JPH06157276A - Skin external preparation - Google Patents

Abstract

PURPOSE:To obtain a skin external preparation containing a specific amine derivative (acid additional salt) and a specific amide derivative, excellent in ability capable of retaining water content of corneum and effect capable of preventing and treating chapped skin and useful for cosmetics, creams, etc. CONSTITUTION:The skin external preparation contains (A) preferably 0.001-2wt.% one or two or kinds of compounds selected from amine derivatives expressed by formula I [R<1> is 4-40C hydrocarbon; R<2> to R<6> are H or 1-10C hydrocarbon; X is O or COO (carbonyl is bound to R<1>)] and its acid additional salt and (B) preferably 0.1-20wt.% one or two or more kinds of compounds expressed by formula II [R<7> is 10-26C hydrocarbon; R<8> is 9-25C hydrocarbon; Y and Z are H or (CH2)nOH [(n) is 1-3]; A is single bond or O-CH2].

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a skin external preparation, and more particularly to a skin external preparation for enhancing the water-retaining ability of the stratum corneum to prevent and improve rough skin.

[0002]

2. Description of the Related Art Generally, it is known that the water content in the stratum corneum is important in order to moisturize the skin and maintain flexibility. Further, in order to retain the water, a water-soluble component contained in the stratum corneum, that is, free amino acid,
It is also known that organic acids, urea, inorganic ions, etc. contribute, and conventionally, a medicated external preparation for skin or a cosmetic containing these water-soluble components alone or in combination is used for the purpose of improving or preventing rough skin. Used in.

In addition to the water-soluble components contained in the stratum corneum, various moisturizing substances having a high affinity with water have been developed and used for the same purpose.

However, when a conventional water-soluble component or moisturizing substance is applied to the skin, its effect is that it exists on the skin keratin and supplies water to the keratin, and its effect is temporary and fundamental. To improve the water retention capacity of the stratum corneum,
It did not essentially prevent or heal skin irritation.

[0005]

Therefore, there has been a demand for the development of an external preparation for the skin which can fundamentally improve the water-retaining ability of the stratum corneum and essentially prevent and cure rough skin.

[0006]

Therefore, the present applicant has been investigating to find a compound that fundamentally improves the water-retaining ability of the stratum corneum, and the following general formula (2 ')

[0007]

[Chemical 3]

[0008] wherein, R ⁹ represents a linear or branched, saturated or unsaturated hydrocarbon group of 10-26 carbon atoms, R ¹⁰ is a saturated or a straight-chain or branched-chain 9 to 25 carbon atoms It was found that the water retention ability of the stratum corneum can be improved by using an amide derivative represented by [showing an unsaturated hydrocarbon group] as a moisturizing agent, and filed previously (Patent No. 1557842).

However, in recent years, it has been desired to further improve the rough skin improving effect, and the present inventors have studied various compounds. As a result, the amine derivative represented by the following general formula (1) or its acid addition salt is shown. It has been found that, when used in combination with an amide derivative represented by the general formula (2) described below, a skin external preparation that further improves the water retention capacity of the stratum corneum and has an extremely excellent effect of preventing and improving rough skin is obtained. The present invention has been completed.

That is, the present invention comprises the following components (A) and (B) (A) the following general formula (1)

[0011]

[Chemical 4]

[In the formula, R ¹ represents a linear, branched or cyclic hydrocarbon group having 4 to 40 carbon atoms which may be substituted with a hydroxyl group, and R ² , R ³ , R ⁴ , R ⁵ and R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with one or more hydroxyl groups, and X represents —O—
Or ^one or more selected from an amine derivative represented by —CO—O— (wherein a carbonyl group is bonded to R ¹ ) and an acid addition salt thereof (B) the following general formula (2)

[0013]

[Chemical 5]

[In the formula, R ⁷ represents a linear or branched saturated or unsaturated hydrocarbon group having 10 to 26 carbon atoms, and R ⁸ represents a linear or branched saturated or unsaturated hydrocarbon group having 9 to 25 carbon atoms. Represents an unsaturated hydrocarbon group, and Y and Z are each a hydrogen atom or-
(CH ₂ ) _n —OH (where n represents a number of 1 to 3), A represents a single bond or —O—CH ₂ — (where an oxygen atom is bonded to R ³ )]. The present invention provides a skin external preparation characterized by containing one or more selected from the represented amide derivatives.

