JP2000154161A - Oligoalkyloxirane derivative, its production and use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject derivative having excellent moisture retention, having no sticky feeling, a proper oily feeling, a slight change in smell with time, useful as a humectant by reacting an alkyloxirane of glycerol. SOLUTION: This derivative is shown by formula I [AO is OCH2CH(CH3) or the like; EO is OCH2CH2; AO and EO may be added randomly or in a blocked state; k, m and n are each a number of addition mols of AO and a, b and c are each a number of addition mols of EO; 1<=k, m, n<=10, 0<=a, b, c<=3, 5<=k, m, n<=10, 0<=a+b+c <=3] and has <=1,040 polydispersity, 40-90 deg.C clouding point of 50 wt.% aqueous solution and <=0.03 saturation degree. The derivative is obtained by bringing an alcoholate catalyst of the formula ROX (R is a 1-4C hydrocarbon; X is potassium) into contact with glycerol, dealcoholizing the resultant substance and reacting the dealcoholized substance with an alkyloxirane.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel and useful oligoalkyloxirane derivative in which alkyloxirane is added to glycerin, a method for producing the same, and a use thereof.
More specifically, the molecular weight distribution is narrow, the cloud point of the aqueous solution is in a certain range, the oligoalkyl oxirane derivative having a low degree of unsaturation, a method for producing the same, and a moisturizer made of the derivative without stickiness and generation of odor over time. The present invention relates to an agent, and a cosmetic or cleaning agent containing the humectant.

[0002]

2. Description of the Related Art At present, due to problems of dry skin and atopy,
Cosmetics, detergents and toilet soaps containing moisturizers are increasing. Examples of the humectant used for these include polyhydric alcohols such as 1,3-butashidiol and glycerin, and polyethylene glycol dialkyl ethers as disclosed in JP-A-10-167948. When a large amount of polyethylene glycol dialkyl ether is used, there is a problem that stickiness is left.

In order to solve this problem, an alkyl oxirane derivative obtained by adding about 1 to 50 moles of an oxirane such as oxirane or methyl oxirane to a polyhydric alcohol having 3 or more functional groups is generally used. is there. Alkyl oxirane derivatives in which alkyl oxirane is added to a polyhydric alcohol having three or more functional groups can change the balance of hydrophilicity / lipophilicity by changing the number of moles of alkyl oxirane, thereby providing an arbitrary feeling of use. Can be adjusted. For this reason, adducts obtained by adding methyloxirane to diglycerin and the like are used as moisturizing ingredients for cosmetics.

[0004]

However, even an alkyl oxirane derivative of a polyhydric alcohol having three or more functional groups is not completely free of stickiness. Stickiness occurs as in the case. In addition, there is also a problem that a stable blending system cannot be formed because the oiliness varies depending on the lot of the raw material. In addition, JP-A-10-87
As described in Japanese Patent No. 983, there is also a problem that an odor is easily generated over time. As described above, the use of humectants consisting of alkyl oxirane derivatives of polyhydric alcohols is limited in spite of their usefulness due to the above-mentioned problems, and improvement is strongly desired at present. It is.

The present inventors have investigated commercially available alkyl oxirane derivatives of polyhydric alcohols having three or more functional groups in order to search for the causative substance of stickiness. In particular, the alkyloxirane derivative having an average addition mole number of about 1 to 15 moles has 1 to 30% of unreacted polyhydric alcohol remaining,
Moreover, alkyl oxirane is added to water molecules in the system.
Functional alkyloxirane derivatives were also produced as by-products, and the molecular weight distribution was found to be broad. Such an unreacted polyhydric alcohol, a bifunctional compound and a compound with a high addition mole number cause stickiness as in the case where the polyhydric alcohol is used alone. On the other hand, if the molecular weight distribution is too wide, the balance between hydrophilicity and lipophilicity of the product will be lost, and the appropriate oily feeling required for the humectant will be impaired.

The present inventors further investigated the cause of the odor of the polyfunctional alkyloxirane derivative,
Commercially available alkyl oxirane derivatives, particularly methyl oxirane derivatives, contain unsaturated compounds having a propenyl group or an allyl group by-produced during the addition reaction (Yoshikazu Goto, Journal of Polymers, vol. 50, No. .2, 12
1-126, 1993), it has been found that these unsaturated compounds are decomposed with time to form propionaldehyde, which is the main cause of odor.

Hitherto, regarding impurities contained in alkyl oxirane derivatives of polyhydric alcohols, impurities have been studied in high molecular weight alkyl oxirane derivatives having a molecular weight of 1000 or more (Yoshikazu Goto, Journal of the Chemical Society of Japan; 1993; (9), 1085-1090) In the low addition mole alkyl oxirane derivative useful as a humectant, the impurity contained therein has never been investigated, and therefore, it is a performance as a humectant. None of them considered stickiness, odor and oiliness from the viewpoint of impurities. Therefore, at present, the prescription for using these as cosmetics or cleaning agents is limited.

An object of the present invention is to provide a novel and useful oligoalkyl which is excellent in moisturizing property, has no stickiness, moderate oiliness, and has little change in odor with time. It is an object of the present invention to provide an oxirane derivative, a method for producing the oxirane derivative, a humectant made of this derivative, which does not have a sticky feeling and does not generate odor over time, and a cosmetic and a cleaning agent containing the humectant.

[0009]

The present inventors have conducted intensive studies to obtain a humectant which can be suitably used. As a result, the present invention relates to an oligoalkyl oxirane derivative having glycerin as a starting material to which a specific number of moles of alkyl oxirane has been added. Oligoalkyloxirane derivatives having a uniform distribution, a cloud point of a 50% by weight aqueous solution within a certain range, and a low degree of unsaturation are excellent in moisturizing properties, have no sticky feeling, have an appropriate oily feeling, and The present inventors have found that the change in odor with time is small and that the odor change can be suitably used as a humectant, and thus arrived at the present invention.

That is, the present invention relates to the following oligoalkyloxirane derivative, a method for producing the same, a humectant comprising the derivative, and a cosmetic and a detergent containing the humectant. (1) It is represented by the following formula (1), the polydispersity is 1.040 or less, and the cloud point of the 50% by weight aqueous solution is 40 to 90.
An oligoalkyl oxirane derivative which has a degree of unsaturation of 0.03 ° C. or less.

