CN101277675A - Carnitine derivative, salt thereof, external skin preparation and cosmetic material - Google Patents

Carnitine derivative, salt thereof, external skin preparation and cosmetic material Download PDF

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CN101277675A
CN101277675A CN200680036145.0A CN200680036145A CN101277675A CN 101277675 A CN101277675 A CN 101277675A CN 200680036145 A CN200680036145 A CN 200680036145A CN 101277675 A CN101277675 A CN 101277675A
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carnitine
anion
carnitine derivative
acid
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CN101277675B (en
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青木裕史
蒲池晴美
仓田洋平
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Lishennoco Co ltd
Resonac Holdings Corp
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Showa Denko KK
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Abstract

The purpose of the invention is to provide novel carnitine derivatives and salts thereof that are resistant to hydrolysis in the presence of aqueous media, and also provide external skin preparations and cosmetics that are excellent in storage stability, product life, skin affinity and percutaneous absorption properties. In particular, to provide novel alpha-branched acyl carnitine derivatives and salts thereof, external skin preparations and cosmetics comprising specific alpha-branched acyl carnitine derivatives and/or salts thereof.

Description

Carnitine derivative, its salt, preparation for external application to skin and cosmetic material
The reference of related application
The application is the application of submitting to according to 35U.S.C. § 111 (a), it requires the provisional application No.60/724 in submission on October 7th, 2005 according to 35 U.S.C. § 111 (b) according to 35 U.S.C. § 119 (e), the No.60/777 that on March 1st, 276 and 2006 submitted to, the right of 551 the applying date.
Invention field
The present invention relates to preparation for external application to skin and cosmetics.More particularly, the present invention relates to contain the preparation for external application to skin and the cosmetics of carnitine derivative and/or its salt and promotion lipid metabolism.The invention still further relates to novel carnitine derivative and salt thereof.
Background technology
Carnitine is known to play an important role in people's lipid metabolism.In cell, carnitine is bonded to from being conveyed into mitochondrion on the fatty acid of fat and with described fatty acid, a kind of organelle of the fat of burning therein by enzymatic.Therefore, carnitine has as the function of the carrier of described fatty acid and is important for lipid metabolism.Described fatty acid in mitochondrion by beta oxidation and change into the energy of ATP form in the live body.
Described lipid is important, and it is not only as energy source but also as the human body constituent.The all cells film is made up of described lipid.On macroscopic view, described lipid is evaporated from health with the form control of sebum and iuntercellular liquid wet the branch.
Because the accumulation of subcutaneous fat, excessive lipid can cause fat, and cause many beauty treatments and QOL (quality of the life) problem, the skin aging that comprises light that liparitosis forms, causes because of excess sebum and fatty skin, seborrheic dermatitis and the alopecia that causes thus, acne, body odour and cause because of the lipid metabolism that goes down.
As mentioned above, described lipid metabolism requires fatty acid to be conveyed in the mitochondrion, and this is that carnitine is responsible for.Therefore, lipid metabolism speed depends on the amount of carnitine in the cell.Carnitine concentration in the raising destination organization can promote lipid metabolism also can prevent and eliminate excessive lipid and relevant with it problem.
For this reason, absorb to promote lipid metabolism (patent documentation 1-4) with the percutaneous that has proposed the multiple preparation for external application to skin that contains carnitine after deliberation.Yet these preparation for external application to skin that contain L-carnitine and salt thereof still can not reach gratifying effect.Reason may be that L-carnitine and salt thereof are very easy to by hydration, so its direct use can cause bad skin affinity and Percutaneously absorbable energy, and enough carnitines almost can not arrive wherein will carry out the tissue of described lipid metabolism.
Proposed the weight-losing and skin external preparation, it contains the straight chain fatty acyl carnitine (wherein using straight chain fatty acid residue modification carnitine) that the dermatological effect can be higher than carnitine itself.For example, a kind of weight-losing and skin external preparation contains palmityl-L-carnitine (L-carnitine cetylate), carnitine, caffeine and coenzyme A (patent documentation 5).
[patent documentation 1] Japan Patent No.3434995
[patent documentation 2] JP-A-H07-309711
[patent documentation 3] JP-A-2000-16916
[patent documentation 4] JP-A-2001-64147
[patent documentation 5] French Patent (FRP) No.2694195
Summary of the invention
[problem solved by the invention]
The straight chain fatty acyl carnitine infiltrates skin and produces the effect of excellent promotion lipid metabolism.Yet this straight chain acyl group is easy to hydrolysis and decomposes in the water base goods as the common type of preparation for external application to skin, particularly cosmetics easily.Therefore, the storage stability difference of described goods and life-span are short.
The present invention relates to address the above problem.Therefore the object of the present invention is to provide storage stability, product life, skin affinity and excellent preparation for external application to skin and the cosmetics of Percutaneously absorbable energy.
Another object of the present invention is to be provided at water-bearing media and have the novel carnitine derivative and the salt thereof of hydrolysis down.
[means of dealing with problems]
The inventor studies assiduously and finds that alpha-branched fatty acyl carnitine derivant, particularly L-carnitine 2-hexyldecanoic acid ester, L-carnitine 2-methyl palmitic acid ester and L-carnitine 2-butyl caprylate have excellent stability in the presence of water-bearing media.Finish the present invention based on this discovery.The present invention relates to following [1] to [26].
[1] preparation for external application to skin, it comprises by the carnitine derivative of formula (1) expression and/or by the salt of the carnitine derivative of formula (2) expression:
Figure A20068003614500111
R wherein 1And R 2Each can have the saturated or undersaturated aliphatic hydrocarbyl of 1-18 carbon atom of side chain naturally;
Figure A20068003614500112
R wherein 1And R 2Suc as formula defined in (1), X -Be that cationic moiety with described carnitine derivative keeps electroneutral inorganic or organic anion, and Y +Be that anionicsite with described carnitine derivative keeps electroneutral inorganic or organic cation.
[2] as [1] described preparation for external application to skin, the R in its Chinese style (1) and (2) 1And R 2Each can have the saturated or undersaturated aliphatic hydrocarbyl of 3-16 carbon atom of side chain naturally.
[3] as [1] described preparation for external application to skin, the R in its Chinese style (1) and (2) 1And R 2One of be the linear alkyl of 6 carbon atoms, and another is the linear alkyl of 8 carbon atoms.
[4] as [1] described preparation for external application to skin, the R in its Chinese style (1) and (2) 1And R 2One of be the linear alkyl of 4 carbon atoms, and another is the linear alkyl of 6 carbon atoms.
[5] as [1] described preparation for external application to skin, the R in its Chinese style (1) and (2) 1And R 2One of be methyl, and another is the linear alkyl of 14 carbon atoms.
[6] as each described preparation for external application to skin in [1]-[5], the X in its Chinese style (2) -It is to be selected from following anion: hydroxide ion, nitrate ion, sulfate ion, carbanion, bicarbonate ion, chloride ion, formate ion, acetate ion, citrate ion, the tartrate anion ion, oxalate denominationby, fumarate ion, saturated or the undersaturated fatty acid anion that can have 3-20 carbon atom of side chain, the carnitine anion, the carnitine derivative anion, ascorbic acid root anion, Ascorbic acid 2-phosphate anion (ascorbylphosphate anion) and Ascorbic acid 2-phosphate derivant anion.
[7] as each described preparation for external application to skin in [1]-[6], the Y in its Chinese style (2) +Be to be selected from following cation: hydrion, sodium ion, potassium ion, calcium ion, magnesium ion, zinc ion, ammonium ion, carnitine cation and carnitine derivative cation.
[8] as each described preparation for external application to skin in [1]-[7], wherein said by formula (1) expression carnitine derivative and/or account for the 0.01-20 quality % of described preparation for external application to skin by the salt of the carnitine derivative of formula (2) expression.
[9] cosmetics, it comprises the salt of each described carnitine derivative in [1]-[7] of 0.01-20 quality % and/or carnitine derivative.
[10] as [9] described cosmetics, it is the cosmetics that are used to promote lipid metabolism.
[11] carnitine derivative of representing by formula (3):
Figure A20068003614500131
R wherein 3And R 4One of be the radical of saturated aliphatic alkyl that can have 1-16 carbon atom of side chain, and another is the radical of saturated aliphatic alkyl that can have 8-16 carbon atom of side chain.
[12] by the salt of the carnitine derivative of formula (4) expression:
Figure A20068003614500132
R wherein 3And R 4One of be the radical of saturated aliphatic alkyl that can have 1-16 carbon atom of side chain, and another is the radical of saturated aliphatic alkyl that can have 8-16 carbon atom of side chain, X -Be that cationic moiety with described carnitine derivative keeps electroneutral inorganic or organic anion, and Y +Be that anionicsite with described carnitine derivative keeps electroneutral inorganic or organic cation.
[13] carnitine derivative of representing by formula (5):
Figure A20068003614500141
R wherein 5And R 6One of be the radical of saturated aliphatic alkyl that can have 2-7 carbon atom of side chain, and another is the radical of saturated aliphatic alkyl that can have 3-7 carbon atom of side chain.
[14] by the salt of the carnitine derivative of formula (6) expression:
Figure A20068003614500142
R wherein 5And R 6One of be the radical of saturated aliphatic alkyl that can have 2-7 carbon atom of side chain, and another is the radical of saturated aliphatic alkyl that can have 3-7 carbon atom of side chain, X -Be that cationic moiety with described carnitine derivative keeps electroneutral inorganic or organic anion, and Y +Be that anionicsite with described carnitine derivative keeps electroneutral inorganic or organic cation.
[15] carnitine derivative of representing by formula (7):
Figure A20068003614500151
[16] by the salt of the carnitine derivative of formula (8) expression:
Figure A20068003614500152
X wherein -Be that cationic moiety with described carnitine derivative keeps electroneutral inorganic or organic anion, and Y +Be that anionicsite with described carnitine derivative keeps electroneutral inorganic or organic cation.
[17] as the salt of [16] described carnitine derivative, the X in its Chinese style (8) -It is to be selected from following anion: hydroxide ion, nitrate ion, sulfate ion, carbanion, bicarbonate ion, chloride ion, formate ion, acetate ion, citrate ion, the tartrate anion ion, oxalate denominationby, fumarate ion, saturated or the undersaturated fatty acid anion that can have 3-20 carbon atom of side chain, the carnitine anion, the carnitine derivative anion, ascorbic acid root anion, Ascorbic acid 2-phosphate anion and Ascorbic acid 2-phosphate derivant anion.
