JP6845650B2 - An oil composition containing a mixture of fatty acid alkanolamide derivatives and a cosmetic containing the same. - Google Patents

Description

The present invention relates to an oil composition optimized for obtaining a cosmetic having a moist feel, a good feeling in use, and excellent stability, and a cosmetic using the same.

In recent years, cosmetics such as milky lotions and creams for the purpose of skin conditioning have been used with a wetting agent such as polyhydric alcohol for the purpose of suppressing water evaporation from the skin and hydrocarbon oil for suppressing water evaporation. , Ester oil, etc. are blended. In addition, the self-milk type bath salt contains a liquid oil agent as an emollient agent for the skin for the purpose of making the bath water milky cloudy, and the conditioners used for hair contain an oil agent as a conditioning agent. There is.

As these oils, liquidity at room temperature is required from the viewpoint of formulation stability, and highly unsaturated triglycerides such as grape seed oil and almond oil, hydrocarbon oils, synthetic ester oils, etc. have been widely used. ..

For the purpose of increasing the water holding capacity of the oil agent, the formulation of lanolin derivatives in the oil agent and the development of amino acid-based derivatives as highly safe oil-based raw materials have also been disclosed (Patent Documents 1 and 2), and fatty acid sterol esters and sterols are specified. A technique relating to a composition for imparting water retention to cosmetics used for skin, scalp and hair mixed in proportion is disclosed. (Patent Document 3)

Further, regarding a mixture of fatty acid alkanolamide derivatives, a multi-chain type highly polar oil agent having a high affinity for hair and skin has been studied (Patent Document 4).

Special Publication No. 54-12908 Special Publication No. 56-12609 Japanese Unexamined Patent Publication No. 2015-040199 Japanese Patent Application No. 2015-078779

However, many of the conventional oils have a weak moist feeling after application and feel oily. In addition, since it is an oil component, there is a problem that separation from a water-soluble component is likely to occur. That is, until now, an oil composition and a cosmetic composition containing an oil that can sufficiently satisfy both the usability / stability of the product have not been developed.

As a result of studies to solve the above problems, the present inventor has found that an oil composition obtained by blending a liquid oil with a mixture of fatty acid alkanolamide derivatives gives a moist feel while suppressing oiliness after skin application. It has been found that cosmetics that can be given and that contain the oil composition have improved stability.
That is, the present invention

［但し、式（１）中 Ｒ^１は炭素数７〜２１の炭化水素鎖を示し、それらの混合物でも良い
Ｒ^２は水素原子、乃至は一般式（２）の置換基を示し、
Ａは水素原子、メチル基、又は −ＣＨ_２ＣＨ_２Ｏ−Ｒ^３基を示し、
Ｒ^３は、水素原子又は一般式（２）の置換基を示し、
Ｒ^２及びＡ、Ｒ^２及びＲ^３が同時に水素原子である場合は除く。］

［但し、式（２）中 Ｒ^４は炭素数７〜２１の炭化水素鎖を示し、それらの混合物でも良い
ｐは０乃至は１の整数を示す。］
（Ｂ）常温で液状の油剤からなり
成分Ｂと成分Ａが重量比で５：５〜９：１の間であることを特徴とする油剤組成物に関する (A) A mixture of fatty acid alkanolamide derivatives represented by the structure of the general formula (1) and

[However, in formula (1), R ¹ represents a hydrocarbon chain having 7 to 21 carbon ^{atoms, and R 2} , which may be a mixture thereof, represents a hydrogen atom or a substituent of the general formula (2).
A represents a hydrogen atom, a methyl group, or -CH ₂ CH ₂ ^{OR 3} groups.
R ³ represents a hydrogen atom or a substituent of the general formula (2).
Excludes cases where R ² and A, R ² and R ³ are hydrogen atoms at the same time. ]

[However, in formula (2), R ⁴ represents a hydrocarbon chain having 7 to 21 carbon atoms, and p, which may be a mixture thereof, represents an integer of 0 to 1. ]
(B) The present invention relates to an oil composition composed of an oil that is liquid at room temperature, wherein the component B and the component A have a weight ratio of 5: 5 to 9: 1.

［但し、Ｒ^１は炭素数７〜２１の炭化水素鎖を示し、それらの混合物でも良い
Ｒ^２は水素原子、乃至は一般式（２）の置換基を示し、
Ｒ^３は、水素原子又は一般式（２）の置換基を示し、
Ｒ^２及びＲ^３が同時に水素原子である場合は除き、式（３）１当量に対してＲ^２、Ｒ^３
に導入される式（２）の置換基の導入が１．２５当量から１．８０当量の間である。］ The fatty acid alkanolamide derivative mixture is preferably a fatty acid alkanolamide derivative mixture represented by the general formula (3).

[However, R ¹ indicates a hydrocarbon chain having 7 to 21 carbon ^{atoms, and R 2} which may be a mixture thereof indicates a hydrogen atom or a substituent of the general formula (2).
R ³ represents a hydrogen atom or a substituent of the general formula (2).
When R ² and ^{R 3} are hydrogen atoms at the same time except, ^R 2, ^{R 3} for Formula (3) 1 equivalent of
The introduction of the substituent of the formula (2) introduced into is between 1.25 equivalents and 1.80 equivalents. ]

Further, it is more preferable that the oil agent liquid at room temperature is selected from one or more selected from hydrocarbon oils, silicone oils, synthetic ester oils, and vegetable oils.
The present invention also relates to a self-emulsifying bath agent, a milky lotion cosmetic, a hair conditioner cosmetic, a lotion cosmetic, and a cream cosmetic containing the above-mentioned oil composition of the present invention.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an oil composition capable of giving a moist feel while suppressing oiliness after application, and a cosmetic containing the oil composition and having improved stability.

Figure 1 is a photograph of the emulsion emulsion prototyped in Table 3.

