JP2001226215A - Cosmetic and method of producing ether derivative of raffinose - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cosmetic soft to the skin and excellent in a feeling. SOLUTION: This cosmetic contains an alkyl ether and/or alkenyl ether- substituted raffinose compound, wherein the alkyl is a 1-24C alkyl, the alkenyl is a 3-24C alkenyl, and the raffinose compound has an average number of substituents of 1-11.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD [0001] The present invention relates to a highly safe,
The present invention relates to cosmetics containing an alkyl ether form and / or an alkenyl ether form of raffinose, which is a new cosmetic raw material, and a method for producing the ether derivative. More specifically, the present invention relates to a cosmetic which is skin-friendly and has a good feel by blending an alkyl ether and / or alkenyl ether of raffinose which is present in a natural system and has an excellent cell protection effect. The present invention also relates to a production method for synthesizing the ether derivative.

[0002]

2. Description of the Related Art Conventionally, raffinose has been described in many published patent publications as a kind of polyhydric alcohols and polysaccharides, and it has been known that raffinose is simply incorporated into cosmetics. Also,
JP-B-47-7762 proposes a raffinose ester-based surfactant.

[0003]

However, these publications do not describe the alkyl ether and alkenyl ether forms of raffinose and their characteristics, and furthermore, the fatty acid ester form of raffinose which is the surfactant of the above publication is not disclosed. In the case of a water-based preparation, depending on the combination of the ingredients in the preparation, the performance may deteriorate over time, or the behavior may be sensitive to a change in pH, and it may be difficult to formulate the formulation.

[0004]

SUMMARY OF THE INVENTION The present inventors have proposed that raffinose can be used to protect its own cells when certain plants, such as legumes, are exposed to harsh environments such as freezing. As a result of intensive studies on the properties of raffinose, it was found that raffinose has some effect on the hydroxyl group of other compounds, and that the raffinose hydroxyl groups interact independently in nuclear magnetic resonance spectra. We have found phenomena such as the fact that there is no unique situation. Then, when synthesizing an alkyl ether form or an alkenyl ether form of raffinose, it is difficult to obtain a polysubstituted form of ordinary saccharides due to steric hindrance, but it is easily obtained with a raffinose. understood. Utilizing this feature, alkyl ether of raffinose having various substitution numbers,
Alternatively, when an alkenyl ether compound was developed and blended into a cosmetic, it was found that these components were gentle on the skin, had excellent feel, and had excellent stability in the preparation.

Further, as a result of examining various reaction conditions when synthesizing an alkyl ether compound and an alkenyl ether compound of raffinose having the above-mentioned excellent characteristics,
In the reaction solvent, in the presence of an alkali, raffinose and an alkyl halide having 1 to 24 carbon atoms and / or 3 carbon atoms.
To produce an alkyl ether of raffinose and / or an alkenyl ether of raffinose. In particular, it has been found that when dimethyl sulfoxide is used as a reaction solvent and the reaction is caused to occur under anhydrous conditions, the target product can be obtained in a high yield, and the production cost can be significantly reduced.

That is, the first invention has a carbon number of 1 to 1.
A cosmetic comprising an alkyl group having 24 or an alkenyl group having 3 to 24 carbon atoms and having an average substitution number of 1 to 11 and containing an alkyl ether of raffinose and / or an alkenyl ether of raffinose. is there.

A second aspect of the present invention is an alkyl group having 6 to 20 carbon atoms or an alkenyl group having 3 to 24 carbon atoms,
A cosmetic comprising an alkyl ether of raffinose and / or an alkenyl ether of raffinose having an average substitution number of 1 to 2.

A third aspect of the present invention is the above-mentioned cosmetic, wherein raffinose is derived from a natural source.

A fourth aspect of the present invention is to produce raffinose by reacting a raffinose with an alkyl halide having 1 to 24 carbon atoms and / or an alkenyl halide having 3 to 24 carbon atoms in a reaction solvent in the presence of an alkali. The present invention relates to a method for producing an alkyl ether of raffinose and / or an alkenyl ether of raffinose.