Embedded image(However, AO is -OCH_TwoCH (CH_Three) -Group or -O
CH_TwoCH (CH_TwoCH_ThreeEO) is -OCH_TwoC
H_Two-AO and EO are randomly added
Or may be added in a block shape. k, m, n are
Each -OCH _TwoCH (CH_Three) -Group or -OCH_TwoC
H (CH_TwoCH_ThreeThe sum of the average number of moles of the group
a, b, and c are each —OCH_TwoCH_Two-Average addition of groups
1 ≦ k, m, n ≦ 4, 0 ≦ a, b, c ≦
3, 5 ≦ k + m + n ≦ 10, 0 ≦ a + b + c ≦ 3
It is the number to do. (2) Formula (2) shown below with respect to 1 mol of glycerin.
Alcoholate catalyst in a proportion of 0.005 to 0.1 mol
After contacting and performing a dealcoholization treatment under reduced pressure,
80 to 11 by adding kiloxirane or oxirane
E) reacting at 0 ° C.
A method for producing a rigoalkyloxirane derivative. ROX (2) (where R is a linear or branched hydrocarbon having 1 to 4 carbon atoms)
An elemental group, X, is potassium or sodium. (3) Formula (2) shown below with respect to 1 mol of glycerin.
Alcoholate catalyst in a proportion of 0.005 to 0.1 mol
After contacting and performing a dealcoholization treatment under reduced pressure,
80 to 11 by adding kiloxirane or oxirane
Reaction at 0 ° C, then adjust the reaction solution to pH 3 or less in the presence of antioxidant
After the alkaline earth metal oxide or alkaline earth gold
Treated with acid adsorbent containing genus hydroxide
The oligoalkyl oxirane derivative according to the above (1)
Manufacturing method. ROX (2) (where R is a linear or branched hydrocarbon having 1 to 4 carbon atoms)
An elemental group, X, is potassium or sodium. (4) The oligoalkyl oxirane derivative according to the above (1)
Moisturizer consisting of body. (5) The oligoalkyloxirane derivative according to (1) above
A cosmetic comprising 2 to 40% by weight of a body. (6) The oligoalkyloxirane derivative according to (1) above
A cleaning agent comprising 2 to 40% by weight of a body.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In the above formula (1), k, m and n are respectively 1 to 4, preferably 1 to 3.
k, m and n are each limited to 1 to 4 because at least 1 mol of each hydroxyl group of glycerin has a sticky feeling when used unless alkyl oxirane is added, and 4 mol is used. If it exceeds, the oily feeling becomes too strong, which is not preferable. Further, k + m + n, which is the total number of moles of alkyloxirane added, is 5 to 10, preferably 5 to 9. The reason why k + m + n is limited to 5 to 10 is that if the total number of added moles is less than 5 moles, the water solubility is too strong to obtain a moist feeling, and if it exceeds 10 moles, conversely the lipophilicity becomes strong. This is because it is not preferable because the feeling of use becomes too close to oil and a sufficient moist feeling cannot be obtained.

In the above formula (1), a, b and c are each 0 to 3, preferably 0 to 2. When a, b and c are 0, the oxyethylene chain is not introduced, but the oxyethylene chain can be introduced as needed in order to adjust the balance between hydrophilicity and lipophilicity. A + b + c which is the total number of added moles of the oxyethylene chain is 0 to
3, preferably 0 to 2. When a + b + c is larger than 3, the hydrophilicity becomes too strong, which is not preferable.

The oligoalkyl oxirane derivative of the present invention represented by the above formula (1) has a polydispersity of 1.040 or less,
Preferably it is 1.035 or less. The polydispersity is an index indicating the molecular weight distribution, and the closer to 1, the narrower the molecular weight distribution and the more uniform the compound. If unreacted raw material glycerin remains in the oligoalkyloxirane derivative or the molecular weight distribution is wide due to a non-uniform addition reaction, the polydispersity increases. In fact, if the polydispersity exceeds 1.040, stickiness during use is likely to occur, which is not preferable.

The polydispersity is generally obtained as an elution parameter of gel permeation chromatography (GPC), and is known to vary greatly depending on a measuring device, a column, a developing solvent and the like. The polydispersity noted in the specification is the weight average molecular weight (M
w) and the number average molecular weight (Mn).
n. Specifically, as a GPC system, SH
ODEX GPC SYSTEM-11 (trademark, manufactured by Showa Denko KK), SHODEXRI as a differential refractometer
-71 (trademark, manufactured by Showa Denko KK), SHODX KF804L (φ8 mm × 300 mm,
Showa Denko Co., Ltd., trademark) were connected in series, and a column constant temperature bath temperature of 40 ° C., tetrahydrofuran (THF) as a developing solvent was flowed at a flow rate of 1 ml / min, and a 0.1% by weight THF solution of the sample was added. 0.1 ml is injected, and the elution curve is analyzed by a BORWIN GPC calculation program manufactured by JASCO Corporation to obtain a polydispersity.

The oligoalkyloxirane derivative of the present invention represented by the above formula (1) has a cloud point of 40 to 90 ° C., preferably 60 to 80 ° C., measured using a 50% by weight aqueous solution of the derivative. The cloud point is determined as a temperature at which a 50% by weight aqueous solution of an oligoalkyloxirane derivative is heated once to make it turbid, and the 50% by weight aqueous solution in which the turbidity is observed is gradually cooled so that the turbidity disappears. When the turbidity of the aqueous solution disappears, it is visually confirmed that the aqueous solution has become transparent.

In general, in an oligoalkyl oxirane derivative, as the number of moles of alkyl oxirane added increases, the hydroxyl group concentration decreases, so that the lipophilicity increases. However, even if the humectant is too hydrophilic, the lipophilicity is high. It is not preferable to be too strong. Since the balance between hydrophilicity and lipophilicity is a matter of sensation, it is easy to change depending on the amount of impurities contained in the compound and the like, and it is difficult to quantify. It was found that a 50% by weight aqueous solution of an oxirane derivative having a cloud point in the range of 40 to 90 ° C. had a favorable balance between hydrophilicity and lipophilicity as a humectant. That is, those having a cloud point of less than 40 ° C. have too much lipophilicity and have only a touch as an oil with a sticky feeling, and those having a cloud point of more than 90 ° C. have too strong a hydrophilic property to obtain a moist feeling. Become. When the cloud point is in this range, the film can be used as a humectant, but in order to obtain a more moist feeling, the cloud point is preferably in the range of 60 to 80 ° C.

In the oligoalkyloxirane derivative represented by the above formula (1), when the number of moles of alkyloxirane added is small, the proportion of hydroxyl groups in the molecular structure increases, the cloud point increases, and the number of moles of alkyloxirane added increases. As the ratio increases and the proportion of hydroxyl groups in the molecular structure decreases, the cloud point decreases. Further, since the oxyethylene chain is a hydrophilic group, the cloud point increases as the number of moles of alkyloxirane added increases. Therefore, the cloud point can be adjusted by selecting the type of alkyloxirane, the number of moles added, and the like.

The oligoalkyloxirane derivative of the present invention represented by the above formula (1) has an unsaturation of 0.03 or less,
Preferably it is 0.02 or less. The degree of unsaturation is an index indicating the content of a group having an unsaturated bond such as an allyl group and a propenyl group contained in the alkyloxirane derivative, and is determined according to JIS K 15576.7.

The fact that the degree of unsaturation is large indicates that the oligoalkyloxirane derivative contains many compounds having an unsaturated bond such as an allyl group and a propenyl group as impurities. Impurities having an allyl group or a propenyl group are decomposed over time to allyl alcohol or propionaldehyde, and such impurities are the main cause of deterioration of odor over time. Therefore, the lower the degree of unsaturation, the better the change in odor with time, and if the degree of unsaturation exceeds 0.03, the change in odor with time increases, which is not preferable as a raw material for cosmetics and cleaning agents.

