JP6845649B2 - Cleansing composition containing a mixture of fatty acid alkanolamide derivatives - Google Patents

Description

The present invention relates to a cleansing composition having a detergency capable of removing hard-to-remove makeup stains such as mascara, capable of quickly removing stains when rinsing, and providing a feeling of use with less oily stickiness after use.

In recent years, due to the evolution of make-up technology, various types have been developed, from light make-up that makes the most of the beauty of bare skin to hard make-up that is resistant to sweat and sebum. Furthermore, due to the advancement of women into society and the diversification of lifestyles, not only the ability to remove make-up, but also those that emphasize the ease of cleansing and washing the face with one product, skin care effects and usability. The variety of cleansing cosmetics is expanding, such as types that emphasize added value.

On the other hand, when the cleansing composition is technically classified, it can be roughly classified into three types: aqueous, emulsified, and oily.
The water-based cleansing composition is mainly composed of water-based components and contains a small amount of a surfactant or oil for removing makeup stains. It has a fresh and non-greasy feel and is impregnated with cotton or non-woven fabric. It is characterized by the convenience of simply wiping it off. Conventionally, surfactants and various additive components have been studied. For example, Patent Document 1 contains polyoxyethylene fatty acid glyceryl and diethoxyethyl succinate, and does not irritate the ocular mucosa. Described is an aqueous cleansing composition that easily removes greasy stains such as makeup and suppresses a sticky feeling after wiping.

The emulsified type cleansing composition is obtained by emulsifying an oil agent using a surfactant, and is characterized in that it has a higher make-up removing ability than an aqueous type and can realize various feelings of use. For example, Patent Document 2 contains oil, polyoxyethylene monofatty acid glyceryl, water, and a thickener, and has quick make-up familiarity, excellent emulsion stability, and easy-to-wash, emulsion-creamy oil-in-water emulsified skin cleansing. The fee is listed.

The oil-based cleansing composition has a high make-up removing ability due to the solvent effect of a large amount of oil, and is also suitable for hard make-up cleansing such as a waterproof type. For example, in Patent Document 3, two specific types of polyglycerin fatty acid esters are used in combination, and an ester oil liquid at 25 ° C. composed of a monohydric alcohol and a fatty acid is combined to provide an excellent cleansing effect, a feeling of application and use. An oily liquid cleansing cosmetic that feels good afterwards is described.

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).

Japanese Unexamined Patent Publication No. 2011-126805 Japanese Unexamined Patent Publication No. 2013-177383 Japanese Unexamined Patent Publication No. 2012-250939 Japanese Patent Application No. 2015-078779

However, in the water-based cleansing, the ability to remove makeup stains may be insufficient.
Emulsification type cleansing is not familiar with makeup and may leave oiliness after use.
Oil-type cleansing compositions may remain oily after use.

That is, until now, no sufficiently satisfactory cleansing agent has been developed.
An attempt to provide a cleansing composition that has a detergency that can remove hard-to-remove makeup stains such as mascara, can quickly wash off stains when washed away, and gives a feeling of use with less oily stickiness after use. Is.

The present inventor has found that a cleansing composition obtained by blending a nonionic surfactant with a mixture of fatty acid alkanolamide derivatives solves the above problems, and has completed the present invention.
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）ノニオン界面活性剤（但し、トリイソステアリン酸ＰＥＧ−２０グリセリルは除く）
を含有するクレンジング組成物に関するものであり、 (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) Nonionic surfactant (excluding PEG-20 glyceryl triisostearate)
It relates to a cleansing composition containing

［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. ]

In addition, nonionic surfactants (excluding PEG-20 glyceryl triisostearate) are derived from polyoxyalkylene alkyl ether polyoxyalkylene fatty acid esters, polyoxyethylene hydrogenated castor oil, polyglycerin fatty acid esters, and polyoxyalkylene sorbitan esters. More preferably, it is one or more selected nonionic surfactants (excluding PEG-20 glyceryl triisostearate).

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a cleansing composition having a high ability to remove makeup stains, excellent stability, less oiliness after use, excellent rinsing property when rinsing, and giving a moist feeling to the skin. ..

［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 present invention will be described.
Consists of a mixture of fatty acid alkanolamide derivatives 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,
The combination of fatty acid methylethanolamide and acylmethylglycine is exemplified, and 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 amount of fatty acid alkanolamide.

