JPH1135443A - Moisturizer, skin-roughening improving agent and skin lotion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a moisturizer that has the moisturizing effect and skin- roughening-improving effect with excellent safety and stability to oxidation and low skin irritation by using a specific lower alkyl tetritol ether as an active ingredient. SOLUTION: This moisturizer contains a lower alkyl tetritol ether of the formula: A-Rn (A is the tetritol residue except n hydrogen atom; R is a 1-4C alkyl having a straight or branched chain, an unsaturated alkyl ; n is an average substitution degree and 1-4) a an active ingredient. This lower alkyl tetritol ether is prepared by mixing (A) tetritol as erythritol, when necessary, dissolved in a solvent, with (B) a compound of (i) the formula: X-R (an eliminating group as Br, I, mesyl, OH) or (ii) a compound of the formula (R1 -R4 are each an alkyl in which the total carbon atoms is 2 in R1 -R4 ) and allowing them to react with each other in the presence of a catalyst at 0-130 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel moisturizing agent, skin roughness improving agent, and a skin external preparation containing the same.
More specifically, a moisturizer and a skin roughness improving agent containing a lower alkyl tetritol ether as an active ingredient, which is highly safe, has a superior moisturizing effect and a skin roughness improving effect, and a moisturizing effect and a skin roughness improving effect containing the same. And a skin external preparation.

[0002]

2. Description of the Related Art Conventionally, skin external preparations have been used for various purposes such as improvement of usability and safety, reduction of skin irritation, and preservation, for example, polyethylene glycol, propylene glycol, and the like.
Glycerin, 1,3-butylene glycol, xylitol,
Sorbitol, maltitol, chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caronic acid, atelocollagen, cholesteryl-12-hydroxystearate, sodium lactate, bile salts, dl-pyrrolidone carboxylate, short-chain soluble collagen, diglycerin (EO ) Moisturizers such as PO adducts, Izayobara extract, Achillea millefolium extract, and melilot extract are incorporated.

[0003]

However, many of these moisturizers have poor functions and the expected effects are not always sufficient, and depending on the type of the compound, the oxidative stability, odor, etc. However, there is a problem in using it for an external preparation for skin.

In view of such circumstances, the present inventors have conducted intensive studies to obtain a skin external preparation having a truly excellent moisturizing effect. As a result, lower alkyl tetris which have never been used as a raw material for cosmetics are disclosed. We have discovered that tall ether has an excellent moisturizing effect and skin roughness improvement effect, and that when it is added to a skin external preparation, it is possible to obtain a skin external preparation that is excellent not only in moisturizing effect but also in skin improvement effect. Thus, the present invention has been completed.

An object of the present invention is to provide a novel moisturizing agent, a roughening agent, and a skin external preparation containing the same and having excellent moisturizing effects and skin roughness improving effects.

[0006]

That is, the present invention provides a humectant characterized by comprising a lower alkyl tetritol ether represented by the following general formula (1) as an active ingredient.

Embedded image A-Rn (1) (A represents a tetritol residue excluding a hydrogen atom n;
Is an alkyl group having 1 to 4 carbon atoms, and may be any of a linear alkyl group, a branched alkyl group, an unsaturated alkyl group, and a hydroxyalkyl group. n represents the average degree of substitution of R;
Is a number in the range. )

The present invention also provides a skin roughness improving agent comprising the above lower alkyl tetritol ether as an active ingredient.

[0008] The present invention further provides a skin external preparation characterized by containing the above-mentioned lower alkyl tetritol ether.

[0009]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The configuration of the present invention will be described below in detail.

The lower alkyl tetritol ether used in the present invention has an excellent moisturizing effect, an effect of improving rough skin,
It is excellent in safety and oxidative stability, and is characterized by being less irritating to the skin. Therefore, it is a compound that can be used in an external preparation for skin as an excellent moisturizing agent and a skin roughness improving agent. Conventionally, a lower alkyl ether of tetritol has not been blended in an external preparation for skin such as cosmetics. In the field of 化合物, it is a new starting compound.

[0011] Tetritol used for producing lower alkyl tetritol ether is a sugar alcohol of tetroses having 4 carbon atoms, for example, erythritol,
D-threitol and L-threitol.

The lower alkyl tetritol ether used in the present invention is represented by the following general formula (1). A is a residue obtained by removing n hydrogen atoms from tetritol.

Embedded image A-Rn (1)

In the general formula (1), A is a residue obtained by removing n hydrogen atoms from tetritol, and R is a group having 1 carbon atom.
It may be any of a straight chain alkyl group, a branched alkyl group, an unsaturated alkyl group, a cycloalkyl group and a hydroxyalkyl group. For example, methyl group, ethyl group, propyl group, butyl group, isopropyl group, s-butyl group,
t-butyl group, allyl group, 2-butenyl group, 3-butenyl group, 2-methyl-2-propenyl group, 2,4-bicyclopropyl group, cyclobutyl group, 2-methylcyclopropyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2-hydroxy1-
Methylethyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxy-2-methylpropyl group, 2-hydroxy-2-methylpropyl group, 2-hydroxy-1,1-dimethylethyl group ,
2,3-dihydroxypropyl group, bis (hydroxymethyl) methyl group, 2,3-dihydroxybutyl group, 2,
4-dihydroxybutyl group, 3,4-dihydroxybutyl group, 2,3-dihydroxy-2-methylpropyl group, 3
-Hydroxy-2-hydroxymethylpropyl group, 1,1
-Bis (hydroxymethyl) ethyl group, tris (hydroxymethyl) methyl group and the like.