The oligoalkyl oxirane derivative of the present invention is excellent in moisturizing properties and has a uniform molecular weight distribution, so that it has no sticky feeling, has an appropriate oily feeling, and has little change in odor with time. For this reason, the oligoalkyl oxirane derivative of the present invention can be used as a very good humectant.

The humectant of the present invention comprises the oligoalkyl oxirane derivative of the present invention. Even if the humectant is composed of only the oligoalkyl oxirane derivative, a known component usually added to the humectant is replaced with another component. It may be included as. The humectant of the present invention can be specifically used as a humectant in cosmetics and cleaning agents.

The cosmetic of the present invention is a cosmetic containing the oligoalkyloxirane derivative of the present invention (ie, the humectant of the present invention) in an amount of 2 to 40% by weight, preferably 5 to 20% by weight. Since the cosmetic of the present invention contains the above-mentioned oligoalkyloxirane derivative of the present invention in the above-described amount, a good moist feeling can be obtained. If the amount of the oligoalkyloxirane derivative is less than 2% by weight, the moisturizing property cannot be sufficiently exhibited and the moist feeling is insufficient, which is not preferable. However, since the amount of other cosmetic components is reduced, the function as a cosmetic cannot be sufficiently exhibited, which is not realistic. A preferable range of the compounding amount is 5 to 20% by weight.

Specific examples of the cosmetic of the present invention include:
Lotion, milky lotion, cleansing cream, hair treatment lotion, hair styling foam, hair styling gel, sunscreen lotion, sunscreen cream, foundation, lipstick, sunscreen cream, cold cream, hand cream, pack, skin cleanser, softening Cosmetics, nutritionalized cosmetics, whitening cosmetics, wrinkle improving cosmetics, anti-aging cosmetics, cleaning cosmetics, rinses, treatments, hair styling agents, hair tonics, mascaras, eye shadows and the like.

The components other than the oligoalkyloxirane derivative contained in the cosmetic of the present invention are not particularly limited, and other known cosmetic components which are usually compounded in cosmetics can be compounded. Specific examples of other cosmetic ingredients include alcohols such as ethyl alcohol, isopropyl alcohol, cetyl alcohol, stearyl alcohol, palmityl alcohol, oleyl alcohol, hexyldecyl alcohol, glycerin, and sorbitol; liquid paraffin, petrolatum, squalane, and the like. Vegetable oils and fats such as beeswax, olive, ground wax, carnauba wax, lanolin, whale wax, animal fats and waxes; stearic acid, palmitic acid, oleic acid, glycerin monostearate, glycerin distearate Fatty acids such as glycerin monooleate, isopropyl myristate, isopropylstearate, butylstearate and the like; polyoxyethylene Emissions hardened castor oil, polyoxyethylene sorbitan monooleate, polyethylene glycol, polypropylene glycol, polyether polyalkylene glycol; polyether-modified silicone, glyceryl ether modified silicone, an emulsifier for silicone oils such as polyether-alkyl-modified silicones;
Thickeners such as methylcellulose, ethylcellulose, carboxymethylcellulose, polyacrylic acid, agar, and gelatin; surfactants, active ingredients, emulsion stabilizers, chelating agents, pH adjusters, pigments, coloring agents, pigments, fragrances, preservatives,
Water.

The detergent of the present invention is a detergent containing the oligoalkyl oxirane derivative of the present invention (that is, the humectant of the present invention) in an amount of 2 to 40% by weight, preferably 5 to 20% by weight. Since the detergent of the present invention contains the oligoalkyloxirane derivative of the present invention in the above-described amount, a good moist feeling can be obtained. If the amount of the oligoalkyloxirane derivative is less than 2% by weight, the moisturizing property cannot be sufficiently exhibited and the moist feeling is insufficient, which is not preferable. However, it is not realistic because the function of the detergent cannot be sufficiently exhibited because the amount of other detergent components is reduced. A preferable range of the compounding amount is 5 to 20% by weight. Specific examples of the detergent of the present invention include body soap, shampoo, cleansing lotion and the like.

The components other than the oligoalkyloxirane derivative contained in the detergent of the present invention are not particularly limited, and other known detergent components which are usually contained in detergents can be blended. Specific examples of other cleaning ingredients include alcohols such as ethyl alcohol, isopropyl alcohol, cetyl alcohol, stearyl alcohol, palmityl alcohol, oleyl alcohol, hexyl decyl alcohol, glycerin, and sorbitol; liquid paraffin, petrolatum, squalane, and the like. Vegetable oils and fats such as beeswax, olive, ground wax, carnauba wax, lanolin, whale wax, animal fats and waxes; stearic acid, palmitic acid, oleic acid, glycerin monostearate, glycerin distearate Fatty acids such as glycerin monooleate, isopropyl myristate, isopropylstearate, butylstearate and the like; polyoxyethylene Emissions hardened castor oil, polyoxyethylene sorbitan monooleate, polyethylene glycol, polypropylene glycol, polyether polyalkylene glycol; polyether-modified silicone, glyceryl ether modified silicone, an emulsifier for silicone oils such as polyether-alkyl-modified silicones;
Thickeners such as methylcellulose, ethylcellulose, carboxymethylcellulose, polyacrylic acid, agar, and gelatin; surfactants, active ingredients, emulsion stabilizers, chelating agents, pH adjusters, pigments, coloring agents, pigments, fragrances, preservatives,
Water.

The oligoalkyloxirane derivative of the present invention can be easily obtained, for example, by the following production method. 1) The above formula (2) per 1 mol of glycerin in the reaction system
Is contacted at a rate of 0.005 to 0.1 mol, preferably 0.008 to 0.07 mol, is subjected to a dealcoholization treatment under reduced pressure, and then alkyl oxirane or oxirane is added. 80-110 ° C
How to react. 2) The above formula (2) per 1 mol of glycerin in the reaction system
Is contacted at a rate of 0.005 to 0.1 mol, preferably 0.008 to 0.07 mol, is subjected to a dealcoholization treatment under reduced pressure, and then alkyl oxirane or oxirane is added. 80-110 ° C
And then, in the presence of an antioxidant,
A method of adjusting the pH to 3 or less, preferably pH 2 to 3, and then treating with an acid adsorbent containing an alkaline earth metal oxide or an alkaline earth metal hydroxide.

Specific examples of the alcoholate catalyst represented by the above formula (2) include alkali metal alcoholates such as sodium methoxide, sodium tertiary butoxide, potassium methoxide, and potassium tertiary butoxide. . These alcoholate catalysts can also be used as a C1-C4 alcohol diluent solution for better handling.

In the production method of the present invention, if the amount of the alcoholate catalyst used is less than the lower limit, sufficient catalytic activity cannot be obtained, and the reaction is difficult to occur, and the reaction time is prolonged. Exceeding the value is not preferable because the hydroxyl group of glycerin is not sufficiently converted to an alcoholate during dealcoholation, and oxirane or alkyl oxirane is easily added to the alcoholate catalyst, which is not preferable.