［但し、式（１）中 Ｒ^１は炭素数７〜２１の炭化水素鎖を示し、それらの混合物でも良い
Ｒ^２は水素原子、乃至は一般式（２）の置換基を示し、
Ａは水素原子、メチル基、又は −ＣＨ_２ＣＨ_２Ｏ−Ｒ^３基を示し、
Ｒ^３は、水素原子又は一般式（２）の置換基を示し、
Ｒ^２及びＡ、Ｒ^２及びＲ^３が同時に水素原子である場合は除く。］

［但し、式（２）中 Ｒ^４は炭素数７〜２１の炭化水素鎖を示し、それらの混合物でも良い
ｐは０乃至は１の整数を示す。］ Hereinafter, embodiments of the present invention will be described.
The fatty acid alkanolamide derivative mixture of the essential component (A) of the oil composition of the present invention will be described.
The fatty acid alkanolamide derivative mixture of the present invention comprises a compound mixture represented by the structure of the general formula (1).

[However, in formula (1), R ¹ represents a hydrocarbon chain having 7 to 21 carbon ^{atoms, and R 2} , which may be a mixture thereof, represents a hydrogen atom or a substituent of the general formula (2).
A represents a hydrogen atom, a methyl group, or -CH ₂ CH ₂ ^{OR 3} groups.
R ³ represents a hydrogen atom or a substituent of the general formula (2).
Excludes cases where R ² and A, R ² and R ³ are hydrogen atoms at the same time. ]

[However, in formula (2), R ⁴ represents a hydrocarbon chain having 7 to 21 carbon atoms, and p, which may be a mixture thereof, represents an integer of 0 to 1. ]

The mixture of the general formula (1) can be easily obtained by heat-dehydrating the fatty acid alkanolamide and the acylamino acid. As a combination of the fatty acid alkanolamide used and the acyl amino acid,
Fatty acid diethanolamide and acylmethyl β-alanine,
Fatty acid monoethanolamide and acylmethyl β-alanine,
Fatty acid methyl ethanolamide and acyl methyl β-alanine,
Fatty acid diethanolamide and acyl hydroxyethyl β-alanine,
Fatty acid monoethanolamide and acyl hydroxyethyl β-alanine,
Fatty acid methyl ethanolamide and acyl hydroxyethyl β-alanine,
Fatty acid diethanolamide and acylmethylglycine,
Fatty acid monoethanolamide and acylmethylglycine,
A combination of fatty acid methyl ethanolamide and acyl methyl glycine is exemplified.

The fatty acid alkanolamide derivative represented by the general formula (1) can be obtained by heat-dehydrating N-acylamino acids equal to or more than the fatty acid alkanolamide.
Examples of fatty acid alkanolamides include lauric acid diethanolamide, lauric acid myristic acid diethanolamide, stearate diethanolamide, oleate diethanolamide, coconut oil fatty acid diethanolamide, palm kernel oil fatty acid diethanolamide, modified coconut oil fat diethanolamide, and coconut oil. Examples thereof include fatty acid methylethanolamide, coconut oil fatty acid monoethanolamide, stearic acid monoethanolamide, lauric acid monoisopropanolamide and lauric acid N-methylethanolamide, and more preferable compounds are diethanolamine derivatives such as lauric acid diethanolamide and lauric acid. Examples thereof include myristic acid diethanolamide, stearic acid diethanolamide, coconut oil fatty acid diethanolamide, and palm kernel oil fatty acid diethanolamide, and lauric acid diethanolamide and coconut oil fatty acid diethanolamide are particularly preferable.

［但し、Ｒ^１は炭素数７〜２１の炭化水素鎖を示し、それらの混合物でも良い
Ｒ^２は水素原子、乃至は一般式（２）の置換基を示し、
Ｒ^３は、水素原子又は一般式（２）の置換基を示し、
Ｒ^２及びＲ^３が同時に水素原子である場合は除き、式（３）１当量に対してＲ^２、Ｒ^３
に導入される式（２）の置換基の導入が１．２５当量から１．８０当量の間である。］ Among the fatty acid alkanolamide derivative mixture represented by the structure of the general formula (1), fatty acid diethanolamide and acylmethylglycine or acylmethyl β-alanine are used as raw materials with respect to 1 equivalent of fatty acid alkanolamide, and acylmethylglycine or acylmethyl β-alanine. The fatty acid alkanolamide derivative mixture mixture represented by the general formula (3) obtained by reacting 1.25 equivalents to 1.80 equivalents is more preferable because a better feeling of use can be obtained.

[However, R ¹ indicates a hydrocarbon chain having 7 to 21 carbon ^{atoms, and R 2} which may be a mixture thereof indicates a hydrogen atom or a substituent of the general formula (2).
R ³ represents a hydrogen atom or a substituent of the general formula (2).
When R ² and ^{R 3} are hydrogen atoms at the same time except, ^R 2, ^{R 3} for Formula (3) 1 equivalent of
The introduction of the substituent of the formula (2) introduced into is between 1.25 equivalents and 1.80 equivalents. ]

Next, the essential component (B) of the oil composition of the present invention, which is liquid at room temperature, will be described.
Preferred examples include hydrocarbon oils, silicone oils, synthetic ester oils, liquid vegetable oils and the like.
As the hydrocarbon oil, for example, liquid paraffin, squalane, squalene, paraffin, isoparaffin, selecin and the like can be used. It is preferable that it consists of one kind or a combination of two or more kinds selected from.
Examples of the silicone oil include chain silicones such as dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane, and cyclic silicones such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. Can be mentioned.
Preferable examples of the synthetic ester oil include isopropyl myristate, octyldodecyl myristate and the like.
Liquid vegetable oils include flaxseed oil, camellia oil, macadamia nut oil, grape seed oil, corn oil, mink oil, olive oil, avocado oil, southern ka oil, sunflower oil, saflower oil, sunflower oil, almond oil, rapeseed oil, sesame oil, Preferable examples include soybean oil and peanut oil.

