (weight/volume: hereinafter simply expressed as "H" means the same meaning).
It can be produced by subjecting a reaction mixture obtained by reacting 20 times or more molar equivalent of K to silica gel column chromatography.

Next, to prepare the cosmetic composition of the present invention, partially methylated CD can be added in the form of a powder or an aqueous solution thereof in any step of manufacturing cosmetics containing an oily agent, but preferably, the partially methylated CD can be added in the form of a powder or an aqueous solution thereof. An aqueous solution or aqueous suspension of partially methylated CD may be prepared in advance, blended with other cosmetic bases, and mixed and dissolved using a cosmetic manufacturing method known per se.

Note that the blending ratio of partially methylated CD and oily agent varies depending on the type of oily agent used, the presence or absence of other cosmetic bases, the type and form of the cosmetics to be applied, and is not unusual, and a person skilled in the art can By examining the characteristics of cosmetics prepared in simple small-scale experiments, the optimum blending ratio can be easily determined.

An example of the blending ratio of the oily agent and partially methylated CD that is preferably used is 0.5 with respect to the atK of water and the oily agent.
~15 weights 1*, preferably 3-10 weights! It is better to set it to t.

Note that the present invention does not limit the addition of water-soluble polymers or surfactants depending on the purpose.

(Function) As shown in FIG. 2, the partially methylated CD used in the present invention exhibits unusually high water solubility compared to β-CD.
It is easily soluble in lower alcohols such as methanol, ethanol, pro9ol, and hexanol, ketones such as acetone and methyl ethyl ketone, and aromatic hydrocarbons such as benzene, toluene, and xylene, and also dissolves in liquid paraffin. Again, hey! Takisu (2,6-G0
-methyl)β-CD and hegutakisu(2,3,6-)
It exhibits superior water solubility compared to (O-methyl)β-CD. On the other hand, it retains the function of including a hydrophobic compound (lipophilic compound) having an appropriate bulkiness into the cavity formed by the molecule, which is a feature of CD. Due to these characteristics, in the present invention, partially methylated CD (1) includes part or all of the oily agent molecule in its cavity, and exhibits a kind of surfactant-like action as a molecular compound.

(11) Alone, it increases the affinity between the oil phase and the water phase (promotes the mutual solubility of both phases).

(lil) Preservatives used in cosmetics, such as methyl p-benzoate, are included to ensure retention in the aqueous phase.

6V) Thoroughly wet the surface of powders of solid substances used in cosmetics, such as titanium oxide, Merck, kaolin, etc.

It is believed that these effects collectively reflect the effects of the present invention.

The present invention will be explained in more detail below by showing examples and effects for each common cosmetic product.

Composition (Control) Instead of PMCD-I (1) β-CD: same amount (2) Triethanolamine: same amount were used respectively.

Production method 2 While dissolving and stirring A, B was added, and then C was added and stirred.

Example 2 Cold cream (W2O type) composition (f (j1%)) Wool alcohol 3.0 Coconut oil 12.5 Beeswax 7.0 Solid Nodarafin 1.5 Liquid Nodarafin 35.7 Kujiroku 7.0 PMCD-12,5 Borax 0.5 Water 28.5 (control) P
The same amount of β-CD was used in place of MCD-I.

Manufacturing method: All components were kneaded.

Example 3 Emollient cream (0/V type) composition (!Amount) C fragrance Appropriate amount (control) The same amount of β-CD was used in place of PMCD-I.

Manufacturing method: A was heated to about 60°C, B was heated to about 70°C, and B was added to A while stirring at high speed. Once emulsified, the speed was set to medium and the flavor was added at 45°C.

Composition (wt%) Stearic acid 15.0 PMCD - Summer
3.5 Mineral oil 1.5 Glycerin 5.0 Sodium alginate 0.2 Water
74.8 Fragrance Appropriate amount (control) Snow chin (8pan manufactured by Near Truss) 60:
PMCD-1 was replaced with 2.0 (wt%) Tween (described above) 60:1.5 (wt%).

Manufacturing method: Stir at high speed until uniform emulsification is obtained.

Example 5/Ringing Rosie Composition (weight f%) C Perfume Appropriate amount (control) The same amount of β-CD was used in place of PMCD-1.

Production Method 2 A was heated to 65°C and B was heated to 70°C and added to Bt-A little by little while stirring, and after the temperature reached room temperature, the fragrance was added and further stirred.