The method of contacting glycerin with the alcoholate catalyst is not particularly limited, and a method of mixing glycerin and the alcoholate catalyst in a reactor can be employed. In the production method of the present invention, a dealcoholation treatment is performed under reduced pressure while glycerin and the alcoholate catalyst are in contact with each other. Alcohol (ie, ROH, where R is R in the above formula (2)) generated from the alcoholate catalyst is removed by the dealcoholation treatment. Since alcohol other than glycerin causes impurities, it is preferable to remove the alcohol as completely as possible so as not to remain in the reaction system.

The dealcoholation treatment is carried out under a flow of an inert gas such as nitrogen at 50 to 100 ° C., preferably 70 to 100 ° C.
At a temperature of 100 mmHg or less, preferably 50 mmHg
g under a reduced pressure of 0.1 g or less, preferably 0.5 to 5 hours.
It is desirable to carry out for up to 2 hours. In the production method of the present invention, since the amount of the alcoholate catalyst used is small, the hydroxyl group of glycerin can be completely converted into an alcoholate under relatively mild conditions as described above.

After the dealcoholation treatment, alkyl oxirane or oxirane is added to the reaction system and reacted with alcoholated glycerin. Specific examples of alkyloxiranes include methyloxirane, ethyloxirane, and the like. Reaction temperature is 80 to 110
° C, preferably 90 to 110 ° C. The reaction time is 1 to 20 hours, preferably 2 to 15 hours, and the pressure is 0.3
-10 kgf / cm ² (gauge pressure), preferably 1-6
It is desirable that the pressure be set to kgf / cm ² (gauge pressure). When the reaction temperature is higher than 110 ° C., many unsaturated compounds having a propenyl group or an allyl group are by-produced. When the reaction temperature is lower than 80 ° C., the addition reaction itself hardly occurs, which is not preferable.

According to the above-mentioned method, the oligoalkyloxirane derivative of the present invention having a low impurity content and high purity can be easily produced without almost producing by-products derived from the alcoholate catalyst. The impurities can be almost completely removed by performing the purification described in the above method 2).

The production method 2) is characterized in that a purification step is provided as a post-treatment, and an unsaturated compound which is slightly produced as a by-product during the reaction is once treated with an acid to cleave the unsaturated group. That is, after the reaction, the reaction solution is adjusted to pH 3 or less in the presence of an antioxidant, and then treated with an acid adsorbent containing an alkaline earth metal oxide or an alkaline earth metal hydroxide.

In the production method 1), when an allyl group is by-produced during the reaction, the allyl group is relatively quickly transferred to a propenyl group, but the propenyl group remains as an impurity. Therefore, in the manufacturing method of the above 2),
The propenyl group is cleaved by adjusting the pH of the reaction solution to 3 or less. The propenyl group is rapidly cleaved under the condition that the pH is 3 or less, and is separated into a compound having a hydroxyl group and propionaldehyde. The separated aldehyde groups are removed by an adsorbent and a treatment under reduced pressure. Thereby, impurities are almost completely removed, and a high-purity oligoalkyloxirane derivative can be obtained.

The acid used at this time is p
Various types can be used as long as H can be reduced to 3 or less. Specifically, hydrochloric acid or phosphoric acid,
Alternatively, water-diluted products thereof may be used.

It is also important to add an antioxidant to the system before treating under acidic conditions. Antioxidants that can be used may be water-soluble or oil-soluble as long as they are compounds having an antioxidant effect, and are not particularly limited. Specific examples of antioxidants include BHT (2,6-di-
-tert-butyl-p-cresol, 2,6-di-tert-butyl-p-cre
sol), butylhydroxyanisole, parahydroxyanisole, propyl gallate, octyl gallate, α
-Tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol, tocopherol acetate, natural vitamishi E, ascorbic acid, sodium ascorbate, ascovir palmitate, ascovir dipalmitate, erythorbic acid, sodium erythorbic acid, orthotolyl biguanide, thiol Dilauryl dipropionate, tea extract, rosemary extract and the like.
Of these, BHT is preferred. One or more antioxidants can be used.

The amount of the antioxidant to be added is not particularly limited as long as it can prevent oxidative deterioration of the polyalkylene glycol chain during the acid treatment. 30 by weight
It is desirable that the content be set to 500 ppm, preferably 50 to 200 ppm. Although it may be added exceeding the above upper limit,
If it is too large, it is not practical because it is disadvantageous in terms of cost.

The acid adsorbent used in the production method of the present invention comprises:
Alkaline earth metal oxides, alkaline earth metal hydroxides,
A mixture thereof, or a mixture thereof. Specific examples of the acid adsorbent include magnesium oxide, calcium oxide, barium oxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, and a mixture thereof. Commercial products containing these compounds can also be used, for example, Kyoward 100, Kyoward 300, Kyoward 500, Kyoward 600,
Kyoward 1000, Kyoward 2000 (trademark, manufactured by Kyowa Chemical Industry Co., Ltd.), Tomix AD100, Tomix AD300, Tomix AD500, Tomix AD600, Tomix AD800 (Tomita Pharmaceutical Co., Ltd.)
Made, trademark), Aidplus SP, Aidplus ML-5
OD (trademark, manufactured by Mizusawa Chemical Industry Co., Ltd.) and the like.

The acid adsorbent may be added at any time after the pH of the reaction solution has been adjusted to 3 or less and before the filtration step. Specifically, a method of adding an acid adsorbent immediately after the completion of the pH adjustment treatment step, dehydrating and then filtering to obtain an intended product; after the pH adjustment treatment step, once performing a dehydration treatment, and then adding the acid adsorbent. And then subjecting the mixture to a reduced pressure treatment, followed by filtration to obtain the desired product.

The amount of the acid adsorbent to be added is not particularly limited as long as it can adsorb excess acid and aldehydes by-produced by cleavage, and is not particularly limited. Since the pH cannot be sufficiently returned to the neutral range, the content in the reaction solution is 0.1%.
３3% by weight is an appropriate amount. A preferred range is 0.5
~ 2% by weight.

By performing the treatment with the acid adsorbent as described above, the pH of the reaction solution returns to 6 to 8. By performing the purification treatment as described above, impurities can be almost completely removed, and a higher-purity oligoalkyloxirane derivative can be obtained.

The oligoalkyloxirane derivative of the present invention is produced by addition polymerization of glycerin with oxirane or alkyloxirane in the presence of an alkali catalyst such as an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide. However, when a compound having a hydroxyl group as described above is used as an alkali catalyst, alkyl oxirane is also added to the hydroxyl group in the catalyst.
A large amount of a functional alkyloxirane derivative is by-produced. Since these by-products cause stickiness, when they are used as humectants, they are preferably used after purification to remove by-products. Therefore, the method 1) or 2) is preferable as the manufacturing method.