Examples of fatty acid alkanolamides include lauric acid diethanolamide, lauric acid myristic acid diethanolamide, stearic acid diethanolamide, oleate diethanolamide, coconut oil fatty acid diethanolamide, coconut oil fatty acid methylethanolamide, palm kernel oil fatty acid diethanolamide, and modified palm. Examples include oil-fat diethanolamide, 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基は、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 acylmethylβ-alanine are used as raw materials with respect to 1 equivalent of fatty acid alkanolamide, and acylmethylglycine or acylmethylβ-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 it gives a better feeling of use when blended in a cleansing agent.

[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 groups, represents a substituent hydrogen atom or a 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. ]

These fatty acid alkanolamide derivative mixtures are blended as an oily component of a cleansing agent and directly affect its detergency and usability.
The fatty acid alkanolamide derivative mixture as the component (A) is preferably blended in the cleansing composition as part or all of the oily component, and the blending amount with respect to the cleansing agent is preferably 0.1 to 50% by weight. More preferably, the blending amount is 5 to 20% by weight based on the cleansing agent. If the blending amount is less than 5% by weight with respect to the cleansing agent, the effect of the present invention cannot be obtained, which is not preferable. Remains unfavorable.

Next, the essential component (B) nonionic surfactant (excluding PEG-20 glyceryl triisostearate) will be described. The component (B) is formulated to provide a function of removing oily components including the component (A) from the surface to be cleaned in the rinsing step after removing oily stains with an oil agent containing the component (A). , The nonionic surfactant composition is selected from nonionic surfactants having a mixed HLB of about 8 to 12.
More specifically, it is preferably one or more selected from polyoxyalkylene alkyl ether polyoxyalkylene fatty acid ester, polyoxyethylene hydrogenated castor oil, polyglycerin fatty acid ester, and polyoxyalkylene sorbitan ester.

｛Ｒ^５は炭素数８〜２２のアルキル基を示し、ＡＯはオキシアルキレン基を示し、qはオキシアルキレン基の平均付加モル数を示し、２〜１０の数である。｝
より最適には、ポリオキシエチレンセチルエーテル、ポリオキシエチレンラウリルエーテルらが挙げられる。 The polyoxyalkylene alkyl ether is a nonionic surfactant represented by the general formula (4).

{R ⁵ indicates an alkyl group having 8 to 22 carbon atoms, AO indicates an oxyalkylene group, and q indicates the average number of moles of the oxyalkylene group added, which is a number of 2 to 10. }
More optimally, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether and the like can be mentioned.

｛Ｒ⁶は炭素数７〜２１のアルキル基を示し、ＡＯはオキシアルキレン基を示し、ｒはオキシアルキレン基の平均付加モル数を示し、２〜１０の数である。｝
より最適には、ポリオキシエチレンイソステアリン酸エステル、モノオレイン酸ポリエチレングリコール等が挙げられる The polyoxyalkylene fatty acid ester is a nonionic surfactant represented by the general formula (5).

{R ⁶ indicates an alkyl group having 7 to 21 carbon atoms, AO indicates an oxyalkylene group, and r indicates the average number of moles of the oxyalkylene group added, which is a number of 2 to 10. }
More optimally, polyoxyethylene isostearic acid ester, polyethylene glycol monooleate and the like can be mentioned.

Preferable examples of the polyoxyethylene hydrogenated castor oil include polyglycerin fatty acid esters such as polyoxyethylene hydrogenated castor oil triisostearate and polyoxyethylene hydrogenated castor oil laurate (provided that PEG-20 triisostearate). Preferable examples of (excluding glyceryl) include polyglyceryl diisostearate, polyglyceryl isostearate and the like.
Preferable examples of the polyoxyalkylene sorbitan ester include polyoxyethylene sodium tetrasorbitan tetraoleate, polyoxyethylene sorbitan triisostearate, and the like.

The amount of the essential component (B) nonionic surfactant (excluding PEG-20 glyceryl triisostearate) to the cleansing agent is preferably 5 to 50% by weight, more preferably 10 to 30% by weight.
If the amount of the essential component (B) nonionic surfactant (excluding PEG-20 glyceryl triisostearate) in the cleansing agent is less than 5% by weight, the rinsing process of the cleansing oil agent is hindered, which is not preferable. If it is blended in excess of% by weight, problems such as impairing the usability will occur, which is not preferable.