(% by weight) C fragrance Appropriate amount (control) The same amount of sodium lauryl alcohol sulfate was used in place of PMCD-1.

Production Method 2 While stirring B at high speed at room temperature, A was added little by little, and C was added at a medium speed.

Example 7 White powder PMCD-I 1.0
Cetyl Alcohol 4.0 Zinc White
2.5 Talc 10.0 Pigment 8.5 Glycerin 12.0 Water ioo, o (control) Use the same amount of β-CD instead of PMCD-1.

Manufacturing method: Thoroughly mix the powder and pigment with half the amount of glycerin and half of the water. PMCD-1 and cetyl alcohol are dissolved in the remaining water, heated to about 70°C, cooled again with stirring, and mixed into the previous powder and pigment mixture.

Examples 8 to 14 In place of PM■-■ in Examples 1 to 7, PMCD-
A similar cosmetic product was manufactured using (2).

Examples 15-21 Instead of PMCD-1 in Examples 1-7, PMC
A similar cosmetic product was produced using D-■.

Examples 22 to 28 In place of PMCD-1 in Examples 1 to 7, PMCD
A similar cosmetic product was produced using -■.

(Efficacy) For each of the cosmetics obtained above, evaluate the appearance of the product, the texture of the appearance, and the feeling of use (stickiness to the skin, spreadability, dryness, powderiness, irritation level 1, etc.) The results are shown in the table below.

[Brief explanation of drawings]

FIG. 1 shows a chromatograph of a sample prepared for calculating the methylation rate of PMCD-■. Figure 2 shows β-CD (Δ) and PMCD-1 (・)
, heptakis-(2,6-di-0-methyl)β-CD (
l relative to water at each temperature of heptakis-(2,3,6-tri-0-methyl)β-CD (marked by O) and heptakis-(2,3,6-tri-〇-methyl)β-CD (marked by Mu)
This shows the Wm property.

Claims (1)

[Scope of Claims] 1. A cosmetic containing an oily agent for cosmetics and a partially methylated cyclodextrin. 2. Partially methylated cyclodextrin is the following A) to C)
Physical and chemical properties A) Average methylation rate 2nd place: 55-64% 3rd place: 43-51% 6th place: 99-100% B) Melting point (capillary method) 142-161°C C) Specific optical rotation [α] ^2^5_D: 158-162° (c=1, water)
The cosmetic according to claim 1, which is mainly composed of a composition that shows the following and gives a single spot in silica gel thin layer chromatography (developing solvent: chloroform/methanol = 9/1). . 3. Partially methylated cyclodextrin is the following A) to C)
Physical and chemical properties A) Average methylation rate 2nd place: 55-66% 3rd place: 39-45% 6th place: 86-88% B) Melting point (capillary method) 159-170°C C) Specific optical rotation [α] ^2^5_D: 156-159° (c=1, water)
The cosmetic according to claim 1, which is mainly composed of a composition that exhibits the following properties and gives a single spot in silica gel thin layer chromatography (developing solvent: chloroform/methanol = 9/1). fee. 4. Partially methylated cyclodextrin is the following A) to C)
Physical and chemical properties A) Average methylation rate 2nd place: 53-61% 3rd place: 38-45% 6th place: 70-77% B) Melting point (capillary method) 167-180°C C) Specific optical rotation [α] ^2^5_D: 167-180° (c=1, water)
The cosmetic according to claim 1, which is mainly composed of a composition that exhibits the following properties and gives a single spot in silica gel thin layer chromatography (developing solvent: chloroform/methanol = 9/1). fee. 5. Partially methylated cyclodextrin is the following A) to C)
Physical and chemical properties A) Average methylation rate 2nd place: 52-55% 3rd place: 41-45% 6th place: 58-64% B) Melting point (capillary method) 178-195°C C) Specific optical rotation [α] ^2^5_D154-157° (c=1, water) and a composition that gives a single spot in silica gel thin layer chromatography (developing solvent: chloroform/methanol = 9/1) as the main component. The cosmetic composition according to claim 1, which is a cosmetic composition according to claim 1. 6. Claims according to any one of claims 1 to 5, wherein the oily agent for cosmetics is a hydrocarbon, a natural vegetable oil, a fatty acid or an ester of these and a lower alcohol, a higher alcohol, a wax, or a sterine. cosmetics.