In the oil composition of the present invention, the component A composed of the component B of the oil that is liquid at room temperature and the mixture of the fatty acid alkanolamide derivative is preferably in a weight ratio of 5: 5 to 9: 1.
When the mixing ratio of component B and component A is less than 9: 1 and the blending amount of component A is small, the effect of adding component A (water embrace, affinity of the oil agent on the skin, droplets at the time of emulsification) Miniaturization, stability during solubilization, etc.) are not improved and are not preferable, and when the component A is blended in an amount exceeding 5: 5, the effect of adding the component A to the liquid oil agent is maintained, but it is not economical.

As a use of the oil composition of the present invention, a cosmetic which is a dosage form of a self-emulsifying bath salt will be described.
The self-emulsifying bath agent is an oil composition having a uniform appearance in which a nonionic surfactant of HLB 8 to 11 is mixed with a liquid oil agent. When added to a large amount of water (warm water), the oil composition is emulsified by the nonionic surfactant in the component, and the water (warm water) becomes cloudy.
It is necessary to match the mixed HLB of the nonionic surfactant according to the required HLB of the oil composition.

The required HLB of the oil composition of the present invention varies depending on the compounding composition, but is usually between 8 and 11, and one or more nonionic surfactants are used to adapt to this. The blending amount of each component in the self-emulsifying bath salt is preferably 95 to 80% by weight of the oil composition of the present invention and 5 to 20% by weight of the nonionic surfactant. If the nonionic surfactant is blended in an amount of more than 20% by weight, there is a problem that the whiteness is insufficient when the nonionic surfactant is added to water (warm water) due to solubilization of a part of the oil agent, which is not preferable. ..

By blending the oil composition of the present invention with a self-emulsifying bath salt, the cloudiness after adding water (warm water) does not separate even in the next morning, and the moist feeling after bathing is increased. ..
Examples of the nonionic surfactant to be used include polyoxyethylene glyceryl triisostearate, polyoxyethylene alkyl ether, and polyoxyethylene sorbitan esters.

As a use of the oil composition of the present invention, a cosmetic which is a dosage form of a milky lotion cosmetic will be described.
The emulsion is solubilized by adding 1 to 10% by weight of a nonionic surfactant to the oil phase component, that is, 2 to 10% by weight of the oil agent of the present invention, and may contain an aqueous phase component, that is, a polyol, purified water (residue). ) Is heated and the oil phase component is mixed with the agitated aqueous phase component to prepare a cosmetic consisting of an O / W type emulsion.

By blending the oil composition of the present invention into an emulsion cosmetic, the emulsion stability of the emulsion itself is improved, the emulsion is well-adapted to the skin, and the moist feeling is enhanced.
Preferable examples of nonionic surfactants used in emulsion cosmetics include ether-type surfactants such as glycerin ether and its alkylene oxide adduct, higher alcohol alkylene oxide adduct, glycerin ester and its alkylene oxide adduct, and the like. Ester-type surfactants, ether-type surfactants such as sorbitan ester and its alkylene oxide adduct, polyoxyalkylene fatty acid ester, glycerin ester, fatty acid polyglycerin ester, sorbitan ester, sucrose fatty acid ester and other ester-type surfactants. Nitrogen-containing nonionic surfactants such as activators, alkyl glucosides, hardened castor oil pyroglutamic acid diesters and their ethylene oxide adducts, and fatty acid alkanolamides, (Acrylate / alkyl acrylate (C10-30)) crosspolymers. Examples of the nonionic activator are particularly preferable, such as ether-type surfactants such as glycerin ether and its alkylene oxide adduct, alkylene oxide adduct of higher alcohol, glycerin ester and its alkylene oxide adduct. Examples thereof include ester-type surfactants, ether ester-type surfactants such as sorbitan esters and alkylene oxide adducts thereof, and polyoxyalkylene fatty acid esters.

As a use of the oil composition of the present invention, a cosmetic which is a dosage form of a hair conditioner cosmetic will be described.
Hair conditioner cosmetics are prepared by adding 0.5 to 10% by weight of a cationic surfactant, which is an essential component, to an oil phase component, that is, 0.1 to 5.0% by weight of the oil of the present invention, and heating and solubilizing the oil. It is a liquid cosmetic composed of an O / W type emulsion produced by heating purified water (residual) which may contain a phase component, that is, a polyol, and mixing an oil phase component with a stirred aqueous phase component.

By blending the oil composition of the present invention into a hair conditioner cosmetic, the emulsification stability of the hair conditioner itself is improved, the hair is well-adapted to the hair, and the moist feeling is increased.
Preferable examples of the cationic surfactant used in hair conditioner cosmetics include behenyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, guahydroxypropyltrimonium chloride and the like.

As a use of the oil composition of the present invention, a cosmetic which is a dosage form of a lotion cosmetic will be described.
Toner cosmetics are purified water (residual) which may contain a polyol by adding 0.5 to 10% by weight of a nonionic surfactant to an oil phase component, that is, 0.5 to 10% by weight of the oil agent of the present invention. ) Is a cosmetic consisting of a heated transparent solution.
By blending the oil composition of the present invention into a cosmetic, the stability of the lotion itself is improved, the skin is well-adapted to the skin, and the moist feeling is increased.

Preferable examples of nonionic surfactants used in cosmetics are ether-type surfactants such as glycerin ether and its alkylene oxide adduct and higher alcohol alkylene oxide adduct, glycerin ester and its alkylene oxide adduct. Such as ester-type surfactants, ether ester-type surfactants such as sorbitan ester and its alkylene oxide adduct, polyoxyalkylene fatty acid ester, glycerin ester, fatty acid polyglycerin ester, sorbitan ester, sucrose fatty acid ester and the like ester type. Surfactants, alkyl glucosides, hardened castor oil pyroglutamic acid diester and ethylene oxide adducts thereof, and nitrogen-containing nonionic surfactants such as fatty acid alkanolamide are mentioned, and particularly preferable nonionic surfactants include glycerin ether and glycerin ether. Ether-type surfactants such as the alkylene oxide adduct and alkylene oxide adducts of higher alcohols, ester-type surfactants such as glycerin ester and its alkylene oxide adduct, ether ester type such as sorbitan ester and its alkylene oxide adduct Examples thereof include surfactants, polyoxyalkylene fatty acid esters, polyoxyethylene hydrogenated castor oil, and castor oil derivatives such as polyoxyethylene castor oil.