In the amine derivative represented by the general formula (1) which is the component (A) used in the present invention, R ¹ is a straight chain, branched chain or cyclic group having 4 to 40 carbon atoms which may be substituted with a hydroxyl group. Shows a saturated or unsaturated hydrocarbon group of
Specific examples thereof include butyl group, hexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, pentadecyl group, hexadecyl group, octadecyl group, docosyl group, dotriacontyl group, methyl-branched isostearyl group, 2-ethylhexyl group, Alkyl groups such as 2-heptylundecyl group and 5,7,7-trimethyl-2- (1,3,3-trimethylbutyl) -octyl group; 9-octadecenyl, 9,12-octadecadienyl group and the like Examples thereof include alkenyl groups; alicyclic hydrocarbon groups such as cyclohexyl groups; aromatic hydrocarbon groups such as phenyl groups and benzyl groups; and hydrocarbon groups such as cholesteryl groups. In addition, R ² , R ³ ,
R ⁴ , R ⁵ and R ⁶ are each a hydrogen atom or have 1 to 10 carbon atoms which may be substituted with one or more hydroxyl groups.
The specific examples of the hydrocarbon groups are hydrogen atom and methyl group, ethyl group, butyl group, hexyl group, phenyl group, benzyl group, hydroxymethyl group, hydroxyethyl group, 1,2-dihydroxyethyl group. , 1, 2, 3
And hydrocarbon groups such as trihydroxypropyl group, 1,2,3,4-tetrahydroxybutyl group, 1,2,3,4,5-pentahydroxypentyl group. Also,
X is -O- or -CO-O- (provided that the carbonyl group is R
Combined with ¹ ).

The amine derivative (1) in the present invention
Of these, X is -O-, and R ², R³, R^Four, R^Five
And R⁶Is an N-acyl derivative of
Intermediate for production of certain amide derivative [the above general formula (2 ')]
Known as (JP-A-62-228048).
Issue). However, regarding its own effects on the skin,
Was not known at all.

Amine derivative (1) used in the present invention
Is synthesized by various known methods. For example, it is synthesized by adding the amine derivative (4) to the glycidyl ether or ester derivative (3) according to the following reaction formula.

[0018]

[Chemical 6]

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶
And X have the same meaning as above]

The amine derivative (1) thus obtained is further subjected, if necessary, to an inorganic acid salt such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or the like, or succinic acid, fumaric acid, hexadecanoic acid, octadecane, according to a conventional method. It may be an organic acid salt such as acid, lactic acid, glycolic acid, citric acid, tartaric acid or benzoic acid.

In the present invention, the amine derivative as the component (A) and the acid addition salt thereof can be used alone or in combination of two or more, and the compounding amount is not particularly limited, but is 0 in the whole composition. 0.0001 to 10% by weight (hereinafter,
(Only shown in%), particularly 0.001 to 2% is preferable. If the blending amount is less than 0.0001%, the effect of the present invention is not sufficiently achieved, and if it exceeds 10%, further improvement of the effect is not recognized.

Further, in the amide derivative represented by the general formula (2) which is the component (B) used in the present invention, R
⁷ represents a linear or branched saturated or unsaturated hydrocarbon group having 10 to 26 carbon atoms, and specific examples thereof include a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, Hexadecyl group, octadecyl group, eicosyl group, docosyl group, tetracosyl group,
Alkyl groups such as pentacosyl group, hexacosyl group, 2-ethyloctyl group, 3-ethyloctyl group; alkenyl groups such as oleyl group, linoleyl group; alicyclic hydrocarbon groups such as anthracenyl group; diphenylmethyl group, naphthyl group, etc. The aromatic hydrocarbon group of Further, in the general formula (2), R ⁸ represents a linear or branched saturated or unsaturated hydrocarbon group having 9 to 25 carbon atoms, and specific examples thereof include a nonyl group and a 2-methyloctyl group. Alkyl groups such as;
An aromatic hydrocarbon group such as a mesityl group; and those having 25 carbon atoms among the above hydrocarbon groups.

The amide derivative (2) can be prepared by a known method [for example, Polish Journal of Chemistry (Pol. J. Chem.) 52 , 1059 (197).
8); ibid. 52 , 1283 (1978); JP-A-54-1.
No. 17421, No. 54-144308, No. 54-14
7937 gazette]. That is, it can be produced by acylating the compound (7) obtained from the glycidyl ether (5) and the alkanolamine (6) according to the reaction formula shown below, and then selectively hydrolyzing the ester group.

[0024]

[Chemical 7]

[Wherein R ⁷ , R ⁸ , Y and Z have the same meanings as described above, and Z'is Z when Z is-(CH ₂ ) _n -OH.
Represents an anion group excluding a hydrogen atom, and represents a single bond when Z is a hydrogen atom.]

Among these amide derivatives, particularly preferable are the following general formulas (2-a) and (2-b).
Is represented by.