The position of the ether bond between the four hydroxyl groups and the lower alkyl group of tetritol is arbitrary and may be at any position. The number of ether bonds is preferably monoether from the viewpoint of solubility in water, but may be any mixture of diether, triether and tetraether.
Further, the alkyl group may be any two or more kinds of conjugates. The average degree of substitution n is in the range of 1 to 4, but is preferably in the range of 0.1 to 2.8 in view of its properties.

The lower alkyl tetritol ether of the present invention is produced by a general etherification reaction. For example, tetritol is dissolved in a non-aqueous solvent such as dimethylformamide, dimethylsulfoxide, dioxane, dimethylacetamide, acetone, N-methylpyrrolidone, N-acetylmorpholine, N-methylsuccinimide, or in a solvent-free solvent. Equation (2)

Embedded image XR (2) (where R is the same as defined in the general formula (1), X is a leaving group or a hydroxyl group, and examples of the leaving group include bromine,
Examples thereof include chlorine, iodine, a mesyl group, and a tosyl group. Or the general formula (3)

Embedded image (Or an alkyl group having a total carbon number of R _{1 to} R ₄ of 2), and the mixture is stirred and reacted at 0 ° C. to 130 ° C. in the presence of a catalyst. . [Robert et al .: Tetrahedron,
35, 2169-2172 (1979)].

Examples of the above catalyst include acids such as sulfuric acid, hydrochloric acid and phosphoric acid, alkalis such as lithium hydroxide, sodium hydroxide, potassium hydroxide and metallic sodium, sodium alcoholates such as sodium methylate and sodium ethylate, N Amines such as -methylbenzylamine and the like.

The molar ratio of the compound represented by the general formula (2) or (3) used in this reaction is 1 when the monoether preferred in the present invention is to be obtained as a main product. : 1 to 3: 1, preferably 2: 1 to 1
3: 1 is more preferred. When the ratio of tetritol to the compound represented by the general formula (1) or (2) is out of this range, that is, when the amount of tetritol is too small, triether or the like is easily generated. Hinders the purification of

When all the compounds represented by the general formula (2) or (3) are consumed, an acid such as acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid or the like is used for the purpose of neutralizing the catalyst of the reaction system. An alkali such as lithium, sodium hydroxide and potassium hydroxide, and a salt such as sodium hydrogen carbonate are added, and the reaction solvent is distilled off under reduced pressure. Alternatively, purification may be carried out without neutralization.

The reaction product thus obtained includes:
A salt and tetritol coexist in addition to the lower alkyl tetritol ether. Therefore, when removing tetritol and salts, extraction with a solvent that does not dissolve erythritol such as methyl alcohol, ethyl alcohol, butyl alcohol, and isopropyl alcohol, or partition with water containing a large amount of salt, methyl ethyl ketone, and n-butanol, It can be purified by separating the solvent layer. In addition, it is also possible to purify using a reverse layer distribution column such as a hyperporous polymer (for example, a high porous resin manufactured by Mitsubishi Chemical Corporation), octadecyl silica, or a silica gel column.

The lower alkyl tetritol ether synthesized as described above may be used after distilling off the extraction solvent or purifying it with a column, or may be used without any particular purification.

The lower alkyl tetritol ether used in the present invention can be a derivative of a lower alkyl tetritol ether having a desired degree of ether substitution by subjecting tetritol to a protecting group with another compound or a derivative. it can.

For example, when trying to obtain a monoether, it can also be obtained by the following synthesis. That is, 1,3
-Butadiene monoeposide is represented by the general formula (4)

## STR6 ## Z-OR (4) (R is the same as defined in the general formula 1. Z is a metal such as sodium or potassium.)
General formula (5) or General formula (6)

Embedded image RO—CH ₂ —CHOH—CH ＝ CH ₂ (5)

Embedded image A compound such as HO—CH ₂ —CHOR—CH ＝ CH ₂ (6) (where R is the same as defined in the general formula (1)) was obtained, and then the double bond was epoxidized. The desired lower alkyl tetritol ether can be obtained by ring-opening diol later or by direct diolation. Further, the desired compound is obtained by subjecting the epoxy group of 1,3-butadiene monoepoxide to ring-opening diol and then epoxidizing the double bond and reacting with a nucleophile represented by the general formula (4). The compound can also be obtained by etherifying a ring-opened diol compound and then diolating the double bond.

Further, cis 2-butene-1,4-diol is converted into a monoacyl ester, further benzylated and then deacylated, and the resulting monobenzylbutene diol is converted into a lower alkyl ether to form a double bond of the obtained compound. Part by diolation and debenzylation,
The lower alkyl tetritol ether used in the present invention can be obtained. In this case, the protecting group is not limited to a benzyl group, and other compounds may be used as long as the bond can withstand acid and alkali.

The lower alkyl tetritol ether has a moisturizing effect and a roughening effect, and can provide a moisturizing agent or a roughening agent containing the same as an effective ingredient. Thus, the skin external preparation of the present invention having a moisturizing effect or a skin roughness improving effect is provided.