A fifth aspect of the present invention is the method for producing an alkyl ether of raffinose and / or an alkenyl ether of raffinose, wherein the reaction solvent is dimethyl sulfoxide.

A sixth aspect of the present invention is the above-mentioned alkyl ether of raffinose and / or raffinose, which is produced by using at least one of sodium hydroxide, potassium hydroxide and sodium alkoxide as an alkali and reacting in an anhydrous state. Or a method for producing an alkenyl ether of raffinose.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Raffinose used in the present invention is a kind of trisaccharide and is O-α-D-galactopyranosyl- (1,6) -O-α-D-glucopyranosyl- (1,1).
2) It has a structure of -β-D-fructofuranoside. Raffinose can be obtained synthetically or naturally, as described in JP-A-10-84773. Natural products are preferred because natural products have excellent images and can be easily obtained with high purity. The natural product is obtained from eucalyptus manna, sugar beet molasses, cotton berries, and the like, and is most preferably derived from sugar beet molasses.

The alkyl ether or alkenyl ether of raffinose used in the cosmetic of the present invention includes:
An alkyl group having 1 to 24 carbon atoms or an alkenyl group having 3 to 24 carbon atoms (an aliphatic group having an unsaturated bond) is converted into an ether through an oxygen atom of all or a part of the 11 hydroxyl groups of raffinose. And preferably etherified with an alkyl or alkenyl group having 6 to 20 carbon atoms, and the average number of substitution is 1 to 1
The ether derivative in the range of 1 can be used, but the ether derivative is used not only as a touch control agent for improving the tackiness or imparting a moist feeling, but also when the average substitution number is in the range of 1 to 2. Is preferred because it has a surfactant activity and can be used as a surfactant. Further, when the average number of substitution is 2 or more, it shows properties as an emulsifier to an oil agent, depending on the alkyl chain length and the alkenyl chain length. Then, as the average substitution number increases, the characteristics of the solid oil come to be exhibited. In the present invention, when an alkyl ether or alkenyl ether of raffinose is used as an oil, it can be used as a liquid oil or a solid oil depending on the characteristics of the dosage form. In the present invention, a linear or branched alkyl group or an alkenyl group having 3 to 24 carbon atoms is substituted in the range of 1 to 24 carbon atoms. The effect as an activator, oil agent or the like can be remarkably obtained. The number of the substituents is, for example, proton NM
It can be measured using R (nuclear magnetic resonance spectrum).

The method for obtaining the alkyl ether and alkenyl ether forms of raffinose in the cosmetic of the present invention will be described in detail in Examples below.
(1) In a reaction solvent such as propylene glycol, in the presence of an alkali such as sodium methoxide, or a surfactant such as sodium stearate, an alkyl bromide or alkyl having 1 to 24 carbon atoms in an amount corresponding to the number of substitutions therein. Alkyl halides such as chlorides, or 3 to 2 carbon atoms
(4) a method of reacting an alkenyl halide such as alkenyl chloride or alkenyl bromide to produce an ether derivative, (2) using a sodium methoxide or sodium hydride in an aprotic solvent such as N, N-dimethylformamide The alkoxide is used to convert the hydroxyl group of raffinose to an alkoxide having an amount of 1 to 24 carbon atoms according to the number of substitution
Reaction of an alkyl halide such as an alkyl bromide or an alkyl chloride, or an alkenyl halide such as an alkenyl chloride or an alkenyl bromide having 3 to 24 carbon atoms to produce an ether derivative; Using a protic solvent, preferably dimethylsulfoxide, which provides a high reaction yield, is used as the reaction solvent, and an alkyl halide having 1 to 24 carbon atoms and / or an alkenyl having 3 to 24 carbon atoms in an amount corresponding to the number of substitutions. Halide and raffinose together with an alkali such as sodium hydroxide, potassium hydroxide, calcium oxide, barium oxide, and sodium alkoxide such as sodium methoxide, preferably sodium hydroxide and hydroxyl which are alkalis capable of obtaining a high reaction yield A method of producing an ether derivative by adding potassium and sodium alkoxides and reacting the same can be mentioned. Particularly, the production method (3) has a high yield, can use general-purpose raw materials as raw materials to be used, and can reduce costs. preferable. In all methods, it is preferable to use an inert gas during the reaction. In this case, it is preferable to analyze the state of the alkyl etherification and the alkenyl etherification using a proton NMR after separating the obtained synthesized product by a column.