[18] as the salt of [16] or [17] described carnitine derivative, the Y in its Chinese style (8) +Be to be selected from following cation: hydrion, sodium ion, potassium ion, calcium ion, magnesium ion, zinc ion, ammonium ion, carnitine cation and carnitine derivative cation.
[19] carnitine derivative of representing by formula (9):
Figure A20068003614500161
[20] by the salt of the carnitine derivative of formula (10) expression:
Figure A20068003614500162
X wherein -Be that cationic moiety with described carnitine derivative keeps electroneutral inorganic or organic anion, and Y +Be that anionicsite with described carnitine derivative keeps electroneutral inorganic or organic cation.
[21] as the salt of [20] described carnitine derivative, the X in its Chinese style (10) -It is to be selected from following anion: hydroxide ion, nitrate ion, sulfate ion, carbanion, bicarbonate ion, chloride ion, formate ion, acetate ion, citrate ion, the tartrate anion ion, oxalate denominationby, fumarate ion, saturated or the undersaturated fatty acid anion that can have 3-20 carbon atom of side chain, the carnitine anion, the carnitine derivative anion, ascorbic acid root anion, Ascorbic acid 2-phosphate anion and Ascorbic acid 2-phosphate derivant anion.
[22] as the salt of [20] or [21] described carnitine derivative, the Y in its Chinese style (10) +Be to be selected from following cation: hydrion, sodium ion, potassium ion, calcium ion, magnesium ion, zinc ion, ammonium ion, carnitine cation and carnitine derivative cation.
[23] carnitine derivative of representing by formula (11):
Figure A20068003614500171
[24] by the salt of the carnitine derivative of formula (12) expression:
Figure A20068003614500172
X wherein -Be that cationic moiety with described carnitine derivative keeps electroneutral inorganic or organic anion, and Y +Be that anionicsite with described carnitine derivative keeps electroneutral inorganic or organic cation.
[25] as the salt of [24] described carnitine derivative, the X in its Chinese style (12) -It is to be selected from following anion: hydroxide ion, nitrate ion, sulfate ion, carbanion, bicarbonate ion, chloride ion, formate ion, acetate ion, citrate ion, the tartrate anion ion, oxalate denominationby, fumarate ion, saturated or the undersaturated fatty acid anion that can have 3-20 carbon atom of side chain, the carnitine anion, the carnitine derivative anion, ascorbic acid root anion, Ascorbic acid 2-phosphate anion and Ascorbic acid 2-phosphate derivant anion.
[26] as the salt of [24] or [25] described carnitine derivative, the Y in its Chinese style (12) +Be to be selected from following cation: hydrion, sodium ion, potassium ion, calcium ion, magnesium ion, zinc ion, ammonium ion, carnitine cation and carnitine derivative cation.
[invention effect]
Because the anti-decomposition in the presence of water-bearing media of described carnitine derivative, preparation for external application to skin of the present invention and cosmetics have the long-life.Therefore, described carnitine derivative in the described goods and the carnitine derivative that comes from described carnitine derivative salt produce excellent effect (activity of the promotion lipid metabolism in skin affinity, Percutaneously absorbable energy and the tissue) steadily in the long term.
Therefore, described preparation for external application to skin and cosmetics can be used to promote lipid metabolism aptly.
The hydrolysis hardly in the presence of water-bearing media of novel carnitine derivative of the present invention and salt thereof.
The accompanying drawing summary
Fig. 1 is the figure that shows the concentration of the free carnitine that comes from test substances that passes to after 24 hours among the embodiment 1 in the corium side room and carnitine derivative; With
Fig. 2 shows the residual rate figure over time that comes from the carnitine derivative of test substances in the aqueous solution of embodiment 2.
The preferred embodiment of invention
Below will describe the present invention in detail.
Preparation for external application to skin of the present invention and cosmetics contain specific carnitine derivative and/or its salt.That is, described preparation for external application to skin and cosmetics can contain any or both in specific carnitine derivative and the salt thereof.
＜carnitine derivative 〉
The carnitine derivative that is used for preparation for external application to skin of the present invention and cosmetics is represented by formula (1):
Figure A20068003614500191
R wherein 1And R 2Each can have the saturated or undersaturated aliphatic hydrocarbyl of 1-18 carbon atom of side chain naturally.Preferably, R 1And R 2One of be the saturated or undersaturated aliphatic hydrocarbyl that can have 1-16 carbon atom of side chain, and another is the saturated or undersaturated aliphatic hydrocarbyl that can have 3-16 carbon atom of side chain.More preferably, R 1And R 2Each can have the saturated or undersaturated aliphatic hydrocarbyl of 3-16 carbon atom of side chain naturally.Again preferably, R 1And R 2Each can have the saturated or undersaturated aliphatic hydrocarbyl of 4-12 carbon atom of side chain naturally.
Carnitine in described carnitine derivative part is the L-type normally.Described carnitine derivative comprises and has R 1And R 2Alpha-branched acyl group.Work as R 1And R 2Not simultaneously, the alpha-carbon atom on the branch point is not asymmetric carbon atom and produces optical isomer.Described optical isomer is not particularly limited.Can use any optical isomer and described mixture of isomers in the present invention.
Described carnitine derivative can stable for extended periods of time, and this may be because they comprise and have R 1And R 2Alpha-branched acyl group, this side chain reduced the effect of the power supply of ester bond so that in the presence of water-bearing media the hydrolysis difficulty of acyl group.
The example of described saturated aliphatic hydrocarbyl comprises for example methyl of line style or branched-alkyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, the 2-methyl amyl, the 3-methyl amyl, the 4-methyl amyl, the 2-ethyl-butyl, n-heptyl, 2-methyl hexyl, 3-methyl hexyl, 4-methyl hexyl, the 2-ethyl pentyl group, the 3-ethyl pentyl group, n-octyl, the 2-methylheptyl, the 3-methylheptyl, the 4-methylheptyl, the 5-methylheptyl, the 6-methylheptyl, the 2-ethylhexyl, the 3-ethylhexyl, the 4-ethylhexyl, 2-propyl group amyl group, n-nonyl, positive decyl, the n-undecane base, dodecyl, the n-tridecane base, the n-tetradecane base, the Pentadecane base, n-hexadecyl, the n-heptadecane base, n-octadecane base and iso stearyl.
The example of described undersaturated aliphatic hydrocarbyl comprises line style or branching thiazolinyl for example 10-undecenyl, 9-hexadecene base, cis-9-vaccenic acid base, 11-vaccenic acid base, cis, cis-9,12-18 carbon dialkylenes, 9,12,15-18 carbon trialkenyl, 6,9,12-18 carbon trialkenyl and 9,11,13-18 carbon trialkenyl.
R 1And R 2Preferred compositions comprise methyl/methyl, methyl/ethyl, methyl/n-pro-pyl, methyl/isopropyl, methyl/normal-butyl, methyl/n-pentyl, methyl/n-hexyl, methyl/n-octyl, methyl/positive decyl, methyl/n-tetradecane base, methyl/n-hexadecyl, ethyl/ethyl, ethyl/n-pro-pyl, ethyl/isopropyl, ethyl/normal-butyl, ethyl/isopropyl, ethyl/normal-butyl, ethyl/n-pentyl, ethyl/n-hexyl, ethyl/n-octyl, ethyl/positive decyl, ethyl/n-tetradecane base, ethyl/n-hexadecyl, n-pro-pyl/n-pro-pyl, n-pro-pyl/normal-butyl, n-pro-pyl/n-pentyl, n-pro-pyl/n-hexyl, normal-butyl/n-hexyl, normal-butyl/n-octyl and n-hexyl/n-octyl.Preparation for external application to skin of the present invention and cosmetics can comprise one or more and have R 1And R 2The carnitine derivative of various combination.
Embodiment by the carnitine derivative of formula (1) expression comprises known compound and noval chemical compound.Representational novel carnitine derivative below will be described.
Described novel carnitine derivative comprises the chemical compound by formula (3) expression:
Figure A20068003614500201
R wherein 3And R 4One of be the radical of saturated aliphatic alkyl that can have 1-16 carbon atom of side chain, and another is the radical of saturated aliphatic alkyl that can have 8-16 carbon atom of side chain.
The example of the radical of saturated aliphatic alkyl of 1-16 carbon atom comprises for example methyl of line style or branched-alkyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, the 2-methyl amyl, the 3-methyl amyl, the 4-methyl amyl, the 2-ethyl-butyl, n-heptyl, 2-methyl hexyl, 3-methyl hexyl, 4-methyl hexyl, the 2-ethyl pentyl group, the 3-ethyl pentyl group, n-octyl, the 2-methylheptyl, the 3-methylheptyl, the 4-methylheptyl, the 5-methylheptyl, the 6-methylheptyl, the 2-ethylhexyl, the 3-ethylhexyl, the 4-ethylhexyl, 2-propyl group amyl group, n-nonyl, positive decyl, the n-undecane base, dodecyl, the n-tridecane base, the n-tetradecane base, Pentadecane base and n-hexadecyl.The example of the radical of saturated aliphatic alkyl of 8-16 carbon atom comprises line style or branched-alkyl for example n-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2-propyl group amyl group, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base and n-hexadecyl.
The different embodiments of described novel carnitine derivative comprises the chemical compound by formula (5) expression:
R wherein 5And R 6One of be the radical of saturated aliphatic alkyl that can have 2-7 carbon atom of side chain, and another is the radical of saturated aliphatic alkyl that can have 3-7 carbon atom of side chain.
The example of the radical of saturated aliphatic alkyl of 2-7 carbon atom comprises line style or branched-alkyl for example ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl, 2-ethyl-butyl, n-heptyl, 2-methyl hexyl, 3-methyl hexyl, 4-methyl hexyl, 2-ethyl pentyl group and 3-ethyl pentyl group.The example of the radical of saturated aliphatic alkyl of 3-7 carbon atom comprises line style or branched-alkyl for example n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl, 2-ethyl-butyl, n-heptyl, 2-methyl hexyl, 3-methyl hexyl, 4-methyl hexyl, 2-ethyl pentyl group and 3-ethyl pentyl group.