As a use of the oil composition of the present invention, a cosmetic which is a dosage form of a cream cosmetic will be described.
Cream cosmetics have 1 to 15% by weight of solid oil and 0.5 to 15% by weight of nonionic surfactant as essential components with respect to the oil phase component, that is, 0.1 to 10.0% by weight of the oil of the present invention. In addition, it is produced by heating and solubilizing, heating purified water (residual) which may contain an aqueous phase component, that is, a polyol, and mixing an oil phase component with the aqueous phase component under stirring. The form of emulsification can be adjusted from O / W to W / O by selecting a nonionic surfactant, but is characterized by having a gel-paste-like appearance at room temperature.
Preferable examples of the solid oil at room temperature, which is an essential component for producing a cream cosmetic using the oil composition of the present invention, include cetostearyl alcohol, behenyl alcohol, stearyl alcohol, and stearic acid.

By blending the oil composition of the present invention into a cream cosmetic, the emulsification stability of the cream itself is improved, the cream itself is well-adapted to the skin, and the moist feeling is increased.
Preferable examples of nonionic surfactants used in cream cosmetics include ether-type surfactants such as glycerin ether and its alkylene oxide adduct, higher alcohol alkylene oxide adduct, glycerin ester and its alkylene oxide adduct, and the like. Ester-type surfactants, ether-type surfactants such as sorbitan ester and its alkylene oxide adduct, polyoxyalkylene fatty acid ester, glycerin ester, fatty acid polyglycerin ester, sorbitan ester, sucrose fatty acid ester and other ester-type surfactants. Nitrogen-containing nonionic surfactants such as activators, alkyl glucosides, hardened castor oil pyroglutamic acid diesters and their ethylene oxide adducts, and fatty acid alkanolamides, (Acrylate / alkyl acrylate (C10-30)) crosspolymers. Examples of particularly preferable nonionic activators include glycerin ethers and ether-type surfactants such as alkylene oxide adducts of higher alcohols, and esters such as glycerin esters and alkylene oxide adducts thereof. Examples thereof include ether ester-type surfactants such as type surfactants, sorbitan esters and alkylene oxide adducts thereof, and polyoxyalkylene fatty acid esters.

The effects of the present invention will be described in more detail with reference to the following examples.
According to Synthesis Examples 1 to 15, various fatty acid alkanolamide derivative mixtures, which are essential components of the present invention, were produced, and evaluation tests were carried out using them as samples.

Synthesis example 1
In a flask, 28.65 g (95.3 mmol) of coconut oil fatty acid diethanolamide and 42.69 g (143 mmol, 1.5 equiv.) Of N-coconut oil fatty acid-N-methyl-β-alanine were heated to 130 ° C. and under reduced pressure for 7 hours. The esterification reaction was carried out by allowing the dehydration reaction. A theoretical amount of water was distilled off, and the O, O'-bis (N-coconut oil fatty acid-N-methyl-β-alanine) ester of this esterified coconut oil fatty acid diethanolamide and O- (N-coconut oil) A mixture of fatty acid-N-methyl-β-alanine) esters was obtained in an amount of 61.64 g.
^The structure was determined by 1 H NMR.
¹ H NMR chemical shift: 0.9ppm (7.5H m), 1.3ppm (42H m), 1.6ppm (5H m), 2.28-2.30ppm (5H t), 2.7ppm (2.5H t), 3.05ppm (4.5H) t), 3.6ppm (7.5H m), 3.8ppm (1H m), 4.2ppm (4H t)

Synthesis example 2
In a flask, 90.00 g (300 mmol) of coconut oil fatty acid diethanolamide and 93.90 g (315 mmol, 1.05 equiv.) Of N-coconut oil fatty acid-N-methyl-β-alanine are heated to 130 ° C. and dehydrated under reduced pressure for 7 hours. The esterification reaction was carried out. A theoretical amount of water was distilled off to obtain 165.65 g of an O- (N-coconut oil fatty acid-N-methyl-β-alanine) ester of coconut oil fatty acid diethanolamide, which is a monoesterified product.
^The structure was determined by 1 H NMR.
¹ H NMR chemical shift: 0.9ppm (6H m), 1.3ppm (33H m), 1.6ppm (4H m), 2.28-2.30ppm (4H t), 2.6-2.7ppm (2H t), 3.05ppm (2H t) ), 3.6ppm (6H m), 3.8ppm (2H m), 4.2ppm (2H t)

Synthesis example 3
In a flask, 90.00 g (300 mmol) of coconut oil fatty acid diethanolamide and 183.36 g (615 mmol, 2.05 equiv.) Of N-coconut oil fatty acid-N-methyl-β-alanine are heated to 130 ° C. and dehydrated under reduced pressure for 12 hours. The esterification reaction was carried out. A theoretical amount of water was distilled off to obtain 256.70 g of this diesterified O, O'-bis (N-coconut oil fatty acid-N-methyl-β-alanine) ester of ethanolamide at the time of coconut oil fatty acid.
^The structure was determined by 1 H NMR.
¹ H NMR chemical shift: 0.9ppm (9H m), 1.3ppm (55H m), 1.6ppm (6H m), 2.25 to 2.35ppm (6H t), 2.6-2.7ppm (4H t), 3.05ppm (8H t) ), 3.6ppm (8H m), 4.2ppm (4H t).