In order to prevent the formation of a bifunctional alkyloxirane derivative which is a by-product, a method of mixing a catalyst and glycerin and then subjecting the system to a reduced pressure treatment under heating conditions to remove water is conceivable. When the catalyst is a compound having a hydroxyl group, the hydroxyl group of glycerin cannot be sufficiently converted to an alcoholate under the temperature range and reduced pressure conditions which can be generally used industrially, so that alkyl oxirane was added to the remaining hydroxyl group derived from the catalyst. A bifunctional derivative is by-produced. Since these by-products cause stickiness, when they are used as humectants, they are preferably used after purification to remove by-products. Therefore, the method 1) or 2) is preferable as the manufacturing method.

As a purification method, a known method such as chromatography can be employed. For example, alkyl oxirane can be converted to reactive glycerin or water molecules from an oligoalkyl oxirane derivative synthesized using an alkyl catalyst by a purification means such as preparative liquid chromatography. A bonded bifunctional alkyloxirane derivative or a derivative having an unsaturated group at a terminal by-produced during the reaction can be removed.

[0046]

The oligoalkyloxirane derivative of the present invention is novel and useful. The oligoalkyl oxirane derivative of the present invention is excellent in moisturizing properties and has a uniform molecular weight distribution, so that there is no sticky feeling and the oily feeling is moderate,
Further, the odor change with time is small, and therefore, it can be suitably used as a humectant.

In the method for producing an oligoalkyl oxirane derivative of the present invention, a specific alcoholate catalyst is brought into contact with glycerin in a specific amount, subjected to a dealcoholization treatment under reduced pressure, and then reacted with alkyl oxirane or oxirane. A high-purity oligoalkyloxirane derivative with few impurities can be easily and efficiently produced at low cost. Since the oligoalkyl oxirane derivative produced by the production method of the present invention hardly contains impurities containing unsaturated groups, the change in odor with time is small. In addition, as a post-treatment, the reaction solution is adjusted to pH 3 or less in the presence of an antioxidant, and then treated with an acid adsorbent to produce an oligoalkyloxirane derivative with less impurities easily, efficiently, and at low cost. can do.

Since the humectant of the present invention is composed of the above-mentioned oligoalkyl oxirane derivative, it has excellent moisturizing properties, no stickiness, moderate oiliness, and little change in odor with time. And detergents. Since the cosmetic of the present invention contains the oligoalkyl oxirane derivative in a specific amount, it has excellent moisture retention, no stickiness, moderate oiliness, and little change in odor with time. Since the detergent of the present invention contains the oligoalkyl oxirane derivative in a specific amount, it has excellent wettability, no stickiness, moderate oiliness, and little change in odor with time.

[0049]

The present invention will be described in detail below with reference to examples and comparative examples. In each example, physical properties were measured by the following methods. << Polydispersity >> SHODEX GP as GPC system
C SYSTEM-11 (trademark, manufactured by Showa Denko KK),
SHODEX RI-71 (trademark, manufactured by Showa Denko KK) as a differential refractometer and SHODX K as a GPC column
F804L (φ8mm × 300mm, Showa Denko KK)
, Trademark) were connected in series, and the column bath temperature was 40
° C, tetrahydrofuran (THF) as a developing solvent
flow at a flow rate of 0.1 ml / min.
0.1 ml of the HF solution was injected, and the elution curve was analyzed with a BORWIN GPC calculation program manufactured by JASCO Corporation to obtain a polydispersity.

<< Cloud Point >> A 50% by weight aqueous solution of an oligoalkyloxirane derivative is placed in a test tube together with a thermometer. This aqueous solution is heated with a thermometer to a temperature that is higher by 2 to 3 ° C. than a temperature at which turbidity occurs, and then cooled, and then the temperature at which the aqueous solution becomes transparent is measured. << Unsaturation >> Determined according to JIS K 1557 6.7.

Example 1 460 g (5 mol) of glycerin and 2.7 g of sodium methylate (0.05 mol → 1 mol to glycerin) were placed in a 5-liter autoclave equipped with a nitrogen blowing tube, an injection tube, a stirrer and a thermometer. %), And a dealcoholization treatment was performed for 1 hour at 80 ± 5 ° C. under a vacuum condition of 50 mmHg or less while blowing nitrogen gas. Then, the inside of the reaction system was set to 1.0 kgf / cm ² with nitrogen gas.
(Gauge pressure), 2376 g of ethyl oxirane
(33 mol) was gradually injected at 100 ± 5 ° C. while controlling the pressure to 3.5 kgf / cm ² (gauge pressure). After the entire amount was injected, stirring was continued at the same temperature for another 8 hours. Then, the temperature was lowered to 80 ± 5 ° C., and the pressure was reduced to 100 mmHg or less while blowing nitrogen gas.
The mixture was treated for an hour to remove the remaining unreacted ethyloxirane.

The internal pressure of the system is set to 1.0 kgf / cm with nitrogen gas.
² (gauge pressure), a 20 g sample of the reaction solution was withdrawn from the sample withdrawal tube into an eggplant flask, and Kyoward 700 (trade name, manufactured by Kyowa Chemical Co., Ltd.)
g, and treated under reduced pressure of 100 mmHg or less for 30 minutes, followed by removal of Kyoward by filtration under reduced pressure to obtain 17.4 g of a hydroxyl value measurement sample. The hydroxyl value of the obtained sample was 320.2, and the molecular weight determined from the hydroxyl value was 525.6. From this, the mole of ethyl oxirane actually added was calculated to be 6.02 mole.

Subsequently, 352 g (8 mol) of oxirane was gradually injected at 100 ± 5 ° C. while controlling the pressure to 4 kgf / cm ² (gauge pressure) or less.
After the entire amount was injected, stirring was continued at the same temperature for another 3 hours. Next, the temperature was lowered to 80 ± 5 ° C., and treatment was performed for 1 hour under a reduced pressure condition of 100 mmHg or less while blowing nitrogen gas to remove remaining unreacted oxirane. Then, the inside of the system was returned to normal pressure with nitrogen gas, 20 g of the sample was withdrawn as an analysis sample, and the entire remaining amount was transferred to a 5-liter four-necked flask. The amount of the obtained reaction solution was 2,926 g.

A stirrer, a nitrogen blowing tube, a thermometer and a vacuum joint were attached to the four-necked flask.
(2,6-Di-tert-butyl-p-cresol; reagent, manufactured by Kanto Chemical)
0.3 g (102 ppm with respect to the reaction solution) was added, and the mixture was stirred until completely dissolved, and then the pH was adjusted to 2.1 with 17.5% hydrochloric acid. While blowing nitrogen gas,
The temperature was maintained at 60 ± 2 ° C., and the mixture was stirred for 1 hour. Then
The temperature was raised to 100 ± 5 ° C., vacuum was started while blowing nitrogen gas, and dehydration was continued for another 2 hours after the degree of vacuum became 50 mmHg or less. Next, 29.3 g (1% by weight based on the reaction solution) of Kyoward 1000 (trade name, manufactured by Kyowa Chemical Industry Co., Ltd.) as an acid adsorbent was added, and the mixture was added at 80 ± 5 ° C. and 100 mmHg or less while blowing nitrogen gas. After stirring was continued for a period of time, the by-product salt and the adsorbent were removed by filtration under reduced pressure to obtain 2840 g of an oligoalkyloxirane derivative (pH 6.8). FIG. 1 shows a chart of gel permeation chromatography (GPC) of the obtained oligoalkyloxirane derivative.