Consider excellent skin affinity, R 5And R 6Preferred compositions comprise ethyl/n-pentyl, ethyl/n-hexyl, ethyl/n-heptyl, n-pro-pyl/normal-butyl, n-pro-pyl/n-pentyl, n-pro-pyl/n-hexyl, n-pro-pyl/n-heptyl, normal-butyl/normal-butyl, normal-butyl/n-pentyl, normal-butyl/n-hexyl, normal-butyl/n-heptyl, n-pentyl/n-pentyl, n-pentyl/n-hexyl, n-pentyl/n-heptyl, n-hexyl/n-hexyl, n-hexyl/n-heptyl and n-heptyl/n-heptyl.
Preferably, the R in the formula (1) 1And R 2One of or formula (3) in R 3And R 4One of be the linear alkyl of 6 carbon atoms, and another is the linear alkyl of 8 carbon atoms.That is to say especially preferably have the carnitine derivative of the combination of n-hexyl and n-octyl, particularly the L-carnitine 2-hexyldecanoic acid ester of following formula (7) expression.This carnitine derivative is especially stable in the presence of water-bearing media.
Figure A20068003614500221
In addition preferably, the R in the formula (1) 1And R 2One of or formula (3) in R 3And R 4One of be methyl, and another is the linear alkyl (just-myristyl) of 14 carbon atoms.Particularly, the L-carnitine 2-methyl palmitic acid ester of preferred following formula (9) expression.In addition preferably, the R in the formula (1) 1And R 2One of or formula (5) in R 5And R 6One of be the linear alkyl of 4 carbon atoms, and another is the linear alkyl of 6 carbon atoms.That is to say preferably have the carnitine derivative of the combination of normal-butyl and n-hexyl, particularly the L-carnitine 2-butyl caprylate of following formula (11) expression.
Figure A20068003614500231
The salt of＜carnitine derivative 〉
The salt that is used for the carnitine derivative of preparation for external application to skin of the present invention and cosmetics is represented by formula (2):
In formula (2), X -Be that cationic moiety with described carnitine derivative keeps electroneutral inorganic or organic anion.The anion that preferred medical science is allowed, the example comprises inorganic ions for example hydroxide ion, nitrate ion, sulfate ion, carbanion, bicarbonate ion and chloride ion; And organic ion for example formate ion, acetate ion, citrate ion, tartrate anion ion, oxalate denominationby, fumarate ion, the saturated or undersaturated fatty acid anion that can have 3-20 carbon atom of side chain, carnitine anion, carnitine derivative anion, ascorbic acid root anion, Ascorbic acid 2-phosphate anion and Ascorbic acid 2-phosphate derivant anion.Wherein, consider the compatibility in preparation for external application to skin, particularly cosmetics, preferred hydroxide ion, chloride ion, citrate ion, carnitine anion and carnitine derivative anion.
In formula (2), Y +Be that anionicsite with described carnitine derivative keeps electroneutral inorganic or organic cation.The cation that preferred medical science is allowed, the example comprises hydrion, sodium ion, potassium ion, calcium ion, magnesium ion, zinc ion, ammonium ion, carnitine cation and carnitine derivative cation.Wherein, consider the compatibility in preparation for external application to skin, particularly cosmetics, preferred hydrion, sodium ion, potassium ion, carnitine cation and carnitine derivative cation.
In formula (2), R 1And R 2Suc as formula defined in (1).
Preparation for external application to skin of the present invention and cosmetics can comprise one or more and have X -, Y +, R 1And R 2The salt of carnitine derivative of various combination.
Salt by the carnitine derivative of formula (2) expression comprises known compound and noval chemical compound.The salt of representational new carnitine derivative below will be described.
The embodiment of the salt of described new carnitine derivative comprises the chemical compound by formula (4) expression:
Figure A20068003614500241
R wherein 3And R 4Suc as formula defined in (3), and X -And Y +Suc as formula defined in (2).
The different embodiments of the salt of described new carnitine derivative comprises the chemical compound by formula (6) expression:
Figure A20068003614500251
R wherein 5And R 6Suc as formula defined in (5), and X -And Y +Suc as formula defined in (2).
Preferably, the R in the formula (2) 1And R 2One of or formula (4) in R 3And R 4One of be the linear alkyl of 6 carbon atoms, and another is the linear alkyl of 8 carbon atoms.That is to say especially preferably have the salt of carnitine derivative of the combination of n-hexyl and n-octyl, particularly the salt of the L-carnitine 2-hexyldecanoic acid ester of following formula (8) expression.The carnitine derivative that comes from this salt is especially stable in the presence of water-bearing media.
Figure A20068003614500252
X wherein -And Y +Suc as formula defining in (2).
In addition preferably, the R in the formula (2) 1And R 2One of or formula (4) in R 3And R 4One of be methyl, and another is the linear alkyl (just-myristyl) of 14 carbon atoms.Particularly, the salt of the L-carnitine 2-methyl palmitic acid ester of preferred following formula (10) expression.In addition preferably, the R in the formula (2) 1And R 2One of or formula (6) in R 5And R 6One of be the linear alkyl of 4 carbon atoms, and another is the linear alkyl of 6 carbon atoms.That is to say preferably have the salt of carnitine derivative of the combination of normal-butyl and n-hexyl, particularly the salt of the L-carnitine 2-butyl caprylate of following formula (12) expression.
Figure A20068003614500261
X wherein -And Y +Suc as formula defined in (2).
The preparation of＜carnitine derivative and salt thereof 〉
Can for example pass through the reaction of L-carnitine class and fatty acid acyl chlorides class by synthetic carnitine derivative and the salt thereof that is used for preparation for external application to skin of the present invention and cosmetics of the commercially available L-carnitine class that gets.
For example, the synthetic of L-carnitine 2-hexyldecanoic acid ester hydrochloride will be described below.In trifluoroacetic acid, mix L-carnitine and 2-hexyldecanoic acid acyl chlorides, then heat down and stir to react at 50-80 ℃.After this, by distilling out trifluoroacetic acid, and in residue, add petroleum ether, in this residue, add water so that described acyl chlorides quencher with its recovery.Then, in described residue, add ethanol and diethyl ether, separate the water-ethanol phase with its extraction.Water-ethanol and n-butyl alcohol are merged and wash with water as required.Distill out n-butyl alcohol to obtain L-carnitine 2-hexyldecanoic acid ester hydrochloride.
Example as the carnitine of the raw material of preparation described carnitine derivative and salt thereof comprises inner salt, inorganic salt for example hydrochlorate and sodium salt, and organic salt for example oxalates, tartrate and fumarate.
＜preparation for external application to skin and cosmetics 〉
Described preparation for external application to skin and cosmetics, the cosmetics that particularly improve lipid metabolism contain above-mentioned carnitine derivative and/or its salt.The described cosmetics that improve lipid metabolism are to be intended to improve skin problem and aging and the fat cosmetics relevant with the lipid metabolism effect of going down with prevention and excessive lipid.The example of the Expected Results of these cosmetics comprises fat-reducing, prevents liparitosis, skin-tightening, prevent owing to glossy and fatty skin due to the excess sebum and the dressing effect of being made dirty (smearedmakeup), improve and prevention seborrheic dermatitis and the alopecia that causes thus, prevent acne, prevent body odour and by promoting that lipid changes into energy and resisting age of skin, activation skin and nursing skin.
In the total amount of described preparation for external application to skin, the content of carnitine derivative and/or its salt is generally 0.01-20 quality %, preferred 0.05-12 quality %, more preferably 0.1-5 quality %.This scale shows when using separately in described carnitine derivative or its salt any its content, and when being used in combination this carnitine derivative and salt thereof their content.
When described preparation for external application to skin contained the carnitine derivative of above-mentioned amount and/or its salt, carnitine derivative and/or its salt infiltrated skin and generation effect as required fast.
Described cosmetics and the cosmetics that improve lipid metabolism contain carnitine derivative and/or its salt of above-mentioned amount with regard to preparation for external application to skin ideally.
Described preparation for external application to skin and cosmetics can contain other components commonly used in general preparation for external application to skin and cosmetics, still reach effect of the present invention simultaneously.