The amount of the lower alkyl tetritol ether to be added to the external preparation for skin according to the present invention is not particularly limited.
1 to 20% by weight, preferably 0.01 to 15% by weight,
Particularly preferably, the content is 0.1 to 10% by weight. If the amount is less than 0.001% by weight, the effect of the external preparation for skin tends to be poor, and if the amount exceeds 20% by weight, the effect cannot be substantially increased, and Formulation also tends to be difficult.

The external preparation for skin of the present invention includes, in addition to the above essential components, other components usually used in external preparations for skin such as cosmetics and pharmaceuticals, such as oils, wetting agents, ultraviolet absorbers, antioxidants, Surfactants, preservatives, other humectants, fragrances, colorants, water, alcohols, thickeners, polymers, powders, drugs, chelating agents, plant extracts, etc. can be appropriately compounded as necessary. .

The dosage form of the external preparation for skin of the present invention is arbitrary,
The essential components of the present invention depending on the target product, such as a solution system, a solubilizing system, an emulsifying system, an oil-liquid system, a gel system, a powder dispersion system, a water-oil two-layer system, a water-oil-powder three-layer system, etc. And the above-mentioned optional components can be blended to produce the compound by a conventional method.

The skin external preparation of the present invention refers to those applied to the outer skin (including the scalp) as cosmetics, pharmaceuticals, and quasi-drugs, and includes, for example, facials such as lotions, emulsions, creams, and packs. Cosmetics, foundation, lipstick,
It can be used for makeup cosmetics such as eye shadows, body cosmetics, aromatic cosmetics, scalp hair cosmetics, cleaning agents, ointments and the like.

[0029]

Next, the present invention will be described in more detail by way of examples. The present invention is not limited by this. All amounts are by weight.

First, a synthesis example of the lower alkyl tetritol ether used in the present invention will be described in detail.

"Synthesis Example 1: Monomethylerythritol E
(1,2,3-trihydroxy-4-methoxy-buta)
N) 73.4 g of cis 2-butene-1,4-diol
(0.6 mol) acetone 240 previously dried
and dissolved in 78 ml of propionic anhydride (0.6 mol).
l) was added and the mixture was heated under reflux for 15 hours. Air cooling at room temperature
Then, the mixture was concentrated under reduced pressure, extracted with 500 ml of ethyl acetate, and purified.
Wash 3 times with water making and dry with anhydrous magnesium sulfate
Then, the mixture is concentrated under reduced pressure.
Purified by a chromatographic method, the colorless oily monopropyl
Onic acid cis 2-butene-1,4-diol ester was added to 3
8.1 g (43.4% yield) was obtained. The monoprop obtained
Acid cis 2-butene-1,4-diol ester 3
8.1 g (264 mmol) of dried
Dissolve in 150 ml of toxicethane and add sodium hydride 2
6.4 g (396 mmol, 60% purity)
After washing under vacuum and drying under reduced pressure, add for 30 minutes
Stir at room temperature. 67.85 g of benzyl bromide (291
mmol) and stirred at room temperature for 3 hours. Methaneau
The reaction was stopped by adding 100 ml of toluene and concentrated under reduced pressure.
Extract with 500 ml of ethyl acetate and wash three times with purified water
did. After drying and filtering with anhydrous magnesium sulfate,
Concentrated to give a colorless oily crude 1-benzyloxy-cis 2
-Butenyl propionate was obtained. The crude 1-ben obtained
Diloxy-cis 2-butenyl propionate was converted to methanol
Dissolved in 300 ml of sodium methylate methanol
Solution (manufactured by Wako Pure Chemical Industries, Ltd.) and heat to reflux overnight.
Was. After concentration under reduced pressure, extract with 500 ml of ethyl acetate
And washed twice with purified water. To anhydrous magnesium sulfate
After drying, the mixture was filtered and concentrated under reduced pressure.
Purified by silica gel column chromatography, colorless
Ill-form 1-benzyloxy-cis 2-buten-4-o
36.8 g (78.3%; cis monopropionate 2)
-Total yield from butene-1,4-diol ester
Rate). 1-benzyloxy-cis 2-bute obtained
30.1 g (169 mmol) of di-4-ol
Dissolve in 200 ml of tyl sulfoxide, and add potassium hydroxide
After addition of 28.4 g (422 mmol) of
Then, 67 g (472 mmol) of methyl iodide was added,
Stirred at room temperature for 5 hours. Extract with 500 ml of ethyl acetate
And washed once with purified water. Anhydrous magnesium sulfate
After drying and filtration at, the mixture was concentrated under reduced pressure.
Purified by silica gel column chromatography, colorless
I-like 1-benzyloxy-4-methoxy-cis 2-bu
30.7 g (94.9% yield) of ten were obtained. 1 obtained
-Benzyloxy-4-methoxy-cis 2-butene 30.
7 g (160 mmol) dissolved in 300 ml of chloroform
And 55.2 g (320 mmol) of mCPBA was added.
And stirred at room temperature overnight. Concentrate under reduced pressure and add ethyl acetate 5
Extract with 100ml, 10% sodium thiosulfate aqueous solution
Once, and once with saturated aqueous sodium hydrogen carbonate solution
Washed once with water. Dried over anhydrous magnesium sulfate,
After filtration, the mixture was concentrated under reduced pressure.
Purified by column chromatography to give a colorless syrup
1-benzyloxy-2-epoxy-4-methoxy-buta
30.4 g (91.2% yield) were obtained. The obtained 1-
Benzyloxy-2-epoxy-4-methoxy-butane 3
0.4 g (146 mmol) of 10% aqueous dimethyl sulf
Dissolve in 200 ml of foxide and crush in advance in a mortar
14 g (248 mmol) of potassium hydroxide
Then, the mixture was stirred at 100 ° C. for 8 hours. Vinegar after air cooling at room temperature
Extract with 500 ml of ethyl acid and wash once with purified water
Was. After drying over anhydrous magnesium sulfate and filtration, the pressure was reduced.
Concentrate and concentrate the resulting concentrate on silica gel chromatography.
1-benzyloxy 2,3 in the form of a colorless syrup
28.7 g of dihydroxy-4-methoxybutane (yield
Rate of 87.0%). 1-benzyloxy 2,3-dihydride
Roxy-4-methoxybutane 31.0 g (137 mmol
l) was dissolved in 200 ml of ethanol, and 10%
2 spatulas of carbon and 6 drops of concentrated hydrochloric acid
Stirred at warm. About 31 l of hydrogen was consumed and filtered. Furnace
The solution was concentrated under reduced pressure and dried under reduced pressure to give a colorless syrupy crude 1-
Methoxy-2,3,4-trihydroxy-butane is obtained.
Was. The obtained crude 1-methoxy-2,3,4-trihydro
Xy-butane is acetylated by a conventional method, and syrupy
1,2,3-triacetoxy-4-methoxy-butane 2
8.7 g (87.0%; 1-benzyloxy-2-epoxy)
(Total yield of ci-4-methoxy-butane). Profit
1,2,3-triacetoxy-4-methoxy-butyl
The analytical values of the tan are shown below.¹ H-NMR (CD_ThreeOD, TMS, ppm) 5.3, 5.2, 4.3, 4.1, 3.5, 3.3,
2.1, 2.1, 2.0 ¹³ C- NMR (CD OD, TMS, ppm) δ 170.5, 170.1, 170.0, 70.7, 7
0.2, 70.0, 62.1, 62.0, 59.2, 2
1.0, 20.7 The resulting 1,2,3-triacetoxy-4-methoxy-
22.71 g of butane is deacetylated by a conventional method, and oil
Erythritol monomethyl ether (1,2,3-
11.5 g of trihydroxy-4-methoxy-butane)
(Yield 97.5%). The obtained erythritol mo
The analytical values of nomethyl ether are shown below. GC / MSD (TMS processing, m / Z) 307, 147, 103, 73¹ H-NMR (CD3 OD, TMS, ppm) 2.0-1.98 (m)¹³ C-NMR (CD3 OD, TMS, ppm) δ 56.1, 61.1, 68.0, 70.1, 72.0