[0027]

[Chemical 8]

[In the formula, R ⁷ and R ⁸ have the same meanings as described above.] In the present invention, the amide derivative of the component (B) can be used alone or in combination of two or more, and the combination thereof. The amount is not particularly limited, but 0.001 to 50%, particularly 0.1 to 20% is preferable in the entire composition.
If the blending amount is less than 0.01%, the effect of the present invention is not sufficiently achieved, and if it exceeds 20%, further improvement of the effect is not observed.

The skin external preparation of the present invention is roughly classified into a medicated skin external preparation and a cosmetic, depending on its use form.

Examples of the external medicated skin preparation include various ointments containing medicinal components. here,
As an ointment, those based on an oily base, oil /
It may be based on water or a water / oil type emulsion base. The oily base is not particularly limited, and examples thereof include vegetable oil, animal oil, synthetic oil, fatty acid and natural or synthetic glyceride. Further, the medicinal component is not particularly limited, and for example, an analgesic / anti-inflammatory agent, an antipruritic agent, a bactericidal disinfectant, an astringent agent, an emollient agent, a hormone agent and the like can be appropriately used as necessary.

As the cosmetics, various forms such as water / oil, oil / water emulsion cosmetics, creams, cosmetic emulsions,
Lotion, oily cosmetic, pack, lipstick, foundation, skin cleanser, hair tonic, hair styling agent, hair nourishing agent,
It can be a skin cosmetic such as a hair restorer.

When the external preparation for skin of the present invention is used as a cosmetic, in addition to the essential ingredients, oils, moisturizers, UV absorbers, alcohols, which are generally used as cosmetic ingredients,
A chelating agent, a pH adjuster, an antiseptic, a thickener, a dye, a fragrance and the like can be optionally combined and blended.

The external preparation for skin of the present invention is obtained by heating and dissolving the above-mentioned essential components (A) and (B) and other oil phase components, and optionally adding an aqueous phase component. In addition, it is preferable to manufacture by mixing.

[0034]

INDUSTRIAL APPLICABILITY The external preparation for skin of the present invention uses the amine derivative or its acid addition salt of the component (A) in combination with the amide derivative of the component (B) to synergistically improve the keratin water retention ability. It has an excellent effect of preventing and healing rough skin.

[0035]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. The evaluation method for the rough skin improving effect in this example is shown below.

(Test Method) Ten females aged 20 to 50 who have rough skin on the cheeks in winter are used as test subjects, and different skin external preparations are applied to the left and right cheeks for 2 weeks. On the day after the application for two weeks was completed, the following items were tested. (1) Skin conductance After washing the face with warm water of 37 ° C. and resting in a room at a temperature of 20 ° C. and a humidity of 40% for 20 minutes, the water content of the stratum corneum was measured with a skin conductance meter (IBS). .
The skin conductance value shows that the smaller the value, the rougher the skin is, and when the value is 5 or less, the rougher the skin is. On the other hand, if the skin conductance value is 20 or more,
Almost no rough skin has occurred. (2) Rough skin score Rough skin was visually observed and judged according to the criteria shown in Table 1 below. The score was shown by the average value +/- standard deviation.

[0037]

[Table 1]

Example 1 W / O type creams having the compositions shown below were prepared, and the effect of improving skin roughness by continuous application was evaluated for each of them.
The structure and blending amount of the amine derivative used are shown in Table 3, the structure and blending amount of the amide derivative are shown in Table 4, and the evaluation results of the rough skin improving effect are shown in Table 5.

[0039]

(Table 2) (Composition) (%) (1) Amine derivative (Table 3) Table 3 (2) Amide derivative (Table 4) Table 4 (3) Cholesterol 0.5 (4) Cholesteryl isostearate 1.0 ( 5) Polyether-modified silicone ^{* 1} 1.5 (6) Cyclic silicone ^{* 2} 20.0 (7) Methylphenylpolysiloxane ^{* 3} 2.0 (8) Methylpolysiloxane ^{* 4} 2.0 (9) Magnesium sulfate 0 .5 (10) 55% ethanol 5.0 (11) Purified water Remaining amount (12) Preservative proper amount (13) Perfume proper amount

* 1: Silicone KF-6015, Shin-Etsu Chemical Co., Ltd.
Made * 2: Silicone SH-244, SH-245 or SH
-244 and SH-245 3: 2 (weight ratio) mixture, manufactured by Toray Dow Corning Silicone Co., Ltd. * 3: Silicone SF-557, Toray Dow Corning
Silicone Co., Ltd. * 4: Silicone KF-96A (6cs), Shin-Etsu Chemical Co., Ltd.