Described component comprises:
Hydrocarbon, for example ceresine (ozokerite), alpha-olefin low polymers, light isoparaffins, light liquid isoparaffin, Squalene, squalane, synthetic squalane, plant squalane, ceresine (ceresin), paraffin, polyethylene powders, polybutene, microwax, liquid isoparaffin, liquid paraffin, mineral oil and vaseline;
Natural fat and oil, native paraffin for example, it comprises Jojoba oil, Brazil wax, candelilla wax, rice bran wax, Lac, lanoline, ermine oil wax, spermaceti, sugarcane wax, sperm oil, Cera Flava and montan wax; American Avocado Tree oil, almond oil, olive oil, special excellent virgin oil, Oleum sesami, Testa oryzae oil, rice oil (rice oil), rice germ oil, Semen Maydis oil, soybean oil, maize embryo oil, peach kernel oil, palm-kernel oil, Petiolus Trachycarpi oil, Oleum Ricini, Oleum Vitis viniferae, Oleum Gossypii semen, Oleum Cocois, hydrogenated coconut oil, Adeps Bovis seu Bubali, hydrogenated oil and fat, house oil, ermine oil, egg oil, the egg yolk fatty oil, the Flos Rosae Multiflorae fruit oil, kukui nut oil, Radix Oenotherae erythrosepalae oil, wheat germ oil, Oleum Arachidis hypogaeae semen, Camellia oil, oil tea oil, cocoa butter, haze tallow, Os Bovis seu Bubali fat, neat's foot oil, Adeps Sus domestica, horse fat, Adeps caprae seu ovis, Adeps Bovis seu Bubali resin, macadamia oil and spiraea oil;
Fatty acid, for example lauric acid, myristic acid, Palmic acid, stearic acid, behenic acid, oleic acid, isostearic acid, 12-hydroxy stearic acid, 9-undecylenic acid and fatty acid distribution of coconut oil;
Higher alcohol, for example isooctadecanol, octyldodecanol, hexyldecanol, cholesterol, plant sterol, lauryl alcohol, myristyl alcohol, spermol, stearyl alcohol, oleyl alcohol, behenyl alcohol and 16 octadecanol mixture;
Alkyl glycerylether, for example batilol .alpha.-hexadecylglyceryl ether, selachyl alcohol and iso stearyl glycerin ether;
Ester, for example isopropyl myristate, butyl myristate, palm fibre eleostearic acid isopropyl ester, ethyl stearte, butyl stearate, ethyl oleate, Ethyl linoleate, the linoleic acid isopropyl ester, sad cetyl ester, lauric acid hexyl ester, the different monooctyl ester of myristic acid, myristic acid ester in the last of the ten Heavenly stems, myristyl myristate, the myristic acid cetyl ester, the myristic acid stearyl, the Palmic acid cetyl ester, the stearic acid stearyl, decyl oleate, oleic acid oil base ester, the ricinoleic acid cetyl ester, lauric acid iso stearyl ester, myristic acid isotridecyl ester, myristic acid isocetyl ester, myristic acid iso stearyl ester, myristic acid octyl group dodecyl ester, Palmic acid 2-Octyl Nitrite, Palmic acid isocetyl ester, Palmic acid iso stearyl ester, stearic acid 2-Octyl Nitrite, stearic acid isocetyl ester, Ceraphyl 140A, oleic acid octyl group dodecyl ester, ricinoleic acid octyl group dodecyl ester;
The isostearic acid ethyl ester, the isostearic acid isopropyl ester, the 2 ethyl hexanoic acid cetyl ester, 2 ethyl hexanoic acid cetyl stearyl, the 2 ethyl hexanoic acid stearyl, the own ester of isostearic acid, Ethylene glycol dicaprylate, two oleic acid glycol esters, two sad propylene glycol esters, two (sad capric acid) propylene glycol ester, the didecyl acid propylene glycol ester, two oleic acid propylene glycol esters, two capric acid DOPCP, two sad DOPCP, tricaprylin, three-2 ethyl hexanoic acid glyceride, three (sad capric acid) glyceride, three (sad capric acid stearic acid) glyceride, three (hendecanoic acid) glyceride, three different tripalmitins, three glyceryl isostearates, three-2 ethyl hexanoic acid trihydroxymethylpropanyl ester, three isostearic acid trihydroxymethylpropanyl esters, four-2 ethyl hexanoic acid pentaerythritol ester, four myristic acid pentaerythritol esters;
Four isostearic acid pentaerythritol esters; four isostearic acids, two glyceride; Elefac I 205; sad isocetyl ester; sad iso stearyl ester; different n-nonanoic acid 2-Octyl Nitrite; the sad hexyl of dimethyl ester in the last of the ten Heavenly stems; the misery basic dodecyl ester of dimethyl-octa; different Palmic acid 2-Octyl Nitrite; isostearic acid isocetyl ester; isostearic acid iso stearyl ester; isostearic acid octyl group dodecyl ester; Lauryl lactate; lactic acid meat myristyl ester; the lactic acid cetyl ester; lactic acid octyl group dodecyl ester; triethyl citrate; acetyl triethyl citrate; acetyl tributyl citrate; trioctyl lemon acid; citric acid three isocetyl esters; citric acid trioctylphosphine dodecyl ester; malic acid two iso stearyl esters; hydroxy stearic acid 2-Octyl Nitrite; succinic acid two-2-Octyl Nitrite; diisopropyl adipate; diisobutyl adipate; dioctyl adipate; adipic acid diheptyl undecyl ester; ethyl sebacate; Dermol DIPS; di-n-octyl sebacate;
Cholesteryl stearate, the isostearic acid cholesterol ester, the hydroxy stearic acid cholesterol ester, Cholesterol 3.beta.-oleate, oleic acid dihydrocholesterol ester, the isostearic acid plant sterol ester, the oleic acid plant sterol ester, 12-stearyl hydroxy stearic acid isocetyl ester, 12-stearyl hydroxy stearic acid stearoyl ester, 12-stearyl hydroxy stearic acid isostearoyl ester, polyoxyethylene (3) polyoxypropylene (1) cetyl ether acetas, polyoxyethylene (3) polyoxypropylene (1) isocetyl ether acetic acid ester, isononyl isononanoate, different octyl pelargonate, different n-nonanoic acid tridecyl ester and different n-nonanoic acid isotridecyl ester;
Silicone oil, for example methyl polysiloxane, methyl phenyl silicone, methylhydrogenpolysi,oxane, the methyl cyclopolysiloxane, octamethylcy-clotetrasiloxane, decamethylcyclopentaandoxane, ten diformazan basic rings, six siloxanes, octamethyltrisiloxane, decamethyl tetrasiloxane, tetradecamethylhexasiloxane, highly polymeric methyl polysiloxane, dimethyl siloxane/methyl (polyoxyethylene) siloxanes/methyl (polyoxypropylene) silicone copolymers, dimethyl siloxane/methyl (polyoxyethylene) silicone copolymers, dimethyl siloxane/methyl (polyoxypropylene) silicone copolymers, dimethyl siloxane/methyl hexadecane oxygen radical siloxane copolymer, the stearic oxygen radical siloxane of dimethyl siloxane/methyl copolymer, polyether-modified silicones, the silicones of alcohol modification, alkyl-modified silicones and amino modified silicones;
Polymer, for example sodium alginate, carrageenin, agar, Furcellaran (furcelleran), Guar gum (cyamoposis gum) Wen pears seed, konjacmannan, tamarind gum, tower draws locust beam gum, dextrin, locust bean gum, Radix Acaciae senegalis, dawa gum (ghatti gum), karaya, Tragacanth, arabinogalactan, pectin, outer coffin (marmelo), chitosan, starch, hot gel (curdlan), xanthan gum, gellan gum, cyclodextrin, dextran, amylopectin, microcrystalline Cellulose, methylcellulose, ethyl cellulose, hydroxyethyl-cellulose, hydroxypropyl cellulose, hydroxypropyl emthylcellulose, carboxymethyl cellulose, carboxyl starch, Poise C-80M, starch phosphate, the cationization Guar gum, carboxymethyl/hydroxypropylation Guar gum, the hydroxypropylation Guar gum, albumin, casein, gelatin, sodium polyacrylate, polyacrylic acid amide, CVP Carbopol ETD2050, polymine;
Highly polymeric Polyethylene Glycol; polyvinyl alcohol, polyvinyl pyrrolidone; polyvinylether; polyacrylamide; acrylic copolymer; methacrylic acid copolymer; maleic acid; vinylpyridine copolymer; ethylene/acrylic acid copolymer; vinyl pyrrolidone polymer; vinyl alcohol/vinylpyrrolidone copolymer; the acrylamide polymer that nitrogen replaces; amino modified siloxanes; cationic polymer; dimethyl propylene enoyl-ammonium polymer; the acrylic anionic polymer; the methacrylic acid group anionic polymer; modified siloxane; acrylic acid/metering system dialkylaminobenzoic acid (C 10-30) ester copolymer and polyoxyethylene/polyoxypropylene copolymer;
Lower alcohol, for example ethanol, isopropyl alcohol, 1-butanols, 2-butanols and benzylalcohol;
Polyhydric alcohol, for example ethylene glycol, diethylene glycol, Polyethylene Glycol, propylene glycol, polypropylene glycol, glycerol, diglycerol, polyglycereol, 1,3 butylene glycol, 2,2'-ethylenedioxybis(ethanol)., dipropylene glycol, 3-methyl isophthalic acid, 3-butanediol, 1,2-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 3-methyl isophthalic acid, 5-pentanediol, 1,2-hexanediol and 1,6-hexanediol;
Anion surfactant, for example fatty acid distribution of coconut oil potassium, fatty acid distribution of coconut oil sodium, the fatty acid distribution of coconut oil triethanolamine, potassium laurate, sodium laurate, the lauric acid triethanolamine, potassium myristate, Sodium myristate, the myristic acid isopropanolamine, potassium palmitate, sodium palmitate, the Palmic acid isopropanolamine, potassium stearate, sodium stearate, triethanolamine stearate, potassium oleate, enuatrol, Castor Oil Fatty Acid sodium, Zinc Undecenoate, Dodecanoic acid, zinc salt, Grillocin P 176, magnesium myristate, Hexadecanoic acid, zinc salt, zinc stearate, calcium stearate, magnesium stearate, aluminium stearate, calcium myristate, magnesium myristate, two aluminium myristates, isostearic acid aluminum;