The cleansing agent containing the fatty acid alkanolamide derivative mixture of the present invention includes components usually blended in cosmetics as long as the effects of the present invention are not impaired, for example, oily bases other than the fatty acid alkanolamide derivative mixture of the present invention, the present invention. (B) Surfactants other than the components, moisturizers, polymer thickeners, polymer gelling agents, antioxidants, preservatives, bactericides, chelating agents, pH adjusters, solvents, ultraviolet absorbers, anti-inflammatory agents, Cooling agents, antihistamines, astringents, stimulants, hair growth agents / blood circulation promoters, vitamins and their derivatives, hydroxy acids, enzymes, nucleic acids, hormones, sugars and their derivatives, inorganic powders, high Molecular powders, fragrances, pigments and the like can be blended.

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. A 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) 64.53 g of a mixture of −β-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 monoesterified 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.

構造式略号
CDE ヤシ油脂肪酸ジエタノールアミド
LDE ラウリン酸ジエタノールアミド
LME ラウリン酸モノエタノールアミド
ACA ヤシ油脂肪酸N−メチル−β-アラニン
ALA ラウロイル−N−メチル−β-アラニン
SLA ラウロイル−N−メチル−グリシン
SCA ヤシ油脂肪酸N−メチル−グリシン The amount of water held is an index showing the ease of compatibility of each oil with water. An oil having a large amount of water (% of water) has a property of being easily emulsified, which improves the ease of rinsing when the cleansing agent is rinsed with water or reduces the reattachment of oily stains transferred to the oil. Can be expected.
The results are shown in Table 1. As a result, it was found that 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 agent used in the commonly used comparative test examples.

Structural formula abbreviation
CDE coconut oil fatty acid diethanolamide
LDE laurate diethanolamide
LME lauric acid monoethanolamide
ACA coconut oil fatty acid N-methyl-β-alanine
ALA lauroyl-N-methyl-β-alanine
SLA lauroyl-N-methyl-glycine
SCA coconut oil fatty acid N-methyl-glycine

An oil cleansing agent containing a mixture of fatty acid alkanolamide derivatives, which are essential components of the present invention, is actually blended according to Table 2, and "lightness", "easiness to stretch", "cleansing power", and "easiness to rinse" are evaluated by sensory evaluation. The items of were evaluated. Each test method is as follows

Evaluation of lightness A 12-person expert panel conducted a usage test on the lightness of each sample when applied to the skin, 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

Evaluation of Ease of Stretching Each sample was subjected to a usage test on the ease of stretching after application to the skin by 12 specialist panels, and the results of the questionnaire were judged 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

Evaluation of cleansing power Each sample was tested for the degree of ease of removal of commercially available oil-based makeup cosmetics by 12 specialist panels, and the results of the questionnaire were judged according to the following criteria.
(Evaluation criteria)
⊚: 10 or more out of 12 responded that it was easy to remove make-up cosmetics ○: 7-9 out of 12 responded that it was easy to remove make-up cosmetics △: 4 out of 12 ~ 6 responded that it was easy to remove makeup cosmetics ×: Of the 12 respondents, 3 or less answered that it was easy to remove makeup cosmetics

※ポリオキシエチレン硬化ヒマシ油 ポリオキシエチレン（６０）硬化ヒマシ Evaluation of ease of rinsing Each sample was tested for ease of rinsing when rinsed with water by 12 expert panels, and the results of the questionnaire were judged 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

* Polyoxyethylene hardened castor oil Polyoxyethylene (60) hardened castor oil

In fact, the oil cleansing agent containing the oil cleansing agent containing the mixture of the essential component fatty acid alkanolamide derivative of the present invention showed superior performance to the comparison target. In particular, it has both ease of rinsing and cleansing power, demonstrating that the cleansing agent according to the present invention is excellent.

The effect of suppressing the amount of water evaporation was compared for the purpose of examining the emollient performance of the fatty acid alkanolamide derivative mixture of Synthesis Example 1. As a comparative control, an unapplied state as a negative control (Comparative Test Example 8), cetyl 2-ethylhexanoate (Comparative Test Example 9) as an oil agent often blended in cleansing cosmetics, and lauroyl, which is a commercially available emollient agent. The effect of suppressing the amount of water evaporation was compared using diglutamic acid (phytosteryl / octyldodecyl) (Comparative Test Example 10).
The test method was to acclimatize to the measurement environment by resting for 30 minutes in a room at room temperature of 20 ° C. The forearm, which is the measurement site, was washed with soap, and the amount of water evaporation (0 minutes before application) 30 minutes after washing was measured. An oil agent was applied to the measurement site, and the amount of water evaporation was measured 10 minutes, 30 minutes, and 60 minutes after the application. This test was conducted by 3 subjects.