Synthesis example 4 (LDE-ALA 1 / 1.5)
In a flask, lauric acid diethanolamide (Kawaken Fine Chemical Co., Ltd. Amizole LDE-G) 30.05 g (100 mmol) and N-lauroyl-N-methyl-β-alanine (Kawaken Fine Chemical Co., Ltd. Alanon ALA) 42.81 g (150 mmol, 1.50) Equiv.) Was reduced to 2 kPa and heated at 125-130 ° C for 9 hours. A theoretical amount of water was distilled off, and the O, O'-bis (N-lauroyl-N-methyl-β-alanine) ester of this condensate, lauric acid diethanolamide, and O- (N-lauroyl-N-methyl) 63.41 g of a mixture of −β-alanine) esters was taken up. After allowing to cool, the structure of the product was determined by 1H-NMR.
¹ H NMR chemical shift: 0.9ppm (7.5H, m), 1.3ppm (41H, m), 1.6ppm (5H, m), 2.3-2.4ppm (5H, m), 2.6-2.7ppm (2.5H, m) ), 2.9-3.1ppm (3H, m), 3.6ppm (7.5H, m), 4.2ppm (2H m)

Synthesis Example 5 (LME + ALA)
In a flask, 24.35 g (100 mmol) of lauric acid monoethanolamide (Amidol LME, Kawaken Fine Chemical Co., Ltd.) and 29.97 g (105 mmol, 1.05 equiv.) Of N-lauroyl-N-methyl-β-alanine were reduced to 2 kPa. It was heated at 130 ° C. for 6 hours. A theoretical amount of water was distilled off, and 51.5 g of this condensate, an O- (N-lauroyl-N-methyl-β-alanine) ester of lauric acid monoethanolamide, was taken up.
The structure was determined by 1H-NMR.
¹ H NMR chemical shift: 0.9ppm (6H, m), 1.3ppm (32H, m), 1.5ppm (4H. M), 2.1ppm (2H, t), 2.3ppm (2H, t), 2.7ppm (2H) , T), 3.3ppm (2H, t), 3.5ppm (3H, s), 3.6ppm (2H, t), 4.1ppm (2H, t).

Synthesis Example 6 (lauric acid-N-methylethanolamide + ALA)
In a flask, 25.74 g (100 mmol) of methyl laurate ethanolamide derived from laurate chloride and methylethanolamine and 28.55 g (100 mmol, 1.0 equiv.) Of N-lauroyl-N-methyl-β-alanine were reduced to 2 kPa. , Heated at 130 ° C. for 7 hours. A theoretical amount of water was distilled off, and 48.31 g of an O- (N-lauroyl-N-methyl-β-alanine) ester of this condensate of methyl laurate was taken up.
The structure was determined by 1H-NMR.
¹ H NMR chemical shift: 0.9ppm (6H, m), 1.3ppm (32H, m), 1.5ppm (4H, m), 2.3ppm (4H, m), 2.7ppm (2H, t), 3.5ppm (8H) , m), 3.6ppm (2H, t), 4.5ppm (2H, t).

Synthesis Example 7 (LDE + SLA = 1: 2)
28.74 g (100 mmol) of diethanolamide laurate and 54.22 g (200 mmol, 2.0 equiv.) Of N-lauroyl-N-methyl-glycine (Soipon SLA, Kawaken Fine Chemical Co., Ltd.) were reduced to 2 kPa in a flask at 130 ° C. Heated for 10 hours. A theoretical amount of water was distilled off, and 68.54 g of an O, O'-bis (N-lauroyl-N-methyl-glycine) ester of this condensate, diethanolamide laurate, was taken up.
The structure was determined by 1H-NMR.
¹ H NMR chemical shift: 0.9ppm (9H, m), 1.3ppm (48H, m), 1.5ppm (6H, m), 2.3ppm (6H, m), 3.5ppm (8H, m), 4.5ppm (4H) , m), 4.9ppm (4H, s).

Synthesis Example 8 (LME + SLA = 1/1)
In a flask, 24.34 g (100 mmol) of monoethanolamide lauric acid and 27.15 g (100 mmol, 1.0 equiv.) Of N-lauroyl-N-methyl-glycine were reduced to 2 kPa and heated at 120 ° C. for 5 hours. A theoretical amount of water was distilled off, and 46.68 g of this condensate, an O- (N-lauroyl-N-methyl-glycine) ester of lauric acid monoethanolamide, was taken up.
The structure was determined by 1H-NMR.
¹ H NMR chemical shift: 0.9ppm (6H, m), 1.3ppm (32H, m), 1.5ppm (4H, m), 2.1ppm (2H, t), 2.3ppm (2H, t), 3.3ppm (2H) , T), 3.5ppm (3H, s), 4.1ppm (2H, t), 4.9ppm (2H, s).

Synthesis example 9 (CDE + ALA = 1 / 1.5)
In a flask, 30.05 g (100 mmol) of coconut oil fatty acid diethanolamide and 42.80 g (150 mmol, 1.5 equiv.) Of N-lauroyl-N-methyl-β-alanine were reduced to 2 kPa and heated at 135 ° C. for 7 hours. The theoretical amount of water was distilled off, and the esterified coconut oil fatty acid diethanolamide O, O'-bis (N-lauroyl-N-methyl β-alanine) ester and O- (N-lauroyl-N-methyl-β) 64.53 g of a mixture of −alanine) esters was taken up.
The structure was determined by 1H-NMR.
¹ H NMR chemical shift: 0.9ppm (7.5H, m), 1.3ppm (42H, m), 1.6ppm (5H, m), 2.3ppm (5H, m), 3.5ppm (10H, m), 4.5ppm ( 5H, m), 4.9ppm (5H, s).

Synthesis Example 10 (CDE + SLA = 1 / 1.5)
In a flask, 30.05 g (100 mmol) of coconut oil fatty acid diethanolamide and 40.70 g (150 mmol, 1.5 equiv.) Of N-lauroyl-N-methyl-glycine were reduced to 2 kPa and heated at 130 ° C. for 9 hours. A theoretical amount of water was distilled off, and the condensate of the coconut oil fatty acid diethanolamide was an O, O'-bis (N-lauroyl-N-methyl-glycine) ester and O- (N-lauroyl-N-methyl-). 65.15 g of a mixture of glycine) esters was taken up.
The structure was determined by 1H-NMR.
¹ H NMR chemical shift: 0.9ppm (7.5H, m), 1.3ppm (41H, m), 1.6ppm (5H, m), 2.3ppm (5H, m), 3.5ppm (10H, m), 4.5ppm ( 5H, m), 4.9ppm (5H, s).