Polyoxyethylene lauryl ether acetic acid; the polyoxyethylene lauryl ether sodium acetate; polyoxyethylene tridecyl ether acetic acid; polyoxyethylene tridecyl ether sodium acetate; sodium stearoyl lactate; the isostearoyl sodium lactate; sodium lauroyl sarcosine; the fatty acid distribution of coconut oil sarcosine; the fatty acid distribution of coconut oil sodium sarcosinate; fatty acid distribution of coconut oil sarcosine triethanolamine (sarcosine triethanolamine coconut fatty acid); Hamposyl L; potassium lauroyl sarcosine; the Hamposyl L triethanolamine; N-Oleoylsarcosine; myristoyl-N-methylaminoacetic acid sodium; stearoyl-glutamic acid sodium; the fatty acid distribution of coconut oil acyl glutamic acid; fatty acid distribution of coconut oil acyl glutamic acid potassium; fatty acid distribution of coconut oil acyl glutamic acid sodium; the fatty acid distribution of coconut oil acyl glutamic acid triethanolamine; the lauroyl acyl glutamic acid; lauroyl acyl glutamic acid potassium; lauroyl acyl glutamic acid sodium; the lauroyl acyl glutamic acid triethanolamine; the myristoyl acyl glutamic acid; myristoyl acyl glutamic acid potassium; myristoyl acyl glutamic acid sodium; the stearyl acyl glutamic acid; stearyl acyl glutamic acid potassium; stearyl acyl glutamic acid disodium; hydrogenated tallow acyl glutamic acid sodium; fatty acid distribution of coconut oil/hydrogenated tallow acyl glutamic acid sodium; fatty acid distribution of coconut oil methylalanine sodium; the lauroyl methylalanine; lauroyl methylalanine sodium; lauroyl methylalanine triethanolamine; myristoyl methylalanine sodium; lauroyl N-methyltaurine sodium; fatty acid distribution of coconut oil N-methyltaurine potassium; fatty acid distribution of coconut oil N-methyltaurine sodium; fatty acid distribution of coconut oil N-methyltaurine magnesium; myristoyl N-methyltaurine sodium; palmityl N-methyltaurine sodium; stearyl N-methyltaurine sodium; oleoyl N-methyltaurine sodium; alkane sulfonate; the tetradecene sodium sulfonate; Sodium docusate; 2-Sulfosuccinic acid lauryl disodium; coconut oil fat acetoacetic ester sodium sulfonate; sodium lauryl sulfate; triethanolamine lauryl sulfate; sodium hexadecyl sulfate; triethanolamine alkyl sulfate (11; 13; 15); alkyl sodium sulfate (12; 13); triethanolamine alkyl sulfate (12; 13); alkylsurfuric acid ammonium (12; 14; 16); diethanolamine alkyl sulfate (12; 13); triethanolamine alkyl sulfate (12-14); triethanolamine alkyl sulfate (12-15); triethanolamine cocos nucifera oil alkylsurfuric acid magnesium; ammonium lauryl sulfate; lauryl potassium sulfate; lauryl magnesium sulfate; the monoethanolamine lauryl sulfate; the diethanolamine lauryl sulfate;
Myristyl sodium sulfate, stearyl sodium sulfate, oil base sodium sulfate, the triethanolamine oleyl sulfate, polyoxyethylene lauryl ether sodium sulfate, triethanolamine polyoxyethylene lauryl ether sulfate, polyoxyethylene (1) alkyl (11,13,15) ether sodium sulfate, triethanolamine polyoxyethylene (1) alkyl (11,13,15) ether sulfate, polyoxyethylene (3) alkyl (11-15) ether sodium sulfate, polyoxyethylene (2) alkyl (12,13) ether sodium sulfate, polyoxyethylene (3) alkyl (12-14) ether sodium sulfate, polyoxyethylene (3) alkyl (12-15) ether sodium sulfate, polyoxyethylene (2) sodium laureth sulfate, polyoxyethylene (3) myristyl ether sodium sulfate, higher fatty acids alkanolamide sodium sulfate, lauryl phosphoric acid, the lauryl sodium phosphate;
Potassium cetyl phosphate, DEA-CETYL PHOSPHATE, polyoxyethylene oleyl ether phosphoric acid, polyoxyethylene lauryl ether phosphoric acid, the polyoxyethylene lauryl ether sodium phosphate, Polyoxyethylene cetyl ether phosphoric acid, the Polyoxyethylene cetyl ether sodium phosphate, polyoxyethylene stearyl acyl ether phosphoric acid, polyoxyethylene oleyl ether phosphoric acid, the polyoxyethylene oleyl ether sodium phosphate, polyoxyethylene alkyl phenyl ether phosphoric acid, the polyoxyethylene alkyl phenyl ether sodium phosphate, the polyoxyethylene alkyl phenyl ether nitranol, polyoxyethylene Octyl Ether phosphoric acid, polyoxyethylene (10) alkyl (12,13) ether phosphoric acid, polyxyethylated (12-15) ether phosphoric acid, polyxyethylated (12-16) ether phosphoric acid, polyoxyethylene lauryl ether nitranol and polyoxyethylene oleyl ether p diethylaminobenzoic acid hydramine;
Cationic surfactant, for example dioctylamine, the dimethyl stearic amine, three lauryl amines, stearic acid diethyl amino yl acetamide, lauryl trimethyl ammonium chloride, hexadecyltrimethylammonium chloride, cetyl trimethyl ammonium bromide, the cetyl trimethyl Saccharin Ammonium salt, the stearyl trimethyl ammonium chloride, alkyl (20-22) trimethyl ammonium chloride, the lauryl trimethylammonium bromide, alkyl (16,18) trimethyl ammonium chloride, the stearyl trimethylammonium bromide, stearyl trimethyl Saccharin Ammonium salt, alkyl (28) trimethyl ammonium chloride, two (polyoxyethylene) oil base ammonio methacrylate (2EO), two polyoxy ethylene stearyl ammonio methacrylates, polyoxyethylene (1) polyoxypropylene (25) diethylmethyl ammonium chloride, three (polyoxyethylene) stearyl chlorination ammonium (5EO), VARISOFT TA100;
Dialkyl group (12-15) alkyl dimethyl ammonium chloride, dialkyl group (12-18) alkyl dimethyl ammonium chloride, dialkyl group (14-18) alkyl dimethyl ammonium chloride, two cocoyl alkyl dimethyl ammonium chlorides, two cetyl alkyl dimethyl ammonium chlorides, iso stearyl lauryl dimethyl ammonium chloride, benzalkonium chloride, the myristyl dimethyl benzyl ammonium chloride, lauryl dimethyl (Ethylbenzyl) ammonium chloride, the stearyl dimethyl benzyl ammonium chloride, lauryl chloride pyridine, hexadecylpyridinium chloride, lauroyl gallbladder carbamoyl methyl chloropyridine, stearyl gallbladder carbamoyl methyl chloropyridine, alkyl bromination isoquinolin, methyl benzethonium chloride and benzethonium chloride;
Amphoteric surfactant, for example 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazole quinoline betanin, alkyl diamino ethyl glycine hydrochloride, lauryl diamino ethyl Glycine sodium, undecyl hydroxyethyl imidazole betanin sodium, undecyl-N-carboxymethyl imidazoles betanin, acyl group-N-carboxyethyl-N-hydroxyethyl-ethylenediamine disodium coconut oil fat acid esters, acyl group-N-carboxyl ethoxyethyl group-N-carboxyethyl ethylenediamine disodium coconut oil fat acid esters, acyl group-N-carboxyl methoxy ethyl-N-carboxymethyl ethylenediamine disodium coconut oil fat acid esters, lauryl alanine sodium, the amino dipropionic acid of lauryl, triethanolamine lauryl aminopropionate, acyl group-N-carboxyethyl-N-hydroxyethyl-ethylenediamine sodium palm oil fatty acid ester, betanin lauryl dimethyl Glycinates, betanin cocos nucifera oil alkyl dimethyl Glycinates, betanin stearyl dimethylamino acetate, stearyl dimethyl betaine sodium, amido propyl betaine coconut oil fat acid esters, amido propyl betaine palm oil fatty acid ester, lauric amide betanin propyl-acetic acid ester, the amido propyl betaine ricinoleate, stearyl dihydroxy ethyl betanin and lauryl hydroxyl sulfo betaine;
Non-ionic surface active agent, for example polyoxyethylene (10) alkyl (12,13) ether, polyoxyethylene lauryl ether, Polyoxyethylene cetyl ether, polyoxyethylene stearyl base ether, polyoxyethylene oleyl ether, polyoxyethylene (3,7,12) alkyl (12-14) ether, the polyoxyethylene tridecyl ether, the polyoxyethylene myristyl ether, polyoxyethylene-secondary alkyl (14) ether, polyoxyethylene isocetyl ether, polyoxyethylene palmityl/octadecyl ether, polyoxyethylene (2,10,20) iso stearyl ether, polyoxyethylene oil base cetyl ether, polyoxyethylene (20) Semen arachidis hypogaeae ether, polyoxyethylene octyl group lauryl ether, Ju oxygen ethylene Shan Yu base ether, NONIN HS 240;
The polyoxyethylene nonylplenyl ether, the polyoxyethylene dinonyl phenyl ether, polyoxyethylene (1) polyoxypropylene (1,2,4,8) cetyl ether, polyoxyethylene (5) polyoxypropylene (1,2,4,8) cetyl ether, polyoxyethylene (10) polyoxypropylene (1,2,4,8) cetyl ether, polyoxyethylene (20) polyoxypropylene (1,2,4,8) cetyl ether, the polyoxyethylene polyoxypropylene lauryl ether, polyoxyethylene (3) polyoxypropylene (34) stearyl ether, polyoxyethylene (4) polyoxypropylene (30) stearyl ether, polyoxyethylene (34) polyoxypropylene (23) stearyl ether, the polyoxyethylene polyoxypropylene cetyl ether, polyoxyethylene polyoxypropylene decyl myristyl ether;
Polyethylene glycol monolaurate, ethylene glycol monostearate, polyethylene glycol mono stearate, polyethylene glycol monooleate, glycol fatty acid ester, but the ethylene glycol monostearate of self emulsifying, diethylene glycol monolaurate, the Polyethylene Glycol myristinate, the Polyethylene Glycol cetylate, diethylene glycol distearate, but the Polyethylene Glycol of self emulsifying (2) monostearate, polyethylene glycol isostearate, glycol dicaprylate, the diethylene glycol dilaurate, polyethylene glycol dilaurate, Polyethylene Glycol (150) dipalmitate, glycol distearate, diethylene glycol distearate, polyglycol distearate, the ethylene glycol bisthioglycolate oleate, the Polyethylene Glycol dioleate;
Polyethylene Glycol two ricinoleates, polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (6) sorbitan monostearate, polyoxyethylene (20) sorbitan monostearate, polyoxyethylene (20) sorbitan tristearate, polyoxyethylene (6) dehydrated sorbitol mono-fatty acid ester, polyoxyethylene (20) dehydrated sorbitol mono-fatty acid ester, polyoxyethylene (20) sorbitan trioleate, sorbitan polyoxyethylene (20) coconut oil fat acid esters, polyoxyethylene (10-80) sorbitan monolaurate, the polyoxyethylene sorbitan tristearate, polyoxyethylene (20) sorbitan isostearate, polyoxyethylene (150) sorbitan tristearate;