As for the conditions during the production, the reaction temperature is preferably 70 to 150 ° C. in the method (1), and the reaction time is, for example, 1 to 8 hours at 120 ° C., and the reaction temperature is 1 to 8 hours in the method (2). The reaction time is preferably 20 to 100 ° C, and the reaction time is, for example, 5 to 60 hours at 45 ° C. In the method (3), the reaction temperature is preferably 60 to 150 ° C, and the reaction time is, for example, 1 to 8 hours at 100 ° C. It is. The raw material ratio is preferably from 0.5 to 8 equivalents of alkyl halide or alkenyl halide to 1 equivalent of raffinose. After the reaction is completed, the reaction solvent is removed under reduced pressure and heating conditions, and the residue is precipitated by adding (1) a solvent in which the ether derivative is not dissolved, such as ethyl acetate, (2)
It can be purified by a method of removing impurities using a column filled with silica gel or the like. If necessary, the salt of the reaction by-product can be removed with a desalting resin.

The cosmetics of the present invention include basic cosmetics, makeup cosmetics, hair cosmetics, body cosmetics, facial cleansers, soaps, perfumes, bath additives and the like. Dosage forms include liquid, cream, gel, solid, powder, sheet, aerosol, and the like. In addition to the above-mentioned cosmetics, besides blending an alkyl ether of raffinose and / or an alkenyl ether of raffinol as an essential component, conventionally known powders, surfactants, oils, humectants, ultraviolet ray protective components, Active ingredients,
Preservatives, pH adjusters, chelating agents, fragrances, dyes, pigments,
A solvent or the like can be appropriately compounded.

The mixing ratio of the alkyl ether of raffinose and / or the alkenyl ether of raffinol to the cosmetic of the present invention is preferably 0.01 to 99% by mass based on the total amount of the cosmetic. More preferably, the content is 0.1 to 50% by mass. In particular, when used as a surfactant, the content is preferably 0.1 to 10% by mass from the viewpoint of the effect.
50% by mass is preferred for the feel, and when used as a feel modifier, 0.1 to 20% by mass is preferred.

[0018]

The present invention will be specifically described below with reference to examples and comparative examples. The sensory evaluation methods for the cosmetics obtained in the examples and comparative examples are shown below.

[Evaluation of Sensory Characteristics] Ten expert panelists were prepared for each evaluation item (however, panelists may be duplicated depending on the item), and evaluation was performed according to the evaluation criteria shown in Table 1, and the total of all panelists was calculated. The evaluation result was given based on the score. Therefore, the higher the score, the higher the usefulness for the evaluation item is shown (full score: 50 points).

(Table 1) Reference points --------------------------------------- -High effect 5 High effect 4 Low effect 3 Low effect 2 Low effect 1

Example 1 (Synthesis example 1 of monododecyl ether of raffinose) In a 1-liter eggplant-shaped flask whose inside was dried with argon gas, 61.3 g of sodium stearate, 200 g of raffinose (anhydrous), propylene glycol 50
0 ml, 1-bromododecane 192 ml, and sodium methoxide 43.2 g were added, and the mixture was heated at 120 ° C. under argon gas.
Left. At first, raffinose and the like did not dissolve, but after 1.5 hours. 2.5 hours 120 from this time
The solution was stirred at ° C. The reaction solution was heated to 160 ° C. under reduced pressure, and propylene glycol, 1-bromododecane,
After removing by-product methanol and dodecyl alcohol, ethanol was added and the mixture was filtered to remove unreacted raffinose,
The sodium stearate was removed. The filtrate was concentrated once, dissolved in methanol, extracted with hexane, and the remaining dodecyl alcohol was removed and concentrated again. After adding water to the concentrate and freeze-drying, white crystals 1
02.1 g were obtained. Dissolve this sample in heavy water and add proton N
When MR was measured, it was confirmed that it was a monododecyl ether of raffinose in which a dodecyl group was bonded to any one of the 11 hydroxyl groups of the raffinose molecule by an ether bond.