"Synthesis Example 2: Synthesis of methyl erythritol ether" 10 g (82 mmol) of erythritol was dissolved in 100 ml of anhydrous dimethyl sulfoxide, and 3.3 g (82 mmol) of pulverized sodium hydroxide was added.
11.6 g (82 mmol) of methyl iodide was added dropwise with stirring. After stirring overnight at room temperature, hydrochloric acid was added to neutralize the reaction system, and the solvent was distilled off under reduced pressure.
Extracted in ml. The obtained methanol layer was concentrated under reduced pressure,
4.5 g of methyl erythritol ether (average degree of substitution n: 1.3) was obtained.

"Synthesis Example 3: Synthesis of methyl threitol ether" 10 g (82 mol) of threitol was dissolved in 100 ml of anhydrous dimethyl sulfoxide, and 3.3 g (82 mmol) of pulverized sodium hydroxide was added. 6 g (82 mmol) were sequentially added dropwise with stirring. After stirring at room temperature overnight, hydrochloric acid was added to neutralize the reaction system, and then the solvent was distilled off under reduced pressure and extracted with 200 ml of methanol. The obtained methanol layer was concentrated under reduced pressure, and 4.3 g of methylthreitol ether (average degree of substitution n;
5) was obtained.

Synthesis Example 4: Synthesis of ethyl erythritol ether 10 g (82 mol) of erythritol was dissolved in 90 ml of anhydrous dimethyl sulfoxide, 3.3 g (82 mmol) of ground sodium hydroxide was added, and 12.8 g of ethyl iodide was added. (82 mmol) were added dropwise with stirring. After stirring at room temperature overnight, hydrochloric acid was added to neutralize the reaction system, and the solvent was distilled off under reduced pressure.
Extracted. The obtained methanol layer was concentrated under reduced pressure, and 5.0 g of ethyl erythritol ether (average degree of substitution n;
1.2) was obtained.

"Synthesis Example 5: Synthesis of ethyl threitol ether" 30 g of ethanol was added to 10 g (82 mol) of threitol, and 3.3 g of ground sodium hydroxide (82 g)
mmol) and heated. After the reaction, the reaction mixture was extracted with methanol, and the obtained methanol layer was concentrated under reduced pressure to obtain 4.8 g of methylthreitol ether (average degree of substitution n: 1.3).