Polyoxyethylene castor oil, polyoxyethylene hydrogenated Oleum Ricini, polyoxyethylene (10) castor oil hydrogenated, polyoxyethylene (20) castor oil hydrogenated, polyoxyethylene (40) castor oil hydrogenated, polyoxyethylene (50) castor oil hydrogenated, polyoxyethylene (60) castor oil hydrogenated, the lipotropy glyceryl monostearate, the lipotropy glycerin mono-fatty acid ester, but the glyceryl monostearate of self emulsifying, the coconut oil fat acid glyceride, glyceryl laurate ester, myristin, glyceryl isostearate, ricinoleic acid glyceride, the monohydroxy tristerin, olein, glyceryl linoleate, erucic acid glyceride behenic acid glyceride, the wheat germ oil fatty glyceride, the safflower oil fatty glyceride, the hydrogenated soybean oil fatty glyceride, saturated fatty acid glyceride;
Cottonseed oil fatty acid glyceride, glycerol list isostearic acid list myristinate, single tallow acid glyceride, single glyceryl Pilus Caprae seu Ovis fatty acid, the glyceryl sesquioleate, the glyceryl distearate, the glyceryl diisopstearate, glyceryl two Semen arachidis hypogaeae acid esters, sorbitan monolaurate, the sorbitan monopalmitate, sorbitan monostearate, sorbitan list isostearate, dehydrated sorbitol mono-fatty acid ester, the sorbitan sesquistearate, NOFABLE SO-992 NOFABLE SO-902, the sorbitan tristearate, sorbitan trioleate, sorbitan coconut oil fat acid esters, sorbitan isostearate, sorbitan sesquialter isostearate, dehydrated sorbitol distearate, the different cetylate of diglycerol, poly-(4-10) glyceryl monolaurate, poly-(10) monomyristin, poly-(2-10) glycerol monostearate, poly-(2-10) glyceryl list isostearate, poly-(2-10) glycerin mono-fatty acid ester, the diglycerol sesquioleate;
Poly-(2-10) glyceryl diisopstearate, poly-(6-10) glyceryl distearate, diglycerol three isostearates, poly-(10) glyceryl tristearate, poly-(10) glyceryl trioleate, poly-(2) glyceryl tetraoctyl stearate, ten glyceryl the five kinds of stiffness in infant fat acid esters, poly-(6-10) glyceryl five oleates, poly-(10) glyceryl seven stearates, ten glyceryls, ten stearates, poly-(10) glyceryl ten oleates, poly-(6) glyceryl ricinoleate of condensation, sucrose fatty acid ester, sucrose coconut oil fat acid esters, alkyl androstanediol, the cocos nucifera oil alkyl dimethyl amine oxide, lauryl dimethyl amine oxide, the dihydroxy ethyl lauryl dimethyl amine oxide, stearyl dimethyl oxidation amine, oil base dimethyl oxidation amine and polyoxyethylene cocos nucifera oil alkyl dimethyl amine oxide;
Natural surfactant, for example saponin, lecithin, soybean phospholipid, hydrogenated soya phosphatide, Semen sojae atricolor lysophosphatide, hydrogenated soybean lysophosphatide, Ovum Gallus domesticus Flavus lecithin, hydrogenation egg yolk LYSO-PHOSPHATIDYLCHOLINE LYSOPC, phosphatidyl choline, PHOSPHATIDYL ETHANOLAMINE, Phosphatidylserine, sphingomyelins, sphingomyelin, ganglioside, bile acid, cholic acid, deoxycholic acid, sodium cholate, NaTDC, perverse spore .gamma.-keto-.beta.-methoxy-.delta.-methylene-.DELTA..alpha.-hexenoic acid. (spiculisporic acid), rhamnolipid, Sargassum glycolipid, sophorolipid and mannose erithritol fat;
UV absorbers, comprise para-amino benzoic acid, the para-amino benzoic acid derivant is ethylaminobenzoate for example, para-amino benzoic acid glyceride, ESCAROL 507 pentyl ester and ESCAROL 507 2-Octyl Nitrite, cinnamic acid derivative is benzyl cinnamate for example, glyceryl di-p-methoxy cinnamic acid list-2-ethylhexanoate, 2,4-diisopropyl methyl cinnamate, 2,4-diisopropyl ethyl cinnamate, p-methoxycinnamic acid potassium, p-methoxycinnamic acid sodium, the p-methoxycinnamic acid isopropyl ester, p-methoxycinnamic acid 2-Octyl Nitrite, to methoxyl group cinnamon acid 2-ethoxy ethyl ester with to the ethoxy-cinnamic acid ethyl ester, urocanic acid, the urocanic acid derivant is the urocanic acid ethyl ester for example
Benzophenone derivates for example 2, the 4-dihydroxy benaophenonel, 2,2 ', 4,4 '-tetrahydroxybenzophenone, 2-hydroxyl-4-methoxyl group-5-diphenylsulfone ketone sodium, 2-hydroxyl-4-methoxy benzophenone-5-sulfonic acid, 2-hydroxyl-4-methoxy benzophenone, 2,2 '-dihydroxy-4,4 '-dimethoxy-benzophenone and 2,2 '-dihydroxy-4,4 '-dimethoxy-5-diphenylsulfone ketone sodium, salicyclic acid derivatives is glycol salicylate for example, salicylic acid 2-Octyl Nitrite, phenyl salicytate, benzyl salicylate, TBS., high menthyl ester of salicylic acid and salicylic acid 3,3,5-3-methyl cyclohexanol ester, 2-(2 '-hydroxyl-5 '-methoxyphenyl) benzotriazole and the 4-tert-butyl group-4 '-methoxy benzoylmethane;
Powder and colored materials, the for example plain powder of Kaolin, silicic acid anhydride, aluminium magensium silicate, sericite, Talcum, boron nitride, Muscovitum, montorillonite clay, hemp, wheaten starch, silk powder, corn starch, nitro dye, azo dye, nitroso-dyes, triphenhlmethane dye, xanthene dye, quinoline dye, anthraquinone dye, bipseudoindoxyl dye, pyrene dyestuff, phthalocyanine dye,
Natural dye, it comprises flavonoid, quinones, porphyrin, water solublity annatto, the Ink sepiellae seu sepiae powder, caramel, guaiene (guaiazulene), gardenia blue, Gardenia Yellow, cochineal, shikonin, Sodium Copper Chlorophyllin, the capsanthin dyestuff, Flos Carthami is red, safflower yellow, laccaic acid and riboflavin butyrate, white carbon black, yellow iron oxide, black iron oxide, red iron oxide, barba hispanica, ultra marine blue, zinc oxide, chromium oxide, titanium oxide, black oxidation titanium, zirconium oxide, chromic oxide gel, aluminium oxide, magnesium oxide, barium sulfate, aluminium hydroxide, calcium carbonate, lithium cobalt titanate, manganese violet and pearlescent pigment;
Plant extract, angelica keiskei koidzumi extract for example, the gambir extract, the American Avocado Tree extract, pool eight silk ball leaf extracts (hydrangea serrata leaf) extract, Herb Gynostemmae Pentaphylli extract, the Herba Gynostemmatis extract, the arnica montana extract, oil-soluble arnica montana extract, the Semen Armeniacae Amarum extract, Aloe extract, the benzoin resin extract, Semen Ginkgo extrac, the Herba Urticae Cannabinae extract, the orrisroot extract, Fructus Foeniculi extract, Rhizoma Curcumae Longae extract, the Rosehips extract, the SONGGUOJU leaf extract, the scutellariae,radix extract, Cortex Phellodendri belongs to bark extract, the Rhizoma Coptidis rhizome extract, the Fructus Hordei Germinatus seed extract, the Flos abelmoschi manihot extract, Herba Hyperici Erecti (hypericum erectum) extract, oil-soluble Herba Hyperici Erecti extract, the Herba Lamii albi flower extract, oil-soluble Herba Lamii albi flower extract, the Radix Ononis hircinae extract, Nasturtium officinale (nasturtiumofficinale) extract, Orange Blossom water, Fructus Kaki tannin (kaki tannin), Radix Puerariae extract, Rhizoma et radix valerianae extract, the Herba Typhae extract, chamomile extract, the oil-soluble chamomile extract, Chamomile water, oat extract, Radix Dauci Sativae extract, the oil-soluble Radix Dauci Sativae extract, carrot oil, the Herba Artemisiae Scopariae extract, Radix Glycyrrhizae extract, the Radix Glycyrrhizae extract powder, flavonoids of Glycyrrhiza, the Mylabris tincture, Fructus Rubi extract, Fructus actinidiae chinensis extract, the Peruvian bark tree peel extract;
Fructus Cucumidis sativi extract, Semen Armeniacae Amarum (apricot kernel) extract Fructus cydoniae oblongae seed extract, the Fructus Gardeniae extract, the Sasa veitchii(Carr.)Rehd. extract, Sophora narrow leaf (sophora angustifolia) extract, the Endocarpium Juglandis extract, the Radix clematidis floridae extract, the brown sugar extract, chlorella extract, mulberry extract, Cortex Cinnamomi, Radix Gentianae extract, Flos Pelargonii medicinal herbs extract, Folium Camelliae sinensis extract, the Flos nymphaeae (Nymphaea teragona Georgi) extract, Radix Arctii extract, the oil-soluble Radix Arctii extract, wheat malt germ extract, the wheat flour of hydrolysis, the Testa oryzae extract, the Testa oryzae fermented product extract, the comfrey extract, asarum (asiasarum) root extract, the Stigma Croci extract, the Saponaria officinalis extract, the oil-soluble sage extract, Crataegi cuneatae (crataegus cuneata) fruit extract, Pericarpium Zanthoxyli belongs to (xanthoxylum) extract, Lentinus Edodes extract, the Lentinus Edodes extract powder, Radix Rehmanniae extract, the syconium extract, oil-soluble syconium extract, Japan's Herba Ocimi extract (Herba Ocimi Pilosi extract), the bodhi tree extract, oil-soluble bodhi tree extract, Ramulus et Folium Spiraeae Salicifolia (filipendula multijuga) extract, crude drug (crude drug) extract, the Semen Coicis seed extract, Rhizoma Zingiberis Recens extract, the oil-soluble Rhizoma Zingiberis Recens extract, the Rhizoma Zingiberis Recens tincture, the Rhizoma Acori Graminei extract, the sprout of birch extract, oil-soluble sprout of birch extract, sprout of birch liquid, Radix Ophiopogonis extract, Herba Equiseti Arvinsis extract, the oil-soluble Herba Equiseti Arvinsis extract;