Synthesis example 11 (CDE + SCA = 1 / 1.5)
In a flask, 30.05 g (100 mmol) of coconut oil fatty acid diethanolamide and 42.62 g (150 mmol, 1.5 equiv.) Of N-coconut oil fatty acid-N-methyl-glycine were reduced to 2 kPa and heated at 130 ° C. for 9 hours. A theoretical amount of water was distilled off, and the condensate of this condensate, O, O'-bis (N-coconut oil fatty acid-N-methyl-glycine) ester of coconut oil fatty acid diethanolamide, and O- (N-coconut oil fatty acid-). 63.70 g of a mixture of N-methyl-glycine) esters was taken up.
The structure was determined by 1H-NMR.
¹ H NMR chemical shift: 0.9ppm (7.5H, m), 1.3ppm (43H, m), 1.6ppm (5H, m), 2.3ppm (5H, m), 3.5ppm (10H, m), 4.5ppm ( 5H, m), 4.9ppm (5H, s).

Synthesis Example 12 (2.25 chain ACA 1.25 equivalent)
In a flask, 30.50 g (100 mmol) of coconut oil fatty acid diethanolamide and 37.29 g (125 mmol, 1.25 equiv.) Of N-coconut oil fatty acid-N-methyl-β-alanine were heated to 130 ° C. and dehydrated under reduced pressure for 5 hours. The esterification reaction was carried out by reacting. A theoretical amount of water was distilled off, and the O, O'-bis (N-coconut oil fatty acid-N-methyl-β-alanine) ester of this esterified coconut oil fatty acid diethanolamide and O- (N-coconut oil) A mixture of fatty acid-N-methyl-β-alanine) ester was obtained in an amount of 60.25 g.
^The structure was determined by 1 H NMR.
¹ H NMR chemical shift: 0.9ppm (6.7H m), 1.3ppm (40H m), 1.6ppm (4.5H m), 2.28-2.30ppm (4.5H t), 2.7ppm (2H t), 3.05ppm (3.7) H t), 3.6ppm (6.5H m), 3.8ppm (6.5H m), 4.2ppm (4H t).

Synthesis Example 13 (2.8 chain ACA 1.8 equivalent)
In a flask, 45.81 g (152 mmol) of coconut oil fatty acid diethanolamide and 81.68 g (274 mmol, 1.8 equiv.) Of N-coconut oil fatty acid-N-methyl-β-alanine were heated to 130 ° C. and dehydrated under reduced pressure for 10 hours. The esterification reaction was carried out. A theoretical amount of water was distilled off, and the esterified coconut oil fatty acid diethanolamide O, O'-bis (N-coconut oil fatty acid-N-methyl-β-alanine) ester and O- (N-coconut oil fatty acid) A mixture of −N-methyl-β-alanine) ester was obtained in an amount of 115.13 g.
^The structure was determined by 1 H NMR.
¹ H NMR chemical shift: 0.9ppm (8.1H m), 1.3ppm (50H m), 1.6ppm (5.5H m), 2.28-2.30ppm (5.5H t), 2.6-2.7ppm (3.5H t), 3.05 ppm (5H t), 3.6ppm (7.5H m), 3.8ppm (6.5H m), 4.2ppm (4H t)

Synthesis Example 14 (1.9 chain ACA 0.9 equivalent)
In a flask, 30.50 g (100 mmol) of coconut oil fatty acid diethanolamide and 26.82 g (90 mmol, 0.9 equiv.) Of N-coconut oil fatty acid-N-methyl-β-alanine were heated to 130 ° C. and dehydrated under reduced pressure for 5 hours. The esterification reaction was carried out by reacting. A theoretical amount of water was distilled off, and the O, O'-bis (N-coconut oil fatty acid-N-methyl-β-alanine) ester of this esterified coconut oil fatty acid diethanolamide and O- (N-coconut oil) 52.98 g of a mixture of fatty acid-N-methyl-β-alanine) esters was obtained.
^The structure was determined by 1 H NMR.
¹ H NMR chemical shift: 0.9ppm (5.8H m), 1.3ppm (33H m), 1.6ppm (3.5H m), 2.28-2.30ppm (3.8H t), 2.7ppm (1.8H t), 3.05ppm ( 2.7H t), 3.6ppm (5.5H m), 3.8ppm (5.8H m), 4.2ppm (4H t)

Synthesis Example 15 (3-chain ACA 2.1 equivalent)
In a flask, 30.51 g (100 mmol) of coconut oil fatty acid diethanolamide and 62.63 g (210 mmol, 2.1 equiv.) Of N-coconut oil fatty acid-N-methyl-β-alanine are heated to 130 ° C. and dehydrated under reduced pressure for 10 hours. The esterification reaction was carried out. A theoretical amount of water was distilled off, and the esterified coconut oil fatty acid diethanolamide O, O'-bis (N-coconut oil fatty acid-N-methyl-β-alanine) ester and N-coconut oil fatty acid-N- 91 g of a mixture of methyl-β-alanine was obtained. A white insoluble matter was precipitated in this product.
^The structure was determined by 1 H NMR.
¹ H NMR chemical shift: 0.9ppm (9H m), 1.3ppm (56H m), 1.6ppm (6H m), 2.25 to 2.35ppm (6H t), 2.6-2.7ppm (4H t), 3.05ppm (8H t) ), 3.6ppm (8H m), 4.2ppm (4H t)