"Synthesis Example 6: Synthesis of a mixture of methyl threitol ether and methyl erythritol ether" 1,
10 g of 3-butadiene monoepoxide (144 mmo
l) was dissolved in 20 ml of dimethyl sulfoxide, 9.3 g (171 mmol) of sodium methylate and 9.9 g (186 mmol) of ammonium chloride were added, and 90 ° C.
The mixture was stirred in a closed system. After the reaction, the reaction mixture was extracted with 200 ml of ethyl acetate and concentrated under reduced pressure.
And dissolved in 4 ml of mCPBA (288 mm
ol) and stirred at room temperature overnight. The mixture was concentrated under reduced pressure, extracted with 300 ml of ethyl acetate, and washed once with a 10% aqueous sodium thiosulfate solution, once with a saturated aqueous sodium hydrogen carbonate solution, and once with purified water. After drying and filtering over anhydrous magnesium sulfate, the solution was concentrated under reduced pressure, and the obtained concentrate was dissolved in 200 ml of 10% aqueous dimethyl sulfoxide, and 7 g of potassium hydroxide previously ground in a mortar.
(124 mmol) and stirred at 100 ° C. for 4 hours. After air cooling at room temperature, the mixture was neutralized with hydrochloric acid, concentrated under reduced pressure, acetylated by a conventional method, and 1,2,3-triacetoxy-
21.5 g of 4-methoxy-butane (57.0%; 1,3
-Butadiene monoepoxide total yield).
The obtained 1,2,3-triacetoxy-4-methoxy-
21.5 g of butane was deacetylated by a conventional method, and a mixture of methylthreitol ether and methylerythritol ether (1,2,3-trihydroxy-4-methoxy-) was obtained.
Butane) was obtained in an amount of 10.8 g (yield 96.5%).

Next, the effect test method and the evaluation method of the present invention will be described. The moisturizing effect on skin and the effect of improving rough skin were evaluated by the following methods.

"Measurement of Moisturizing Effect by Moisture Evaporation Rate" As a test for measuring the moisturizing effect of the humectant, the samples shown in Table 1 were measured for the moisture evaporation rate. That is, 2.0
After dropping 10 μl of the test solution onto a × 2.0 cm 2 filter paper, the weight loss was measured every minute for 10 minutes, and the weight loss per minute was determined. The humectant was prepared by dissolving the dried residue in water and adjusting the concentration to 5% as a sample solution. Distilled water was used as a target. The moisturizing effect was evaluated according to the following criteria, and the results are shown in Table 2. As is clear from Table 2, it was confirmed that the example of the humectant of the present invention had a better moisturizing effect than the comparative example of the conventional humectant. (Criterion criteria) A: Water evaporation rate 0.50 μg / min. Less than ○: Water evaporation rate 0.50 to 0.55 μg / min. Δ: Water evaporation rate 0.55 to 0.60 μg / min. ×: Water evaporation rate 0.60 μg / min. that's all

[0039]

[Table 1]

[0040]

[Table 2]

"Skin moisturizing effect test" The moisturizing effect on the skin was evaluated using panels of 20 men and women. As an evaluation method, a sample was applied after washing the upper arm, and as described below, changes in TWL and skin conductance before the test were measured to test the moisturizing effect of the skin. The evaluation was performed according to the following evaluation criteria, and the results are shown in Table 3. As is clear from Table 3, it was confirmed that the example of the moisturizing agent of the present invention had a better skin moisturizing effect than the comparative example of the conventional moisturizing agent. Conductance change rate = conductance change amount / conductance value before use TWL change rate = TWL change amount / TWL value before use (Evaluation criteria) ：: Conductance change rate + 10% or more △: Conductance change rate + 3% or more + less than 10% ×: Conductance change rate + 3% or less ○: TWL change rate + 10% or more △: TWL change rate + 3% or more and less than + 10% ×: TWL change rate + 3% or less

[0042]

[Table 3]

"Skin roughness improvement effect test" The skin roughness improvement effect was evaluated using panels of 20 men and women. In the evaluation method, the inner skin of the upper arm is treated with a 3% aqueous solution of sodium dodecyl sulfate to create rough skin. Two hours later, the samples in Table 1 are adjusted to a 5% aqueous solution, and 40 μl of the sample is open-applied. This is 5
The test was repeated for one day, and on the sixth day, the effect of improving skin roughness was visually determined. The criteria are as follows: the lower the score, the more severe the skin becomes rough, and the higher the score, the more beautiful the skin. (Criterion criteria) Rating 1: Drying, turning over, and strong erythema of a wide range of stratum corneum are recognized. Score 2: Dry, turned-up, moderate erythema of the stratum corneum is recognized. Score 3: Drying of the stratum corneum is observed, but no turning is observed. Weak erythema is observed. Score 4: Drying and turning of the stratum corneum are not recognized, but slight erythema is recognized. Rating 5: Neither dryness, turning over, nor erythema was recognized. The evaluation was carried out by an average value based on the scores, and the evaluation was made according to the following evaluation criteria. The results are shown in Table 4. As is clear from Table 4, it was confirmed that the example of the humectant of the present invention, which is a humectant of the present invention, has a better skin roughness improvement effect than the comparative example of the conventional humectant. (Evaluation criteria) ◎: Average score is 4 or more and 5 or less ○: Average score is 3 or more and less than 4 △: Average score is 2 or more and less than 3 ×: Average score is 1 or more and less than 2

[0044]

[Table 4]