Example 2 (Synthesis example 2 of monododecyl ether of raffinose) 200 mg of sodium hydride and 10 ml of dimethyl sulfoxide were added to a dried 200 ml eggplant-shaped flask, and raffinose (anhydrous) dissolved in 12 ml of dimethyl sulfoxide was added. 2.5 g). 2.5 hours later, 2.5 g of raffinose (anhydrous) dissolved in 12 ml of dimethyl sulfoxide was added to the reaction solution, and then 1-
1.2 ml of bromododecane was gradually added dropwise, and the mixture was stirred at 45 ° C., and the reaction was terminated after 46.5 hours. The reaction solution was extracted by adding n-hexane and methanol, and methanol and dimethyl sulfoxide were removed while heating the methanol phase under reduced pressure to 120 ° C. Isopropanol and methanol were added to the residue, followed by stirring at room temperature for 2 hours, followed by filtration. The filtrate was concentrated and purified by a silica gel flash column to obtain 3.36 g of cream crystals. The crystals were dissolved in heavy water and subjected to proton NMR measurement to confirm that the crystals were a radonose monododecyl ether.

Example 3 (Synthesis Example of Raffice Polyoctyl Ether Form) 24 g of sodium hydride and 25 ml of N, N-dimethylformamide were added to a 1-liter separable flask whose inside was dried with argon gas. After 1 hour, 20.18 g of raffinose (anhydrous) and 250 ml of N, N-dimethylformamide were added. After 3 hours, 56 ml of 1-bromooctane and 30 ml of N, N-dimethylformamide were added, followed by stirring at room temperature under argon. After 16 hours, the reaction temperature was adjusted to 60 ° C., and after 65 hours, 400 ml of water was added to terminate the reaction. After adding n-hexane to the reaction solution and extracting, saturated aqueous sodium bicarbonate was added to the n-hexane phase, washed, dried over anhydrous magnesium sulfate and concentrated to obtain 47.72 g of a crude product (dark brown oil). Was. The crude product was purified using a silica gel flash column to obtain the following three fractions in ascending order of polarity. (A) 8.95 g of a brown solid (B) 4.04 g of orange crystals (C) 2.68 g of orange crystals Also, after concentrating the aqueous phase at the time of the previous extraction, pyridine and acetic anhydride were added and acetylated. Deacetylation,
(D) 6.72 g of ocher crystals were obtained. Regarding the above samples, (A) to (C) are deuterated chloroform, (D)
Was dissolved in heavy water and proton NMR was measured to find the following octyl group introduction rate. (A) 7 to 11 octyl groups (average number of substitution 9) (B) 3 to 7 octyl groups (average number of substitution 5) (C) 3 to 5 octyl groups (average number of substitution 4) (D ) 1 to 3 octyl groups (average number of substitution 2)

Example 4 (Synthesis Example of Dodecyl Ether Form of Raffinose) According to the following reaction method, synthesis of dodecyl raffinose was attempted by changing the alkali used, the amount used and the amount of 1-chlorododecane as shown in Table 2. . 504 mg of raffinose (anhydrous) and 5 ml of dimethyl sulfoxide were added into a reaction vessel, and the mixture was stirred at 100 ° C. for 30 minutes. Then, in the presence of an inert gas, each alkali and 1-chlorododecane were added and reacted for 3 hours. After the reaction, the raffinose content of the solution was quantified by high performance liquid chromatography (HPLC), and the reaction rate of raffinose was calculated. Table 2 shows the results. An example using barium oxide (No. 1)
In No. 0), raffinose could not be quantified by HPLC, but it was confirmed by thin-layer chromatography analysis that the reaction had progressed to the same extent as in the case of using calcium oxide (No. 9). Was.