Increase spermin, Stevia rebaudiana (Bertoni) Hemsl extract, Caulis Hederae Sinensis extract, the Crataegus Oxyacantha extract, the Fols sambuci williamsii extract, ocean Juniperus rigida Sieb.et Zucc. extract, the achillea millefolium extract, oil-soluble achillea millefolium extract, the Mentha piperita extract, sage extract, the oil-soluble sage extract, Salvia japonica Thunb. water, the Radix Malvae sylvestris extract, Herba Apii graveolentis extract, Rhizoma Chuanxiong (cnidium officinale) extract, Rhizoma Chuanxiong water, Japan's Herba Swertiae bimaculatae (swertiajaponica) extract, soybean extract, the Fructus Jujubae extract, Thymi Serpylli Herba extract, the Flos Camelliae Japonicae leaf extract, Flos Camelliae Japonicae drying and distilling liquid, the Camellia extract, the Flos Caryophylli extract, Citrus reticulata Blanco extract, the Camellia extract, Herba Centellae extract, the oil-soluble Juglans regia L. extract, duke (duke) extract, the Terminalia catappa L. extract, the east Radix Angelicae Sinensis extract, oil-soluble east Radix Angelicae Sinensis extract, Dong Dangguishui, Flos Inulae extract, the oil-soluble Flos Inulae extract, soy milk powder, the peach extract, the bigarabe extract, Herba Houttuyniae extract, Fructus Lycopersici esculenti extract, the septfoil root extract, natto extract, Radix Ginseng extract, the oil-soluble Radix Ginseng extract, Bulbus Allii extract, rose hip extract;
The oil-soluble rose hip extract, Fructus Hordei Germinatus extract, the root of Cornu Cervi Pantotrichum extract, Radix Ophiopogonis extract, parsley extract, Folium Hordei Vulgaris juice concentrate, distillatory aqua methnae, Radix Hamamelidis Mollis water, the Radix Hamamelidis Mollis extract, moss rose (rosa centifolia) flower extract, the wall pellitory extract, Spica Prunellae (isodonisjaponicus) extract, Folium Eriobotryae fermented product, the oil-soluble Folium Eriobotryae fermented product, Flos Farfarae extract, Poria extract, the butchers broom root extract, butchers broom root extract powder, Fructus Vitis viniferae extract, extract of red vine leaves, Fructus Vitis viniferae water, the dry flower extract, Luffa cylinder berry extract, Luffa cylinder fruit water, Flos Carthami extract, oil-soluble broad-leaved Hibiscus syriacus flower extract, broad-leaved Hibiscus syriacus water, the root of Paeonia suffruticosa Ardr. extract, Flos lupuli (Flos Humuli Lupuli) extract, the oil-soluble Flos lupuli (Flos Humuli Lupuli) extract, Lapland pine Balls berry extract, the Herba Silybi mariani fruit extract, the Aesculus chinensis Bunge extract, oil-soluble Aesculus chinensis Bunge extract, the Cortex Sapindi Mukorossi extract, the lemon mint extract, melilotus extract, the Folium Persicae extract, oil-soluble Folium Persicae extract, the bean sprout extract, the cyani flos extract, cyani flos water, eucalyptus extracts, Herba Saxifragae extract, the Bulbus Lilii extractive form corm, Semen Coicis extract, the oil-soluble Semen Coicis extract, the Artemisia princeps Pamp. extract, Artemisia princeps Pamp. water, Herba Lysimachiae foenum-graeci extract, lavender liquid, Fructus Mali pumilae extract, Ganoderma extract, Caulis et Folium Lactucae sativae extract, the Herba Astragali Melilotoidis (Herba Astragali Sinici) extract, rose water, Herba Rosmarini Officinalis extract, the oil-soluble Herba Rosmarini Officinalis extract, anthemidis flos extract and Radix Sanguisorbae root extract;
Aminoacid and peptide, for example collagen of the elastin laminin of glycine, valine, leucine, isoleucine, serine, threonine, phenylalanine, tyrosine, tryptophan, cystine, cysteine, methionine, hydroxyproline, aspartic acid, agedoite, glutamic acid, glutamine, histidine, γ-An Jidingsuan, DL-2-pyrrolidone-5-carboxylic acid, episilon amino caproic acid, hydrolysis, water solublity elastin laminin, hydrolysis, water solublity collagen, casein, glutathion, wheat peptide and soybean peptide;
Vitamin and vitamin agent, comprise vitamin A for example retinol, retinal, tretinoin, retinol acetate and retinyl palmitate, carotenoid is alpha-carotene, beta-carotene, gamma carotene, δ-carotene, lycopene, cryptoxanthin, kryptoxanthin, echinenone and astaxanthin for example, vitamin B1 is thiamine for example, vitamin B2 is riboflavin, vitamin B6 pyridoxol, 2-methyl-3-hydroxy-4-formyl-5-hydroxymethylpyridine. and pyridoxamine, vitamin B12 cyanocobalamin for example for example for example
Folic acid, nicotinic acid, nicotiamide, pantothenic acid, biotin, vitamin C is the L-ascorbic acid for example, the L-sodium ascorbate, stearic acid L-acid ascorbyl ester, Palmic acid L-acid ascorbyl ester, two Palmic acid L-acid ascorbyl esters, four different Palmic acid L-acid ascorbyl esters, L-resists bad blood ester sulphuric acid disodium, the L-Magnesium ascorbate, L-ascorbyl sodium phosphate, ascorbic acid-2-phosphoric acid and L-ascorbic acid-2-glucoside, vitamin D is ergocalciferol and cholecalciferol for example, and vitamin E is the d-alpha-tocopherol for example, the DL-alpha-tocopherol, the dl-alpha-tocopherol acetate, dl-alpha-tocofecol succinic acid ester, betatocopherol, Gamma-Tocopherol and d-Delta-Tocopherol, the ubiquinone class, vitamin K, carnitine, ferulic acid, gamma oryzanol, alpha-lipoic acid and orotic acid;
Antiseptic, for example benzoic acid, sodium benzoate, 9-undecylenic acid, salicylic acid, sorbic acid, potassium sorbate, dehydroactic acid, dehydro sodium acetate, to the oxybenzoic acid isobutyl ester, to oxybenzoic acid isopropyl ester, ethylparaben, butyl p-hydroxybenzoate, propyl p-hydroxybenzoate, benzyl p-hydroxybenzoate, methyl parahydroxybenzoate, P-hydroxybenzoic acid sodium methide, phenyl phenol, photosensitizer No.101, photosensitizer No.201 and photosensitizer No.401;
Antioxidant, for example Butylated hydroxyanisole, butylated hydroxytoluene, propyl gallate, arabo-ascorbic acid, sodium erythorbate, p-hydroxyanisole and gallateoctylester;
The sequestering agent that comprises metal ion compound, for example ethylenediamine ethoxy triacetic acid trisodium, ethylenediaminetetraacetic acid, disodiumedetate, sodium versenate, tetrasodium ethylenediamine tetraacetate, sodium citrate, gluconic acid, phytic acid, sodium polyphosphate and Polymeric sodium metaphosphate.;
Humidizer, for example hyaluronic acid, hyaluronate sodium, sodium chondroitin sulfate, sodium lactate, pyrrolidone sodium carboxylate, betanin, lactic acid bacteria culture solution, yeast extract and ceramide;
Antiinflammatory, for example glycyrrhizic acid, trisodium glycyrrhetinate, glycyrrhizic acid dipotassium, monoammonium glycyrrhizinate, β-enoxolone, enoxolone glyceride, enoxolone stearyl, lysozyme chloride, hydrocortisone and allantoin;
PH regulator agent, for example sodium hydroxide, potassium hydroxide and triethanolamine;
Salt, for example sodium chloride, potassium chloride, magnesium chloride and sodium sulfate;
'alpha '-hydroxy acids, for example citric acid, glycolic, tartaric acid and lactic acid;
Brightening agent, for example Arbutin, α-Arbutin and intacellin;
Quintessence oil, for example Radix Angelicae Sinensis oil, the blue essential oil of clothing, elemi oil, Germany's Flos Matricariae chamomillae oil, Flos Matricariae chamomillae oil, Cardamom oil, oil of Rhizoma Acori Graminei, kahikatea Oleum sesami, Oleum Camphora, Fructus Dauci Sativae oil, clary sage oil, Oleum Caryophylli, Oleum Cinnamomi, Fructus Coriandri oil, Resina Cupressi, sandalwood oil, oleum Cunninghamiae lanceolatae, citronella oil, the cassia tree leaf oil, jasminun sambae aif, juniper berry oil, Rhizoma Zingiberis Recens extract, Oleum menthae, sage oil, Cedrus deoclar (Roxb.) G. Don oil, Oleum Pelargonii Graveolentis, thyme oil, tea tree oil, Semen Myristicae oil, niaouli oil, orange blossom oil, Oleum Pini, basil oil, Oleum menthae, patchouli oil, palmarosa oil, Oleum Anisi Stellati, petitgrain oil, Fructus piperis nigrum oil, blue red oil, vetiver oil, Fructus Piperis peppermint oil, oleum bergamottae, Benzoinum oil, rosewood oil (aniba rosaeodora oil), marjoram oil, Myrrha, melissa oil, eucalyptus oil, Luo Wenshaye (ravensara) oil, lavandin oil, Essential lavender oil, gamma hch oil, Oleum Rosae Rugosae, bois de rose oil, oil of rosemary and lovage oil;
Terpenes, for example pinene, terpinene, terpinolene, myrcene and longifolene;
Spice and water.
Ingredients and form to described preparation for external application to skin and cosmetics are not particularly limited, as long as they directly use on skin.More preferably with this preparation for external application to skin and cosmetic application near the skin metabolism place of expectation subcutaneous fat.Broadly, this preparation for external application to skin and cosmetics comprise any ingredients of directly using, for example milk milky lotion on skin, protective skin cream, vanishing cream, massage cream, cleansing cream, shaving cream, cleaning foam, cosmetic water, lotion, the bag agent, lip pomade, lipstick, eye shadow, nial polish, soap, body shampoo, the hands soap, shampoo, conditioner, hair oil, handle regulator, suppurative mastitis, hair jelly, the hair growth promoting tonic, anti-alopecia agent, hair dyeing is plain, shaping glue, depilatory, dandruff removing agent, toothpaste, dental adhesive, mouthwash, agent for permanent hair waving, setting lotion, setting agent, ointment, the skin patching viscose glue, sizing agent, bath shampoo, Antiperspirant and opacifier.This preparation for external application to skin and cosmetics can be regardless of the sex of user and ages and are used, and can be used for animal skin and human skin.
Preparation for external application to skin of the present invention and cosmetics can be arbitrary forms, comprise solid, liquid, semisolid, gas, powder, granule, tablet, gel and foam.
Although optional, preferred ingredients and the form of selecting to comprise water-bearing media because the present invention improve aspect bad stable in aqueous compositions of conventional carnitine derivative and salt thereof effective especially.In this case, water can account for the 0.01-99.99 quality % of described preparation for external application to skin or cosmetics aptly.