(Production method) Oil phase component [(1) to (5),
(7), (8)] heated and dissolved at 80 ° C., and an aqueous phase component [(9), (1
1) and (12)] are added and emulsified, and after stirring and cooling to 50 ° C., (6), (10) and (13) are added, and the mixture is further cooled to room temperature with stirring to prepare a W / O cream. did.

[0042]

[Table 3]

[0043]

[Table 4]

[0044]

[Table 5]

Example 2 An O / W cream having the following composition was prepared. This improved the water retention capacity of the stratum corneum and was excellent in the effect of preventing and healing rough skin.

[0046]

(Table 6) (Composition) (%) (1) Polyoxyethylene (10) hydrogenated castor oil 1.0 (2) sorbitan monostearate 0.5 (3) sodium stearoylmethyl taurine 0.5 (4) cetostearyl Alcohol 2.0 (5) Stearic acid 1.8 (6) Amine derivative ^{* 5} 0.3 (7) Amide derivative ^{* 6} 3.0 (8) Cholesterol 1.5 (9) Cholesteryl isostearate 1.0 ( 10) Neopentyl glycol dicaprate 8.0 (11) Methylpolysiloxane ^{* 7} 5.0 (12) Glycerin 5.0 (13) 1,3-Butylene glycol 3.0 (14) Preservative A suitable amount (15) Purification Remaining amount of water (16) Perfume proper amount

[0047]

[Chemical 9]

(Manufacturing method) To an oil phase component [(1) to (11)] heated and dissolved at 80 ° C, an aqueous phase component [(12) to (15)] heated to 80 ° C with stirring was added. After emulsifying, stir and cool to 50 ° C, then add (16),
The mixture was further cooled to room temperature with stirring to prepare an O / W cream.

Example 3 An ointment having the following composition was prepared. This improved the water retention capacity of the stratum corneum and was excellent in the effect of preventing and healing rough skin.

[0050]

[Table 7] (Composition) (%) (1) Amine derivative ^{* 8} 1.0 (2) Amide derivative ^{* 9} 6.0 (3) White petrolatum remaining (4) Cholesteryl isostearate 3.0 (5) Liquid paraffin 10.0 (6) Glyceryl ether ^{* 10} 1.0 (7) Glycerin 10.0

[0051]

[Chemical 10]

(Production method) (1) to (7) were heated and dissolved, and then cooled to prepare an ointment.

Example 4 An O / W cream having the following composition was prepared. This improved the water retention capacity of the stratum corneum and was excellent in the effect of preventing and healing rough skin.

[0054]

[Table 8] (Composition) (%) (1) Polyoxyethylene (10) hydrogenated castor oil 1.0 (2) sorbitan monostearate 0.5 (3) sodium stearoylmethyl taurine 0.5 (4) cetostearyl Alcohol 2.0 (5) Stearic acid 1.8 (6) Amine derivative ^{* 11} 0.3 (7) Amide derivative ^{* 12} 3.0 (8) Cholesterol 1.5 (9) Cholesteryl isostearate 1.0 ( 10) Neopentyl glycol dicaprate 8.0 (11) Methyl polysiloxane ^{* 13} 5.0 (12) Glycerin 5.0 (13) 1,3-Butylene glycol 3.0 (14) Preservatives Amount (15) Purification Remaining amount of water (16) Perfume proper amount

[0055]

[Chemical 11]

(Manufacturing method) To an oil phase component [(1) to (11)] heated and dissolved at 80 ° C, an aqueous phase component [(12) to (15)] heated to 80 ° C with stirring was added. After emulsifying, stir and cool to 50 ° C, then add (16),
The mixture was further cooled to room temperature with stirring to prepare an O / W cream.

Claims (1)

[Claims] 1. The following components (A) and (B) (A) having the following general formula (1): [In the formula, R ¹ has 4 carbon atoms which may be substituted with a hydroxyl group.
To 40 linear, branched or cyclic hydrocarbon groups, R
² , R ³ , R ⁴ , R ⁵ and R ⁶ are each a hydrogen atom or 1
Alternatively, it represents a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with two or more hydroxyl groups, and X is -O- or -CO-.
O- (provided that the carbonyl group is bonded to R ¹ )]
One or more selected from amine derivatives and acid addition salts thereof represented by (B) the following general formula (2): [In the formula, R ⁷ represents a linear or branched saturated or unsaturated hydrocarbon group having 10 to 26 carbon atoms, and R ⁸ represents 9 to 2 carbon atoms.
5 represents a linear or branched, saturated or unsaturated hydrocarbon group, Y and Z are each a hydrogen atom or a - (CH _{2) n} -O
H (where n is a number of 1 to 3) indicates, A represents a single bond or -O-CH ₂ - (provided that the oxygen atom binds to R ³⁾
The external preparation for skin comprising one or more selected from amide derivatives represented by