[Table 2]

Example 5 (Production Example of Purified Dodecyl Ether Form of Raffinose) A raffinose (anhydride) (5.044 g) and dimethyl sulfoxide (50 ml) were added to a 200-ml eggplant flask, and the mixture was stirred at 80 ° C. while reducing the pressure with an aspirator. did.
After 1 hour, the pressure was released and the inside of the reaction vessel was replaced with an inert gas. Then, 1.74 g of potassium hydroxide and 4.71 ml of 1-chlorododecane were added, and the mixture was stirred at 100 ° C. for 3 hours. After completion of the reaction, the reaction solution was largely removed at 120 ° C. under reduced pressure with a vacuum pump, and a small amount of methanol was added to the residue, followed by addition of ethyl acetate to precipitate. The precipitate was separated by filtration, thoroughly dried, and then desalted. The filtrate was lyophilized to give white crystals (including raffinose) containing 4.55 g of dodecyl raffinose. In addition, the number of substitution of the dodecyl group of the obtained dodecyl ether of raffinose is 1 to
In 2, the average substitution number was about 1.5.

Example 6 (Synthesis example of dodecyl ether form of raffinose) In Examples 4 and 5, 1-chlorododecane was used. A dodecyl ether form of raffinose can be synthesized. Raffinose (anhydrous) 50
4 mg and 5 ml of dimethyl sulfoxide were added to the reaction vessel, and the mixture was stirred at 100 ° C. for 30 minutes, and then, in the presence of an inert gas,
Each alkali and 1-bromododecane 480 shown in Table 3
μl was added and the reaction was performed for 3 hours. Table 3 shows the results.

[Table 3]

Example 7 (Synthesis example of dodecyl ether of raffinose) In Examples 5 and 6, dimethyl sulfoxide was used as a solvent. However, even if N-methylpyrrolidinone was used, a desired dodecyl ether of raffinose was synthesized. can do. Add 504 mg of raffinose (anhydrous anhydride) and 5 ml of N-methylpyrrolidinone into a reaction vessel and add 1
After stirring at 00 ° C. for 30 minutes, 174 mg of potassium hydroxide and 471 μm of 1-chlorododecane were added in the presence of an inert gas.
1 was added and the reaction was carried out for 3 hours. As a result of quantifying unreacted raffinose, the reaction rate of raffinose was 29.9%.

Example 8 (Synthesis example of octyl ether of raffinose) Although the above description has been about dodecyl etherification of raffinose, other alkyl ethers can be synthesized in the same manner. An example using 1-chlorooctane will be described as an example. 504 mg of raffinose and 5 ml of dimethyl sulfoxide were added into a reaction vessel, and the mixture was stirred at 100 ° C. for 30 minutes. Then, 87 mg of potassium hydroxide and 85 μl of 1-chlorooctane were added in the presence of an inert gas, followed by a reaction for 3 hours. As a result of quantifying unreacted raffinose, the reaction rate of raffinose was 36.1%. The number of octyl groups substituted in the octyl ether of raffinose was 1-2, and the average number of substitutions was about 1.5.

The following cosmetics were prepared using the alkyl ether of raffinose obtained in the above Examples.

Example 9 A lotion was produced according to the formulation and production method shown in Table 4. The unit of the compounding amount is mass% (the same applies hereinafter).

[Table 4] (1) Ethanol 10.0 (2) Polyoxyethylene hydrogenated castor oil (60EO) 0.5 (3) Dodecyl ether of raffinose (Example 1) 1.0 (4) ) Glycerin 11.0 (5) 1,3-butylene glycol 2.0 (6) Methyl paraoxybenzoate 0.2 (7) Citric acid 0.1 (8) Sodium citrate 0.3 (9) Fragrance 1 (10) Remaining amount of purified water

[Production method] Components (1) to (6) and component (9) are mixed and dissolved. This is converted to components (7) and (8)
And (10) are added to the mixed solution. After stirring well, the mixture was filtered and filled in a container to obtain a lotion.

Example 10 The procedure of Example 9 was repeated, except that the dodecyl ether of raffinose obtained in Example 5 was used instead of the dodecyl ether of raffinose obtained in Example 1. Thus, a lotion of Example 10 was obtained.