"Surface roughness improvement effect actual use test" An actual use test was conducted by the following method. A replica of the skin surface morphology of the face of a healthy female was made with a silicone resin, and observed with a microscope (17 ×). In other words, the following examples were applied to the left and right half of the face using a group of 10 persons (rough panel) determined to have skin roughness evaluations 1 and 2 based on the following criteria based on the following criteria based on the state of the skin pattern and the peeling state of the stratum corneum. The lotions 1 to 6 and Comparative Examples 1 to 7 were applied twice a day. Two weeks later,
The replica was again taken and the condition of the skin was judged as described above. The criteria are as follows. The lower the score, the more severe the skin becomes rough, and the higher the score, the more beautiful the skin. (Judgment Criteria) Rating 1: Elimination of skin sulcus and skin ridge. Extensive stratum corneum turning. Score 2: Skin grooves and skin hills are unclear. Turn of the stratum corneum. Score 3: Skin grooves and skin ridges were observed, but flat. Score 4: Skin groove and skin hills are clear. Score 5: The skin sulcus and skin hills are clear and well-ordered. The evaluation was made according to the following evaluation criteria, and the results are shown in Table 5. As is clear from Table 5, it was confirmed that the example of the humectant of the present invention, which is a humectant of the present invention, has a better skin roughness improvement effect than the comparative example of the conventional humectant. (Evaluation Criteria) 割 合: The percentage of panels evaluated as 4 and 5 is 90% or more ○: The percentage of panels evaluated as 4 and 5 is 75% or more and less than 90% Δ: Evaluated as 4 and 5 ×: The proportion of panels evaluated as score 4 or 5 is less than 25%.

[0046]

[Table 5]

"Examples 1 to 6, Comparative Examples 1 to 6: Lotion" The following lotions were produced by a conventional method. Propylene glycol 5.0% Citric acid 4.0 Drugs (described in Table 1) 3.0 95% ethanol 8.0 POE (20) lauryl ether 2.0 Preservatives / antioxidants Appropriate amount Fragrance Appropriate amount Ion-exchanged water residue Extra

Hereinafter, other examples of a skin external preparation using the humectant and the skin roughness improving agent of the present invention will be described.

Example 7: Vanishing cream Stearic acid 5.0 Stearic alcohol 4.0 Stearic acid butyl alcohol ester 8.0 Glycerin monostearate 2.0 Ascorbic acid distearate 1.0 Propylene glycol 10.0 Monomethyl erythritol 1.0 Preservative / Antioxidant Appropriate amount Fragrance Appropriate amount Ion-exchanged water residue (Preparation method) Add monomethylerythritol and propylene glycol to ion-exchanged water, dissolve and heat to 70 ° C (aqueous phase). The other components are mixed, melted by heating and kept at 70 ° C. (oil phase). The oil phase is gradually added to the water phase, and after the addition is completed, the temperature is maintained for a while to cause a reaction.
Thereafter, the mixture is uniformly emulsified with a homomixer and cooled to 30 ° C. while stirring well.

Example 8: Vanishing cream Stearic acid 6.0 Sorbitan monostearate 2.0 Polyoxyethylene (20 mol) Sorbitan monostearate 1.5 Arbutin 7.0 Propylene glycol 10.0 Mono Ethyl erythritol 5.0 Preservative / Antioxidant Appropriate amount Fragrance Appropriate amount Ion-exchanged water residue (Preparation method) Add monoethylerythritol, arbutin and propylene glycol to ion-exchanged water and heat.
Keep at ° C (aqueous phase). Mix with other ingredients and heat and melt to 70
C (oil phase). Add oil phase to water phase, pre-emulsify,
After uniformly emulsifying with a homomixer, the mixture is cooled to 30 ° C. while stirring well.

Example 9 Neutral Cream Stearyl Alcohol 7.0 Stearic Acid 2.0 Hydrogenated Lanolin 2.0 Squalane 5.0 2-Octyldo Deserial Call 6.0 Polyoxyethylene (25 mol) Cetyl Alcohol ether 3.0 Glycerin monostearate 2.0 Placenta extract 0.1 Propylene glycol 5.0 Methylerythritol (average degree of substitution n; 1.5) 10.0 Perfume Appropriate Preservative / Antioxidant Appropriate Ion-exchanged water Residue (Preparation method) Methylerythritol (average degree of substitution n; 1.5), placenta extract and propylene glycol are added to ion-exchanged water, and heated to 70 ° C. (aqueous phase). The other components are mixed, melted by heating and kept at 70 ° C. (oil phase). The oil phase is added to the water phase to perform preliminary emulsification, and after uniform emulsification with a homomixer, the mixture is cooled to 30 ° C. while stirring well.

Example 10 Cold Cream Solid Paraffin 5.0 Beeswax 10.0 Vaseline 15.0 Liquid Paraffin 41.0 Glycerin Monostearate 2.0 Polyoxyethylene (20 mol) 2.0 Sorbitan Monolaurate ester Kojic acid 2.0 Soap powder 0.1 Borax 0.2 Ethyl erythritol ether (average degree of substitution n; 1.3) 0.1 Ion-exchange water Residual perfume Appropriate amount Preservative / antioxidant Appropriate amount ( Production method) Ethyl erythritol ether (average degree of substitution n: 1.3), kojic acid, soap powder and borax are added to ion-exchanged water, heated and dissolved, and kept at 70 ° C (aqueous phase). The other components are mixed, melted by heating and kept at 70 ° C. (oil phase). The oil phase is gradually added to the aqueous phase while stirring to carry out the reaction. After the completion of the reaction, the mixture is uniformly emulsified with a homomixer, and cooled to 30 ° C. while stirring well after emulsification.