試験例１４では、塗布後の水分蒸散量が１０分後、３０分後、６０分後の３点ともに塗布前より減少していた。一方、未塗布の比較試験例８では６０分後に５％増、油剤の２-エチルヘキサン酸セチルを塗布した比較試験例９では６０分後で９％増、市販のエモリエント剤であるラウロイルグルタミン酸ジ（フィトステリル/オクチルドデシル）を塗布した比較試験例１０では、１０分後の７％増えたが６０分後には塗布前の値と同じである０％に減少していた。
試験例１４は、比較試験例８〜１０の試験結果と比べて水分蒸散量が減少しており、比較対照とした２−エチルヘキサン酸セチルやラウロイルグルタミン酸ジ（フィトステリル/オクチルドデシル）と比べても高い水分蒸散量の抑制効果を持つことが分かった。 Table 3 shows the increase / decrease (%) of the water transpiration amount 0 minutes before application with the water transpiration amount as 100%, and the measured value (mean value) of the water transpiration amount.

In Test Example 14, the amount of water transpiration after application was lower than that before application at all three points after 10 minutes, 30 minutes, and 60 minutes. On the other hand, in Comparative Test Example 8 which was not applied, it increased by 5% after 60 minutes, and in Comparative Test Example 9 where the oil agent cetyl 2-ethylhexanoate was applied, it increased by 9% after 60 minutes. In Comparative Test Example 10 to which (phytosteryl / octyldodecyl) was applied, it increased by 7% after 10 minutes, but decreased to 0%, which was the same as the value before application, after 60 minutes.
In Test Example 14, the amount of water transpiration was reduced as compared with the test results of Comparative Test Examples 8 to 10, and even when compared with the comparative control of cetyl 2-ethylcaproate and di lauroyl glutamate (phytosteryl / octyldodecyl). It was found that it has a high effect of suppressing the amount of water evaporation.

Cleansing agents were prepared according to the formulations shown in Table 4.
That is, the components of the oil phase shown in Table 4 were dissolved and mixed at 50 ° C. under heating. After cooling the oil phase to room temperature, the aqueous phase component was added and further mixed to obtain a cleansing agent. The usability of the oil-based cleaning agents of each formulation was evaluated for lightness at the time of application, ease of spreading, cleansing power, and ease of rinsing by the above-mentioned evaluation method. In addition to this, the following evaluation of "moist feeling" after rinsing was also carried out.

表４の結果よりいずれの実施例も比較例より評価の高いクレンジング剤であることが示された。 Evaluation of moist feeling Each sample was subjected to a usage test for moist feeling after rinsing with water by 12 specialist panels, and the results of the questionnaire were judged according to the following criteria.
(Evaluation criteria)
⊚: 10 or more out of 12 responded that there was a moist feeling ○: 7-9 out of 12 responded that there was a moist feeling △: 4-6 out of 12 responded that there was a moist feeling ×: Of the 12 respondents, 3 or less answered that they had a moist feeling.

From the results in Table 4, it was shown that all the examples were cleansing agents with higher evaluation than the comparative examples.

INDUSTRIAL APPLICABILITY According to the present invention, there is provided a cleansing composition which has a detergency capable of removing hard-to-remove makeup stains such as mascara, can quickly wash off stains when washed away, and gives a feeling of use with less greasy stickiness after use. it can.

Claims (4)

(A) the general formula (1) with a fatty acid alkanolamide derived body及beauty represented

[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) Nonionic surfactant (excluding PEG-20 glyceryl triisostearate)
A cleansing composition containing . Formula fatty alkanolamides derived that is represented by (1), the general formula (3) cleansing 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. ] Said nonionic surfactant is a polyoxyalkylene alkyl ether, polyoxyalkylene fatty acid esters, polyoxyethylene hardened castor oil, polyglycerol fatty acid esters and one or two or more at a claim selected from polyoxyalkylene sorbitan esters, The cleansing composition according to 1 or 2. Formula (1) cleansing composition according to any one of claims 1 to 3, having 0.1 to 50 wt% free fatty acid alkanolamides derived that is represented by.