From the GPC, the polydispersity of the obtained oligoalkyloxirane derivative was 1.03. The hydroxyl value of the obtained compound was 284.2, and the degree of unsaturation was 0.00. The cloud point of the 50% by weight aqueous solution was 68.7 ° C. The molecular weight determined from the hydroxyl value was 592.2. From the molecular weight obtained here and the molecular weight obtained after the completion of the addition of ethyl oxirane, the number of moles of oxirane was determined.
Mole was added.

Therefore, the structure of the obtained oligoalkyloxirane derivative can be estimated to be the following formula (3).

Embedded image

Example 2 In a 5 liter autoclave equipped with a nitrogen blowing tube, injection tube, stirrer and thermometer, 460 g (5 mol) of glycerin and 22.4 g of potassium tertiary butylate were added.
(0.2 mol → 4 mol% based on glycerin)
50mmHg at 90 ± 5 ℃ while blowing nitrogen gas
A dealcoholization treatment was performed for 1 hour while stirring under the following vacuum conditions. Then, the reaction system was filled with nitrogen gas at 1.0 kgf /
cm ² (gauge pressure)
36 g (42 mol) with a pressure of 3.35 kgf / cm
² (Gauge pressure) The pressure was gradually injected at 100 ± 5 ° C. while controlling the pressure to not more than ² (gauge pressure). After press-fitting the whole amount, 3 more
Stirring was continued at the same temperature for hours. Then, the temperature was lowered to 80 ± 5 ° C., and the mixture was treated under a reduced pressure of 100 mmHg or less for 1 hour while blowing nitrogen gas to remove remaining unreacted methyloxirane. Then, the inside of the system was returned to normal pressure with nitrogen gas, and the whole amount was transferred to a 5-liter four-necked flask. The obtained reaction solution was 2752 g.

A stirrer, a nitrogen blowing tube, a thermometer, and a vacuum joint were attached to the four-necked flask, and the pH was adjusted to 2.5 using 85% phosphoric acid. While blowing in nitrogen gas, the mixture was stirred for 1 hour while maintaining the temperature at 60 ± 2 ° C. Next, 55.1 g of Kyoward 1000 (trade name, manufactured by Kyowa Chemical) as an acid adsorbent (2% by weight based on the reaction solution)
Was added, the temperature was raised to 100 ± 5 ° C., and vacuum was started while blowing nitrogen gas. After the degree of vacuum became 50 mmHg or less, dehydration was continued for another 2 hours. The salt and adsorbent produced as by-products were removed by filtration under reduced pressure to obtain 2670 g of an oligoalkyloxirane derivative (pH 7.0).
2).

The polydispersity of the obtained oligoalkyloxirane derivative was 1.028 and the hydroxyl value was 296.5.
And the degree of unsaturation was 0.01. 50% by weight
The cloud point of the aqueous solution was 64.8 ° C. The molecular weight determined from the hydroxyl value was 567.6. When the number of moles of added methyloxirane was determined from this, 8.2 moles of methyloxirane was added in total.

Therefore, the structure of the obtained oligoalkyloxirane derivative can be estimated to be the following formula (4).

Embedded image

Example 3 In a 5 liter autoclave equipped with a nitrogen blowing tube, an injection tube, a stirrer and a thermometer, 460 g (5 mol) of glycerin and 13.5 g of sodium methylate (0.25 mol → 5 to glycerin) were added. Mol%), and the mixture was subjected to a dealcoholization treatment at 80 ± 5 ° C. for 1 hour with stirring under a vacuum condition of 50 mmHg or less while blowing nitrogen gas. Then, the inside of the reaction system was set to 1.0 kgf / cm ² with nitrogen gas.
(Gauge pressure), 792 g of ethyl oxirane
(11 moles) and 957 g (16.5 moles) of methyl oxirane were mixed with 100 ± 5 while controlling the pressure to 3.5 kgf / cm ² (gauge pressure) or less.
The pressure was gradually increased at ℃. After the entire amount was injected, stirring was continued at the same temperature for another 5 hours. Then, the temperature was lowered to 80 ± 5 ° C., and the mixture was treated under a reduced pressure of 100 mmHg or less for 1 hour while blowing nitrogen gas to remove remaining unreacted methyloxirane and ethyloxirane. Then, the inside of the system was returned to normal pressure with nitrogen gas, and the whole amount was transferred to a 4-liter 4-neck flask.
The obtained reaction solution was 2078 g.

A stirrer, a nitrogen blowing tube, a thermometer, and a vacuum joint were attached to the four-necked flask, and 17.5.
The pH was adjusted to 2.7 using% hydrochloric acid. While blowing in nitrogen gas, maintain the temperature at 100 ± 2 ° C. and start vacuuming while blowing in nitrogen gas.
g, the dehydration was continued for another 2 hours. The by-product salt and the adsorbent were removed by filtration under reduced pressure,
2 g of oligoalkyloxirane derivative was obtained (pH
7.0).

The oligoalkyl oxirane derivative obtained had a polydispersity of 1.032 and a hydroxyl value of 400.7.
And the degree of unsaturation was 0.02. 50% by weight
The cloud point of the aqueous solution was 76.8 ° C. The molecular weight determined from the hydroxyl value was 420. From this, when the number of moles of methyloxirane and ethyloxirane added was calculated from the mixing ratio, 2.1 moles of ethyloxirane and 3.0 moles of methyloxirane were added.

Therefore, the structure of the obtained oligoalkyloxirane derivative can be estimated to be the following formula (5).

Embedded image

Comparative Example 1 Synthesis was attempted by a method generally used industrially.
In a 5 liter autoclave equipped with a nitrogen blowing tube, an injection tube, a stirrer and a thermometer, 460 g (5 mol) of glycerin and 8.0 g of sodium hydroxide (0.2 mol → 4 mol% based on glycerin) were charged. 1.0 with gas
kgf / cm ² (gauge pressure), and 2668 g (46 mol) of methyl oxirane was added at a pressure of 5.0 kgf / cm ^2.
2 (Gauge pressure) The pressure was gradually increased at 130 ± 5 ° C. while controlling so as to be not more than (gauge pressure). After press-fitting the whole amount, 2 more
Stirring was continued at the same temperature for hours. Then, the temperature was lowered to 80 ± 5 ° C., and the mixture was treated under a reduced pressure of 100 mmHg or less for 1 hour while blowing nitrogen gas to remove remaining unreacted methyloxirane. Then, the inside of the system was returned to normal pressure with nitrogen gas, and the whole amount was transferred to a 4-liter 4-neck flask. The amount of the obtained reaction solution was 2,968 g.