Example 11: Emulsion Polyoxyethylene (20 mol) Polyoxypropylene (2 mol) Cetyl alcohol 1.0 Silicone KF96 (20cs) (Shin-Etsu Chemical) 2.0 Liquid paraffin (medium viscosity) 0 Propylene glycol 5.0 Arbutin 2.0 Glycerin 2.0 Ethyl alcohol 15.0 Carboxyvinyl polymer 0.3 Hydroxypropylcellulose 0.1 2-Aminomethylpropanol 0.1 Preservative Appropriate amount Monomethylerythritol / monomethyltriitol mixture 20.0 Ion-exchanged water residue (Preparation method) A mixture of monomethylerythritol / methyltriol and arbutin are heated and dissolved in ion-exchanged water and ethanol, and water-soluble components such as propylene glycol or less are further dissolved and kept at 70 ° C. Aqueous phase) The other oil components are mixed, heated and melted and kept at 70 ° C. (oil phase). The oil phase is added to the water phase, preliminarily emulsified, homogenized with a homomixer, emulsified, and cooled to 30 ° C. while stirring well.

“Example 12: Emulsion” Polyoxyethylene (20 mol) Polyoxypropylene (2 mol) Cetyl alcohol 1.0 Silicone KF96 (20cs) (Shin-Etsu Chemical) 2.0 Liquid paraffin (medium viscosity) 0 Propylene glycol 5.0 Sodium ascorbic acid-2-sulfate 5.0 Glycerin 2.0 Ethyl alcohol 15.0 Carboxyvinyl polymer 0.3 Hydroxypropylcellulose 0.1 2-Aminomethylpropanol 0.1 Preservative Suitable amount Mono Ethyl erythritol / monoethyl threitol mixture 7.0 Ion-exchanged water residue (Preparation method) Heat-dissolve the monoethyl erythritol / monoethylthreitol mixture in ion-exchanged water and ethanol, and further dissolve water-soluble components below propylene glycol To 70 ° C One (aqueous phase). Mix with other oily ingredients,
Heat to melt and maintain at 70 ° C (oil phase). The oil phase is added to the water phase, preliminarily emulsified, and uniformly emulsified by a homomixer. After emulsification, the mixture is cooled to 30 ° C. while stirring well.

Example 13: Emulsion Polyoxyethylene (20 mol) Polyoxypropylene (2 mol) Cetyl alcohol 1.0 Silicone KF96 (20cs) (Shin-Etsu Chemical) 2.0 Liquid paraffin (medium viscosity) 0 Propylene glycol 5.0 Glycerin 2.0 Ethyl alcohol 15.0 Carboxyvinyl polymer 0.3 Hydroxypropylcellulose 0.1 2-Aminomethylpropanol 0.1 Preservative Appropriate amount Placental extract 5.0 Methyl erythritol (average substitution) Degree n; 1.8) 7.0 Ion-exchanged water residue (Preparation method) Methylerythritol (average degree of substitution n; 1.8) and placenta extract are dissolved by heating in ion-exchanged water and ethanol, and propylene glycol or less Are dissolved and kept at 70 ° C. (aqueous phase). The other oil components are mixed, heated and melted and kept at 70 ° C. (oil phase). Add oil phase to water phase, pre-emulsify, homogenize uniformly with homomixer,
After emulsification, cool to 30 ° C while stirring well.

Example 14: Emulsion Polyoxyethylene (20 mol) Polyoxypropylene (2 mol) Cetyl alcohol 1.0 Silicone KF96 (20cs) (Shin-Etsu Chemical) 2.0 Liquid paraffin (medium viscosity) 0 Propylene glycol 5.0 Glucerin 2.0 Ethyl alcohol 15.0 Carboxyvinyl polymer 0.3 Hydroxypropylcellulose 0.1 2-Aminomethylpropanol 0.1 Preservative Appropriate amount Kojic acid 3.0 Ethyl erythritol (Average degree of substitution n; 1.2) 3.0 ion-exchanged water residue (Preparation method) Ethyl erythritol (average degree of substitution n; 1.2) and kojic acid are dissolved by heating in ion-exchanged water and ethanol, and further, an aqueous solution of propylene glycol or less Dissolve the acidic components and maintain at 70 ° C. (aqueous phase). The other oil components are mixed, heated and melted and kept at 70 ° C. (oil phase). Add oil phase to water phase, pre-emulsify, homogenize uniformly with homomixer,
After emulsification, cool to 30 ° C while stirring well.

Example 15 Emulsion 1.5 Stearic Acid 1.5 Cetyl Alcohol 0.5 Beeswax 2.0 Polyoxyethylene (20 mol) Monooleate 1.0 Glycerin Monostearate 1.0 Quince Seed Extract (5% aqueous solution) 20.0 Ethyl alcohol 10.0 Arbutin 20.0 Propylene glycol 5.0 Butyl erythritol (Average degree of substitution n; 0.8) 3.0 Ion-exchanged water Residual perfume Appropriate preservative Antioxidant Appropriate amount (Preparation method) Add butylerythritol (average degree of substitution n: 0.8), arbutin and propylene glycol to ion-exchanged water, dissolve by heating, and maintain at 70 ° C (aqueous phase). Add flavor to ethyl alcohol and dissolve (alcohol phase). Other components except the quince seed extract are mixed, heated and melted, and kept at 70 ° C. (oil phase). The oil phase is added to the water phase, pre-emulsified, and homogenized uniformly with a homomixer. While stirring, add the alcohol phase and the quince seed extract. Then, cool to 30 ° C with stirring.