1. 1. Measurement of the amount of water held by the oil (% of water held) In order to compare the performances prepared in Synthesis Examples 1 to 15, which are a mixture of fatty acid alkanolamide derivatives which are essential components of the present invention, the amount of water held was measured.
Di (phytosteryl / octyldodecyl) lauroyl glutamate, lauroyl sarcosine isopropyl, triethylhexanoin, cetyl ethylhexanoate, and liquid paraffin were used as comparative test examples.
The oil and water were weighed into a vial according to Table 1. The values shown in the items of each oil agent in Table 1 indicate the g number of each oil agent. The mixture was stirred at room temperature for 10 minutes using a magnetic stirrer. Stirring was stopped and the mixture was allowed to stand, and after 24 hours, the underlying water was pipette removed. The increase in the weight of the remaining oil agent is shown in Table 1 as the amount of water held.
The amount of water held is an index showing the ease of compatibility of each oil with water. An oil agent having a large amount of water holding (% water holding) has a property of being easily emulsified, and can be expected to improve the emulsification stability and the stability at the time of solubilization.
The results are shown in Table 1. As a result, it was found that the oil composition containing the fatty acid alkanolamide derivative mixture, which is an essential component of the present invention, exhibits a higher water holding amount (water holding%) than the oil used in the commonly used comparative test examples.

Emulsions were prepared according to the formulations of Examples 14-28 and Comparative Examples 8 and 9 shown in Table 2. The indicated value is% by weight.
That is, the aqueous phase component was dissolved in a warm bath at 80 ° C., and the oil phase component was added while stirring.
After mixing the two phases well, the mixture was cooled to room temperature to obtain a milky lotion.
The obtained emulsion was stored at 50 ° C. for 10 days to confirm the presence or absence of separation. The item of 50 ° C. storage stability in Table 2 shows the number of days when separation was confirmed.

この結果、実施例１４〜２８に示した乳液は、比較例８及び比較例９の乳液と比較して長い日数分離が見られず乳化安定性が高いことを示された。合成例１〜１５の脂肪酸アルカノールアミド誘導体が乳化安定性を向上させる効果を持つことが判明した。

As a result, it was shown that the emulsions shown in Examples 14 to 28 had high emulsion stability without long-day separation as compared with the emulsions of Comparative Examples 8 and 9. It was found that the fatty acid alkanolamide derivatives of Synthesis Examples 1 to 15 have an effect of improving emulsion stability.

Emulsions were prepared according to the formulations of Examples 29-31 and Comparative Examples 10-12 shown in Table 3. The notation in Table 3 is% by weight.
That is, the aqueous phase component was dissolved in a warm bath at 80 ° C., and the oil phase component was added while stirring.
After mixing the two phases well, the mixture was cooled to room temperature to obtain a milky lotion.
An optical micrograph of the obtained emulsion is shown in FIG. The scale bar at the bottom of the photo shows 50 μm as measured using the scale of the Baker-Turk hemocytometer taken in advance.
In Comparative Examples 10 to 12, oil-phase droplets were confirmed, but in Examples 30 and 31, droplets could not be confirmed with an optical microscope, and in Example 29, fine droplets could be confirmed with an optical microscope.
Further, the droplet sizes of Examples 29 to 31 and Comparative Examples 10 to 11 were measured and shown in the droplet sizes in Table 3.
The droplet sizes of Comparative Examples 10 to 11 are average values obtained by measuring the sizes of five points from the droplets of the microscope image, and Examples 29 to 31 are measured by a dynamic light scattering method (LB-550 manufactured by HORIBA). The median value was shown as the droplet size.
As a result, it was found that the droplet size of Examples 29 to 31 to which the compound of Synthesis Example 1 was added was reduced to 1/1000 to 1/1000.

The feeling of use at the time of application was evaluated using the emulsions of Examples 29 to 31 and Comparative Examples 10 to 12. The evaluation method of the usability of the emulsion will be described.
[Good growth]
Twelve expert panels conducted a usage test on the goodness of elongation of each sample when an appropriate amount was applied to the back of the hand, and judged from the results of the questionnaire according to the following criteria.
(Evaluation criteria)
⊚: 10 or more out of 12 responded that they were good ○: Of 12 respondents, 7-9 responded that they were good △: Of 12 respondents, 4-6 responded that they were good ×: Of 12 respondents, 3 or less answered that it was good

[Familiarity]
Twelve expert panels conducted a usage test on the familiarity of each sample when an appropriate amount was applied to the back of the hand, and judged from the results of the questionnaire according to the following criteria.
(Evaluation criteria)
⊚: 10 or more out of 12 responded that they were good ○: Of 12 respondents, 7-9 responded that they were good △: Of 12 respondents, 4-6 responded that they were good ×: Of 12 respondents, 3 or less answered that it was good

[Sticky]
Twelve expert panels conducted a usage test on the stickiness of each sample after applying an appropriate amount to the back of the hand, and judged from the results of the questionnaire according to the following criteria.
(Evaluation criteria)
⊚: 10 or more out of 12 responded that they were not sticky and good ○: 7 to 9 out of 12 responded that they were not sticky and good △: 4 to 6 out of 12 responded that they were not sticky and good ×: Of the 12 respondents, 3 or less responded that they were not sticky and were good.

[Moist feeling]
Twelve expert panels conducted a usage test on the moist feeling of each sample after applying an appropriate amount to the back of the hand, and judged from the results of the questionnaire according to the following criteria.
(Evaluation criteria)
⊚: 10 or more out of 12 responded that they had a moist feeling ○: 7 to 9 out of 12 responded that they had a moist feeling △: 4 to 6 out of 12 responded that they had a moist feeling ×: Of the 12 respondents, 3 or less responded that they felt moist.

本発明油剤組成物を含む乳液化粧料である実施例２９〜３１の使用感は、比較例１０〜１１と比較して全ての測定項目で優れた評価を得た。

The usability of Examples 29 to 31, which are emulsion cosmetics containing the oil composition of the present invention, was excellently evaluated in all the measurement items as compared with Comparative Examples 10 to 11.