Next, Kyoward 7 which is an alkali adsorbent
80 g (trade name, manufactured by Kyowa Chemical Industry Co., Ltd.) is placed in the above four-necked flask, and a stirrer, a nitrogen blowing tube, a thermometer, and a vacuum joint are attached. , Vacuum degree is 200mmH
g, the adsorption treatment was continued for another hour. The adsorbent was removed by filtration under reduced pressure to obtain 2852 g of the compound (pH 6.9). FIG. 2 shows a chart of gel permeation chromatography (GPC) of the obtained oligoalkyloxirane derivative.

The obtained compound had a polydispersity of 1.062, a hydroxyl value of 281.3 and an unsaturation of 0.02.
Nine. The cloud point of the 50% by weight aqueous solution is 58.4.
° C. The molecular weight determined from the hydroxyl value was 598.3. When the number of moles of added methyloxirane was determined from this, 8.73 moles of methyloxirane was added in total.

Comparative Example 2 In the same manner as in Comparative Example 1, the addition mole of methyloxirane was
An attempt was made to synthesize a large number of samples. Nitrogen injection pipe, injection
5 liter autoclave with tube, stirrer and thermometer
In the reave, 276 g (3 mol) of glycerin and hydroxylated
6.0 g of sodium (0.15 mol → based on glycerin)
5 mol%) and 1.0 kgf / cm 2 with nitrogen gas. ^Two
(Gauge pressure), 2871 g of methyl oxirane
(49.5 mol) with a pressure of 5 kgf / cm^Two(gauge
Pressure) 130 ± 5 while controlling to be below
The pressure was gradually increased at ℃. After press-fitting the entire amount, the same temperature for another 2 hours
And continued stirring. Then lower the temperature to 80 ± 5 ° C,
Depressurizing condition of 100mmHg or less while blowing gas
For 1 hour to remove residual unreacted methyloxirane.
I left. Then, the inside of the system is returned to normal pressure with nitrogen gas, and the total amount is 5 l.
ter was transferred to a four-necked flask. The reaction solution obtained was 290
It was 5 g.

A stirrer, a nitrogen blowing tube, a thermometer and a vacuum joint were attached to the four-necked flask, and the pH was adjusted to 2.5 using 85% phosphoric acid. 120 ±
The temperature was raised to 5 ° C., and vacuum was started while blowing nitrogen gas.
Dehydration continued for hours. The salt produced as a by-product was removed by filtration under reduced pressure to obtain 2840 g of the compound (pH 7.4).

The resulting compound had a polydispersity of 1.081, a hydroxyl value of 175.1 and an unsaturation of 0.1.
It was 7. The cloud point of the 50% by weight aqueous solution is 34.2.
° C. The molecular weight determined from the hydroxyl value was 961.1. When the number of moles of methyl oxirane was determined in this way, 15.0 moles of methyl oxirane was added in total.

Comparative Example 3 Synthesis was performed in the same manner as in Comparative Example 1, except that oxirane was used instead of alkyloxirane. In a 5-liter autoclave equipped with a nitrogen blowing tube, an injection tube, a stirrer and a thermometer, 460 g (5 mol) of glycerin and 8.0 g of sodium hydroxide (0.2 mol → 4 mol% based on glycerin) were taken. 1.0kgf / cm with gas
² (gauge pressure) and 1848 g of oxirane (42
Mol) was gradually injected at 130 ± 5 ° C. while controlling the pressure to be 5.0 kgf / cm ² (gauge pressure) or less. After the entire amount was injected, stirring was continued at the same temperature for another 2 hours. Then, the temperature was lowered to 80 ± 5 ° C., and the mixture was treated under a reduced pressure of 100 mmHg or less for 1 hour while blowing nitrogen gas to remove remaining unreacted oxirane. Then, the inside of the system was returned to normal pressure with nitrogen gas, and the whole amount was extracted into a 4-liter 4-neck flask. The obtained reaction solution was 2,216 g.

Next, Kyoward 7 which is an alkali adsorbent
80 (made by Kyowa Kagaku Kabushiki Kaisha) was placed in a four-necked flask, fitted with a stirrer, a nitrogen blowing tube, a thermometer, and a vacuum joint. The temperature was raised to 90 ± 5 ° C., and vacuum was started while blowing nitrogen gas. After the degree of vacuum became 200 mmHg or less, the adsorption treatment was continued for another hour. The adsorbent was removed by filtration under reduced pressure to obtain 2158 g of the compound (pH 6.8).

The polydispersity of the obtained compound was 1.052,
The hydroxyl value was 370.6, the degree of unsaturation was 0.07, and 5
The cloud point of the 0% by weight aqueous solution was 97 ° C. or higher (no cloud point was observed at the time of 97 ° C. Any further temperature rise was impossible due to boiling of the measurement system). The molecular weight determined from the hydroxyl value was 454.1. When the number of moles of oxirane added was determined in this way, 8.2 moles of oxirane were added in total.

The structural formula of this compound is represented by the following formula (6).

Embedded image

Example 4 A cleansing cream was prepared using the oligoalkyloxirane derivative of the present invention. That is, after heating the oil phase portion having the following composition to 60 ° C. and dissolving it uniformly,
The aqueous phase was added at the same temperature while stirring. Sensory evaluation of the feeling of use of the obtained cleansing cream was performed. The aging of the formulation after storage at 50 ° C. for 1 week was examined.

The sensory evaluation was carried out by 10 expert panelists, who were familiar with the skin during use, had no sticky feeling, had a comprehensive evaluation of moist feeling, and had no sticky feeling after use and had passed overnight. The remaining moist feeling was evaluated on a five-point scale. The evaluation method followed the following criteria. Table 1 shows the total points for each item. 1: Satisfactory. 2: Satisfied. 3: Normal. no change. 4: Not satisfied. Somewhat dissatisfied. 5: Unsatisfactory.

<< Oil Phase >> Cetanol 2.0% by weight Beeswax 6.0% by weight Vaseline 5.0% by weight Squalane 30.0% by weight Isopropyl myristate 5.0% by weight Glycerin monostearate 2.0% by weight 0.5% by weight of stearic acid Perfume Appropriate Preservative Appropriate << Aqueous Phase >> Compound of Example 3 8.0% by weight Purified Water Balance

Example 5 A cleansing lotion was prepared using the compound of the present invention. That is, the oil phase portion having the following composition was heated to 60 ° C.
After heating to obtain a uniform solution, the aqueous phase was added at the same temperature while stirring. The obtained cleansing lotion was evaluated in the same manner as in Example 1. Table 1 shows the results.