Example 16: Emulsion Microcrystalline wax 1.0 Beeswax 2.0 Lanolin 2.0 Liquid paraffin 20.0 Squalane 10.0 Sorbitan sesquioleate 4.0 Polyoxyethylene (20 mol) 1.0 Sorbitan monooleate Arbutin 5.0 Kojic acid 5,0 Propylene glycol 7.0 Mixture of methylerythritol / methylthreitol 2.0 (Average degree of substitution n; 1.6) Ion-exchanged water Residual perfume Appropriate amount Preservative / Antioxidant Appropriate amount (Preparation method) Methylerythritol / methylthreitol mixture 2.0 (average degree of substitution n; 1.6) in ion-exchanged water,
Arbutin, kojic acid and propylene glycol are added and heated to 70 ° C. (aqueous phase). The other components are mixed, dissolved by heating and kept at 70 ° C. (oil phase). While stirring the oil phase, the aqueous phase is gradually added to the oil phase, and the mixture is uniformly emulsified with a homomixer. After emulsification, cool to 30 ° C with good stirring.

Example 17 Jelly 95% ethyl alcohol 10.0 dipropylene glycol 15.0 polyoxyethylene (15 mol) oleyl alcohol ether 2.0 arbutin 0.5 ascorbic acid distearate 0.5 carboxyvinyl Polymer (trade name: Carbopol 941) 1.0 Caustic potash 0.15 L-arginine 0.1 Hydroxyethylthreitol (average degree of substitution n; 1.3) 2.0 Methylerythritol (average degree of substitution n; 1.5) 1.0 1.0 Perfume Appropriate amount Preservative Appropriate amount Ion-exchange water residue (Preparation method) Hydroxyethylthreitol (average degree of substitution n; 1.3), methylerythritol (average degree of substitution n; 1.5) in ion-exchanged water , Arbutin and Carbopol 9
41 is dissolved uniformly, while dipropylene glycol, polyoxyethylene (15 mol) oleyl alcohol ether and other components are dissolved in 95% ethanol and added to the aqueous phase. Then, it is neutralized with caustic potash and L-arginine to increase the viscosity.

“Example 18: Peel-off type pack” (alcohol phase) 95% ethanol 10.0 polyoxyethylene (15 mol) oleyl alcohol ether 2.0 preservative appropriate amount perfume appropriate amount (aqueous phase) monoethyl erythritol・ Monoethylthreitol mixture 4.0 Arbutin 1.0 Polyvinyl alcohol 12.0 Glycerin 3.0 Polyethylene glycol 1500 1.0 Ion-exchanged water Residue (Preparation method) Prepare an aqueous phase at 80 ° C and cool to 50 ° C I do.
Then, the alcohol phase prepared at room temperature is added, mixed uniformly, and left to cool.

“Example 19: Pack with powder” (Alcohol phase) 95% ethanol 2.0 Preservatives Appropriate amount Flavors Appropriate amount Colorant Appropriate amount Ascorbic acid diolate 1.0 (Aqueous phase) Ethylthreitol ( Average substitution degree n; 1.3) 7.0 Arbutin 1.0 Propylene glycol 7.0 Zinc white 25.0 Kaolin 20.0 Ion-exchanged water Residue (Preparation method) An aqueous phase is uniformly prepared at room temperature. Then, the alcohol phase prepared at room temperature is added and mixed uniformly.

“Example 20: Water-absorbing ointment” Vaseline 40.0 Stearyl alcohol 18.0 Mokurou 20.0 Polyoxyethylene (10 mol) monooleate 0.25 Hydroxyethyl erythritol (Average degree of substitution n: 1.5 0.25 Placental extract 1.0 Baringlyserine ester / hydrochloride 10.0 Ion-exchanged water residue (Preparation method) Add hydroxyethylerythritol (average degree of substitution n; 1.5) and placenta extract to ion-exchanged water , 70
Keep at ° C (aqueous phase). Other components are mixed and dissolved at 70 ° C. (oil phase). The oil phase is added to the aqueous phase, and the mixture is uniformly emulsified with a homomixer and then cooled.

The skin external preparations obtained in the present invention all showed skin roughening improvement effects in the actual use test conducted in Examples 1 to 6 in which the skin roughening improvement effect was recognized.

[0064]

According to the present invention, it is possible to provide a novel moisturizing agent and a skin roughness improving agent having an excellent moisturizing effect and a skin roughness improving effect. In addition, it is possible to provide a skin external preparation that is highly safe, has an excellent moisturizing effect and a skin roughness improvement effect, and is excellent in usability.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hideo Nakajima 1050 Nippa-cho, Kohoku-ku, Yokohama-shi, Kanagawa Inside Shiseido Daiichi Research Center Co., Ltd.

Claims (3)

[Claims] 1. A humectant comprising a lower alkyl tetritol ether represented by the following general formula (1) as an active ingredient. A-Rn (1) (A represents a tetritol residue excluding a hydrogen atom n;
Is an alkyl group having 1 to 4 carbon atoms, and may be any of a linear alkyl group, a branched alkyl group, an unsaturated alkyl group, and a hydroxyalkyl group. n represents the average degree of substitution of R;
Is a number in the range. ) 2. A skin roughness improving agent comprising the lower alkyl tetritol ether according to claim 1 as an active ingredient. 3. An external preparation for skin, comprising the lower alkyl tetritol ether according to claim 1.