A self-emulsifying bath salt containing the oil composition of the present invention was blended according to Table 4. The notation in Table 4 is% by weight.
Twelve specialist panels added and dispersed 60 mL of each bath salt to 180 L of hot water in a bathtub kept at 40 degrees Celsius, and then bathed. The moist feeling of the skin after bathing was scored according to the following criteria.
Regarding the emulsification stability, we asked them to observe the condition of the bath water (room temperature) the next morning. The bath salt of Example 32 was in a stable cloudy state in Yoshicho, but the bath salt of Comparative Example 13 was observed to have oil floating like a suminagashi in 7 cases / 12 cases.

(Evaluation criteria)
⊚: 10 or more out of 12 responded that they had a moist feeling ○: 7 to 9 out of 12 responded that they had a moist feeling △: 4 to 6 out of 12 responded that they had a moist feeling ×: Of the 12 respondents, 3 or less responded that they felt moist.

本発明の油剤組成物を配合した入浴剤の方が優れた使用感を有し、乳化状態が安定であることが示された。

It was shown that the bath salt containing the oil composition of the present invention had an excellent feeling of use and the emulsified state was stable.

Hair conditioner cosmetics containing the oil composition of the present invention were blended according to Table 5. The notation in Table 5 is% by weight.
Each composition was subjected to a use test by 12 panelists, and sensory evaluation was performed on the moist feeling of the hair after drying and the gloss of the hair after drying, as per the fingers when rinsing the hair rinse.

Finger passage during rinsing (evaluation criteria)
⊚: Of the 12 respondents, 10 or more responded that finger passage during rinsing was good.
◯: Of the 12 respondents, 7 to 9 responded that finger passage during rinsing was good.
Δ: 4 to 6 out of 12 responded that finger passage during rinsing was good.
X: Of the 12 respondents, 3 or less responded that finger passage during rinsing was good.

Moist feeling of hair after drying (evaluation criteria)
⊚: Of the 12 people, 10 or more answered that they felt moist after drying.
◯: Of the 12 respondents, 7 to 9 responded that they felt moist after drying.
Δ: 4 to 6 out of 12 responded that they felt moist after drying.
X: Of the 12 respondents, 3 or less responded that they felt moist after drying.

Hair gloss after drying (evaluation criteria)
⊚: Of the 12 people, 10 or more answered that the gloss was good.
◯: Of the 12 people, 7 to 9 answered that the gloss was good.
Δ: 4 to 6 out of 12 responded that the gloss was good.
X: Of the 12 respondents, 3 or less responded that the gloss was good.

本発明の油剤組成物を含有する実施例３４は、優れた伸び性をもった。使用しやすいクリームを得ることができ、使用後のしっとり感に優れていた。
A cream cosmetic containing the oil composition of the present invention was blended according to Table 6. The notation in Table 6 is% by weight.
Each composition was subjected to a use test by 12 panelists, and the performance was evaluated by the same method as the evaluation of the emulsion.

Example 34 containing the oil composition of the present invention had excellent extensibility. An easy-to-use cream could be obtained, and the moist feeling after use was excellent.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an oil composition optimized for obtaining a cosmetic having a moist feel to the skin, a good feeling of use, and excellent stability, and a cosmetic using the same. ..

Claims (8)

(A) and fatty acid alkanolamides derived derivatives represented by the general formula (1)

[In the formula (1), R ¹ is indicates a hydrocarbon chain of 7 to 21 carbon atoms,
R ² represents a hydrogen atom or a substituent of the general formula (2).
A represents a hydrogen atom, a methyl group, or -CH ₂ CH ₂ ^{OR 3} groups.
R ³ represents a hydrogen atom or a substituent of the general formula (2).
Excludes cases where R ² and A, R ² and R ³ are hydrogen atoms at the same time. ]

[In the formula (2), ^{R 4} is shows a hydrocarbon chain of 7 to 21 carbon atoms,
p represents an integer of 0 to 1. ]
(B) consists of a oil which is liquid at room temperature,
An oil composition comprising a component ( B ) and a component ( A ) in a weight ratio of 5: 5 to 9: 1 . Formula fatty alkanolamides derived that is represented by (1), the general formula (3) oil agent composition of claim 1 wherein the fatty acid alkanolamides derived body indicated by.

[In the formula (3), ^{R 1} is indicates a hydrocarbon chain of 7 to 21 carbon atoms,
R ² represents a hydrogen atom or a substituent of the general formula (2).
R ³ represents a hydrogen atom or a substituent of the general formula (2).
Except when R ² and R ³ are hydrogen atoms at the same time, the introduction of the substituent of the formula (2) introduced into ^{R 2} and R ^{3 is from 1.25 equivalents to 1.} Between 80 equivalents. ] The oil liquid is at room temperature, hydrocarbon oils, synthetic ester oils, silicone oils, claims 1 to 2 oil composition according selected from vegetable oils. A self-emulsifying bath agent containing 95 to 80% by weight of the oil composition according to any one of claims 1 to 3 and 5 to 20% by weight of a nonionic surfactant . Contains 2.0 to 10.0% by weight of the oil composition according to any one of claims 1 to 3, 1.0 to 10.0% by weight of a nonionic surfactant, and purified water (residual). Emulsion cosmetics to do . Hair containing 0.1 to 5.0% by weight of the oil composition according to any one of claims 1 to 3, 0.5 to 10% by weight of a cationic surfactant, and purified water (residual). Conditioner cosmetics . Contains 0.5 to 10.0% by weight of the oil composition according to any one of claims 1 to 3, 0.5 to 10.0% by weight of a nonionic surfactant, and purified water (residual). Toner cosmetics . 2.0 to 5.0% by weight of the oil composition according to any one of claims 1 to 3, 1.0 to 15.0% by weight of the solid oil at room temperature, 0.5 to 0.5% by weight of the nonionic surfactant. A cream cosmetic containing 15% by weight and purified water (residual) .

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