<< Oil Phase >> Cetanol 1.0% by weight Liquid paraffin 10.0% by weight Vaseline 2.0% by weight Glycerin monostearate 2.0% by weight Stearic acid 0.5% by weight Appropriate amount of fragrance Preservative Appropriate amount << Aqueous phase >> Compound of Example 1 5.0% by weight Triethanolamine 0.5% by weight Purified water balance

Example 6 A hair treatment lotion was prepared using the compound of the present invention. That is, polyoxyethylene (60) hydrogenated castor oil, perfume, stearyltrimethylammonium chloride, a preservative, and the compound of Example 2 were added to ethanol at room temperature, mixed uniformly, and then purified water was added. The hair treatment lotion obtained was applied to the hair at the time of use in the same manner as in Example 1. Table 1 shows the results.

Compound of Example 2 10.0% by weight Ethanol 5.0% by weight Preservatives qs Flavor qs Purified water balance

Example 7 A hair styling foam was prepared in the same manner as in Example 6 using the compound of the present invention. The obtained hair styling foam was evaluated in the same manner as in Example 6. Table 1 shows the results.

Compound of Example 1 26.0% by weight Ethanol 6.0% by weight Preservatives appropriate amount Perfume appropriate amount Liquefied petroleum gas 7.5% by weight Purified water

Example 8 A hair styling gel was prepared in the same manner as in Example 6 using the compound of the present invention. The obtained hair styling gel was evaluated in the same manner as in Example 6. Table 1 shows the results.

Compound of Example 1 37.5% by weight Ethanol 5.0% by weight Carboxyvinyl polymer 0.5% by weight Preservatives appropriate amount Perfume appropriate amount Purified water remaining

Example 9 A sunscreen was prepared using the compound of the present invention. That is, of the base having the following composition, the oil phase containing an emulsifier was heated to 60 ° C. to uniformly dissolve it, and then the aqueous phase was added at the same temperature while stirring. The obtained sunscreen was evaluated in the same manner as in Example 1. Table 1 shows the results.

<< Oil Phase >> Ethyl paraaminobenzoate 2.0% by weight 0.5% by weight of dimethylpolysiloxane 7.0% by weight of cetyl 2-ethylhexanoate 6.0% by weight of the compound of Example 3 6.0% by weight of ethanol 15.0 weight% Perfume Appropriate amount Preservative Appropriate amount << Aqueous phase >> Purified water balance

Example 10 A body soap was prepared using the compound of the present invention.
That is, after stirring, while heating, to 50 ° C. to dissolve the base having the following composition other than purified water, purified water was added at the same temperature while stirring. The obtained body soap was evaluated in the same manner as in Example 1. Table 1 shows the results.

[0089] Sodium laurate 2.0% by weight Lauric acid diethanolamide 3.0% by weight Compound of Example 2 7.0% by weight Preservatives qs perfume qs purified water remaining

Comparative Example 4 The procedure of Example 4 was repeated, except that the compound of Comparative Example 2 was used instead of the compound of Example 3. Table 1 shows the results.

Comparative Example 5 The procedure of Example 5 was repeated except that the compound of Comparative Example 1 was used instead of the compound of Example 1. Table 1 shows the results.

Comparative Example 6 The procedure of Example 6 was repeated, except that glycerin, a typical humectant, was used instead of the compound of Example 2. Table 1 shows the results.

Comparative Example 7 The procedure of Example 7 was repeated, except that the compound of Comparative Example 2 was used instead of the compound of Example 1. Table 1 shows the results.

Comparative Example 8 Table 1 shows the results obtained in the same manner as in Example 8, except that glycerin as a representative humectant was used instead of the compound of Example 1.

Comparative Example 9 The procedure of Example 9 was repeated, except that the compound of Comparative Example 1 was used instead of the compound of Example 3. Table 1 shows the results.

Comparative Example 10 The procedure of Example 10 was repeated, except that the compound of Comparative Example 3 was used instead of the compound of Example 2. Table 1 shows the results.

[0097]

[Table 1]

[Brief description of the drawings]

FIG. 1 is a GPC chart of an oligoalkyloxirane derivative obtained in Example 1.

FIG. 2 is a GPC chart of the oligoalkyloxirane derivative obtained in Comparative Example 1.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A61K 7/50 A61K 7/50 B01J 31/02 101 B01J 31/02 101X C07C 41/03 C07C 41/03 C08G 65/28 C08G 65/28 // C07B 61/00 300 C07B 61/00 300 F term (reference) 4C083 AA082 AC012 AC022 AC072 AC102 AC122 AC182 AC242 AC352 AC422 AC432 AC442 AC582 AC642 AC692 AD051 AD052 AD092 AD152 CC05 CC19 CC23 CC32 CC33 DD08 DD23 DD31 DD41 EE06 EE12 EE17 FF01 4H006 AA01 AB12 AB68 AB70 AC43 AD17 AD40 BA02 BA32 BC10 BC34 BC53 BD20 BD21 BE11 GN06 GP01 GP10 4H039 CA61 CF90 4J005 AA04 AA12 BB04

Claims (6)

[Claims] 1. The method according to claim 1, wherein the polydispersity is 1.
040 or less and the cloud point of the 50% by weight aqueous solution is 4
0 to 90 ° C. and the degree of unsaturation is 0.03 or less
Oligoalkyloxirane derivatives. Embedded image(However, AO is -OCH_TwoCH (CH_Three) -Group or -O
CH_TwoCH (CH_TwoCH_ThreeEO) is -OCH_TwoC
H_Two-AO and EO are randomly added
Or may be added in a block shape. k, m, n are
Each -OCH _TwoCH (CH_Three) -Group or -OCH_TwoC
H (CH_TwoCH_ThreeThe sum of the average number of moles of the group
a, b, and c are each —OCH_TwoCH_Two-Average addition of groups
1 ≦ k, m, n ≦ 4, 0 ≦ a, b, c ≦
3, 5 ≦ k + m + n ≦ 10, 0 ≦ a + b + c ≦ 3
It is the number to do. ) 2. The following formula (2) per mole of glycerin:
After contacting the alcoholate catalyst represented by the formula at a ratio of 0.005 to 0.1 mol and performing a dealcoholization treatment under reduced pressure, alkyl oxirane or oxirane was added to the mixture to give 8
The method according to claim 1, wherein the reaction is carried out at 0 to 110 ° C. ROX (2) (where R is a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and X is potassium or sodium) 3. The following formula (2) per mole of glycerin:
After contacting the alcoholate catalyst represented by the formula at a ratio of 0.005 to 0.1 mol and performing a dealcoholization treatment under reduced pressure, alkyl oxirane or oxirane was added to the mixture to give 8
The reaction is performed at 0 to 110 ° C., and then the reaction solution is adjusted to pH 3 or less in the presence of an antioxidant, and then treated with an acid adsorbent containing an alkaline earth metal oxide or an alkaline earth metal hydroxide. The method for producing an oligoalkyloxirane derivative according to claim 1, wherein ROX (2) (where R is a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and X is potassium or sodium) 4. A humectant comprising the oligoalkyloxirane derivative according to claim 1. 5. A cosmetic comprising the oligoalkyloxirane derivative according to claim 1 in an amount of 2 to 40% by weight. 6. A cleaning agent containing the oligoalkyloxirane derivative according to claim 1 in an amount of 2 to 40% by weight.