Example 11 A cream was produced according to the formulation and production method shown in Table 5.

[Table 5] (1) Squalane 10.0 (2) Octyldodecyl myristate 5.0 (3) Stearic acid 1.0 (4) Glycerin monostearate 1.5 (5) Oil oxyethylene monolaurate Sorbitan 1.0 (20EO) (6) Dioctyl ether of raffinose (D component of Example 3) 1.0 (7) Cetanol 3.0 (8) Methyl paraoxybenzoate 0.1 (9) Paraoxy Ethyl benzoate 0.1 (10) Butyl paraoxybenzoate 0.1 (11) Glycerin 15.0 (12) Dipropylene glycol 3.0 (13) Fragrance 0.2 (14) Remaining amount of purified water

[Production Method] Components (1) to (10) were added to 80
Heat to ℃ and mix and dissolve. This is referred to as component (11), (1
Add 2) and (14) to the mixture dissolved at 80 ° C. and stir well. The component (13) was added at 70 ° C., cooled, and filled in a container to obtain a cream.

Example 12 The procedure of Example 11 was repeated, except that the dioctyl ether of raffinose, which is the D component obtained in Example 3, was used instead of the octyl ether of raffinose obtained in Example 8. In the same manner as in Example 11, a cream of Example 12 was obtained.

Comparative Example 1 A lotion was obtained in the same manner as in Example 9 except that raffinose myristate, which is an ester, was used instead of the dodecyl ether of raffinose used in Example 9.

Comparative Example 2 A cream was obtained in the same manner as in Example 11, except that purified water was used in place of the octyl ether of raffinose used in Example 11.

Tables 6 and 7 show the evaluation results of the examples and comparative examples. The stability over time in Table 6 was evaluated from changes in external color, smell, and odor when stored in a thermostat at 40 ° C. for one month.

[0043]

Table 7 shows the results of the sensory evaluation when using the product.

[Table 7] Skin is moisturized when used continuously. Excellent in refreshing feeling. No abnormality. ---------------------------- --------------------------------------- Example 9 50 45 48 Example 10 50 46 48 Example 11 50 48 43 Example 12 50 47 45 Comparative Example 1 43 44 44 Comparative Example 2 38 34 22

From the results shown in Table 6, it can be seen that Examples of the present invention are superior to Comparative Example 1 in stability over time. Also, from the results in Table 7, it can be seen that each of the examples of the present invention exerts no burden on the skin and has a moist and refreshing feel to the skin as compared with the comparative examples.

[0047]

As described above, the present invention provides a skin-friendly and feel-friendly by blending an alkyl ether form of raffinose or an alkenyl ether form of raffinose which is a natural component and has an excellent cell protection effect. It is clear that excellent cosmetics can be obtained.

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Claims (6)

[Claims] 1. An alkyl group having 1 to 24 carbon atoms or an alkenyl group having 3 to 24 carbon atoms, wherein an alkyl ether of raffinose and / or an alkenyl ether of raffinose having an average substitution number of 1 to 11 are used. Cosmetics characterized by containing. 2. An alkyl ether having 6 to 20 carbon atoms or an alkenyl group having 3 to 24 carbon atoms, and an alkyl ether of raffinose having an average substitution number of 1 to 2 and / or
Or a cosmetic containing an alkenyl ether of raffinose. 3. The cosmetic according to claim 1, wherein the raffinose is of natural origin. 4. A raffinose produced by reacting raffinose with an alkyl halide having 1 to 24 carbon atoms and / or an alkenyl halide having 3 to 24 carbon atoms in a reaction solvent in the presence of an alkali. A method for producing an alkyl ether compound and / or an alkenyl ether compound of raffinose. 5. The method for producing an alkyl ether of raffinose and / or an alkenyl ether of raffinose according to claim 4, wherein the reaction solvent is dimethyl sulfoxide. 6. The alkyl ether of raffinose and / or raffinose according to claim 4, characterized in that it is produced by using at least one of sodium hydroxide, potassium hydroxide and sodium alkoxide as an alkali and reacting in an anhydrous state. Or a method for producing an alkenyl ether of raffinose.