Cosmetics of the present invention can contain the existing cosmetic composition except that said components in addition and still realize effect of the present invention simultaneously.The example of described composition is included in those that enumerate in the following document: (Japanese Pharmacopoeia association edits and by Yakuji Nippo for Japanese cosmetic ingredient standard (The Japanese Standards of Cosmetic Ingredients) the 2nd edition, Ltd. publish (1984)), Japanese cosmetic becomes sectional lists (The Japanese Cosmetic Ingredients Codex) (by Ministry of Health and Welfare, Pharmaceutical Examination Division (Health and human services department medicine examination department) editor and by Yakuji Nippo, Ltd. publish (1993)), Japanese cosmetic becomes sectional lists to replenish (Supplement to The Japanese Cosmetic IngredientsCodex) (by Ministry of Health and Welfare, Pharmaceutical ExaminationDivision (Health and human services department medicine examination department) editor and by Yakuji Nippo, Ltd. publish (1993)), the comprehensive approval standard of cosmetics (The Comprehensive Licensing Standards ofCosmetics by Category) is (by Ministry of Health and Welfare, Pharmaceutical Examination Division (Health and human services department medicine examination department) editor and by Yakuji Nippo, Ltd. publish (1993)), Japanese cosmetic composition directory index (The JapaneseCosmetic Ingredients Codex by Category) is (by Ministry of Health andWelfare, Pharmaceutical Examination Division (Health and human services department medicine examination department) editor and by Yakuji Nippo, Ltd. publish (1997)), cosmetic ingredient dictionary (Dictionaryof Cosmetic Ingredients) (Nikko Chemicals, Co.Ltd. (1991)) and 300 up-to-date cosmetics functional materials (300 Latest Cosmetic Functional Materials) (CMSPublishing Co., Ltd. (2002)).
Can be according to ingredients by conventional method, for example by mentioned component is made preparation for external application to skin of the present invention and cosmetics with scheduled volume dissolving, mixing or dispersion.
Below will the present invention be described in more detail by embodiment.Yet, should be construed to and the invention is not restricted to described embodiment.In an embodiment, unless otherwise mentioned, % by mass.
Embodiment
[synthetic embodiment 1]
Synthesizing of L-carnitine 2-hexyldecanoic acid ester hydrochloride
In ice bath, 45.6g (0.283mol) L-carnitine is dissolved in the 150ml trifluoroacetic acid.In gained solution, times dropping 116.6g (0.425mol) the 2-hexyl decanoyl chloride with 10 minutes then heats and stirred 4 hours at 80 ℃.Distilling off solvent under the pressure that reduces.The gained dark brown oily mater of the 264.6g that weighs is washed 3 times with the 200ml normal hexane, collect 200ml dark oil material.With 20ml ethanol, 30ml n-butyl alcohol and 60ml water this oily mater of 3.0g is extracted.The organic facies that obtains with the 60ml water washing, and with the mixture washing of 20ml ethanol and 60ml water.With organic facies 60ml water washing, collect and drying.Distill out described solvent and produce 2.0g L-carnitine 2-hexyldecanoic acid ester hydrochloride.
Distinguish the structure of gained chemical compound by NMR, liquid chromatography-mass spectrography (LC/MS) and elementary analysis.
<NMR>
1H-NMR(CDCl 3)：0.90ppm(6H，t，7.0Hz)，1.29-1.62ppm(24H，m)，2.41ppm(1H，m)，2.76ppm(2H，d，6.0Hz)，3.21ppm(9H，s)，3.75ppm(1H，d，14.6Hz)，3.92ppm(1H，dd，8.2，14.6Hz)，5.60-5.64ppm(1H，m)
NMR equipment: Burker Advance 500
Sample solution concentration: the heavy chloroform of 40mg sample/422mg
Temperature: ambient temperature
＜liquid chromatography-mass spectrography (LC/MS) 〉
MS(ESI)m/z：400.5[M +](LC/MS)
Liquid chromatograph (LC): Agilent 1100 series
Chromatographic column: Shodex silicon dioxide C8-5B
Column temperature: 40 ℃
Elute soln: 20mM ammonium acetate solution/acetonitrile (30/70)
Flow velocity: 1.0ml/min
Sample solution concentration and injection rate: 10 μ g * 5mg/ml elute soln
Detect: photodiode array UV 200-700nm
Mass spectrum (MS): Thermoquest LCQ Advantage
Ioning method: ESI (electro-spray ionization)
Sweep limits: m/z 50-1000 (alternately positive and negative charge)
MS/MS collision energy: 40%
＜elementary analysis 〉
Elementary analysis: C:62.8%, H:10.6%, N:3.5%, O:14.9%, Cl:8.2%
C, H, N and O: organic element analyzer CHNS-932 and oxygen analysis option VTF-900 (making) by LECO
Object of reference: symmetrical rhenocure CA (being used for the analysis of C, H and N), paranitroanilinum (being used for the analysis of O)
Cl: chromatography of ions (is incited somebody to action just in time sample and elute soln (the 1.8mM Na of 1mg 2CO 3+ 1.7mM NaHCO 3) be mixed to the 100ml standardize solution, and analyze to determine the Cl in the sample with anion chromatographic (DIONEX DX-500).)
Chromatographic column: Shodex SI-90 4E
Flow velocity: 1.0ml/min
Injection rate: 25 μ L
Detector: conductivity detector
Suppressor: ASRS-I
[synthetic embodiment 2]
Synthesizing of L-carnitine 2-methyl palmitic acid ester hydrochloride
In ice bath, 45.6g (0.283mol) L-carnitine is dissolved in the 150ml trifluoroacetic acid.In gained solution, times dropping 122.4g (0.425mol) the 2-methyl Hexadecanoyl chloride with 10 minutes then heats and stirred 4 hours at 80 ℃.Distilling off solvent under the pressure that reduces.The gained dark brown oily mater of the 278.0g that weighs is washed 3 times with the 200ml normal hexane, collect 200ml dark oil material.With 20ml ethanol, 30ml n-butyl alcohol and 60ml water this oily mater of 3.0g is extracted.The organic facies that obtains with the 60ml water washing, and with the mixture washing of 20ml ethanol and 60ml water.With organic facies 60ml water washing, collect and drying.Distill out described solvent and produce 2.2g L-carnitine 2-methyl palmitic acid ester hydrochloride.
By the structure of distinguishing the gained chemical compound as NMR, liquid chromatography-mass spectrography (LC/MS) and elementary analysis described in the synthetic embodiment 1.
<NMR>
1H-NMR(CDCl 3)：2.50ppm(1H，m)，2.75ppm(1H，dd，6.2，1.5Hz)，2.80ppm(1H，m)，3.73ppm(1H，d，14.4Hz)，3.91ppm(1H，dd，14.4，8.5Hz)，5.61-5.65ppm(1H，m)
＜liquid chromatography-mass spectrography (LC/MS) 〉
MS(ESI)m/z：414.5[M +]
＜elementary analysis 〉
Elementary analysis: C:64.3%, H:10.3%, N:3.2%, O:14.2%, Cl:8.0%
[synthetic embodiment 3]
Synthesizing of L-carnitine 2-butyl caprylate hydrochlorate
In ice bath, 45.6g (0.283mol) L-carnitine is dissolved in the 150ml trifluoroacetic acid.In gained solution, times dropping 92.7g (0.425mol) the 2-butyl caprylyl chloride with 10 minutes then heats and stirred 4 hours at 80 ℃.Distilling off solvent under the pressure that reduces.The gained dark brown oily mater of the 250.0g that weighs is washed 3 times with the 200ml normal hexane, collect 200ml dark oil material.With 20ml ethanol, 30ml n-butyl alcohol and 60ml water this oily mater of 3.0g is extracted.The organic facies that obtains with the 60ml water washing, and with the mixture washing of 20ml ethanol and 60ml water.With organic facies 60ml water washing, collect and drying.Distill out described solvent and produce 1.6g L-carnitine 2-butyl caprylate hydrochlorate.
By the structure of distinguishing the gained chemical compound as NMR, liquid chromatography-mass spectrography (LC/MS) and elementary analysis described in the synthetic embodiment 1.
<NMR>
1H-NMR(CDCl 3)：2.76ppm(1H，d，6.0Hz)，2.80ppm(1H，m)，3.76ppm(1H，d，14.4Hz)，3.94ppm(1H，dd，14.4，8.2Hz)，5.60-5.64ppm(1H，m)
＜liquid chromatography-mass spectrography (LC/MS) 〉
MS(ESI)m/z：344.5[M +]
＜elementary analysis 〉
Elementary analysis: C:60.1%, H:9.5%, N:3.5%, O:16.7%, Cl:10.2%
[embodiment 1]
The Percutaneously absorbable energy
Test following 5 kinds of materials:
1) L-carnitine hydrochloride (Sigma-Aldrich)
2) L-carnitine cetylate hydrochlorate (Sigma-Aldrich)
3) L-carnitine 2-hexyldecanoic acid ester hydrochloride (synthetic embodiment 1)
4) L-carnitine 2-methyl palmitic acid ester hydrochloride (synthetic embodiment 2)
5) L-carnitine 2-butyl caprylate hydrochlorate (synthetic embodiment 3)
Test substances (1) and (2) are markers.
Described test substances is dissolved in separately contains 5 quality %1, among Dulbecco ' the s PBS (-) of 2-hexanediol, then add 1N NaOH and regulate pH to 7.As a result, make 0.3 quality % solution of described test substances.With the threedimensional model (TESTSKIN of two chambers by the application on human skin tissue TMLSD-d, from TOYOBO CO., LTD. obtains) separate.Each test substances solution of 3ml is put into the chamber of epidermis side, 3ml Dulbecco ' s PBS (-) is put into the chamber of corium side.They were stirred 24 hours under 35 ℃ with magnetic stirring apparatus.
After 24 hours, collect the 1ml buffer solution in corium one side room, analyze the collected solution of 0.5ml and determine free carnitine.The remainder of collected solution is adjusted to pH 11 with 1N NaOH, is encapsulated in the 1.5ml screw-cap vial, and places 6 hours at 80 ℃, then cooling.With the pH to 7 of 1N HCl regulator solution, make all fatty acyl carnitine derivants resolve into free carnitine thus.These solution are merged with the acetone soln of 0.02ml 1N hydrochloric acid, 0.1ml 1.6 quality %1-amino anthracenes and 0.1ml 16 quality %EDC (1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride) aqueous solution separately, then fully stir.Make solution at room temperature leave standstill 20 minutes also with the washing of 3ml diethyl ether.Filter described water and by reversed-phase high-performance liquid chromatography (RPHPLC) (chromatographic column: Phenomenex Synergi-RP, elute soln: 45% acetonitrile, flow velocity: 1.0ml/min) analyze peak intensity (excitation wavelength: 248nm, wavelength of fluorescence: 418nm) with the carnitine of determining to belong to the modification of 1-amino anthracene.Calculate and determine by above-mentioned peak intensity and come from the carnitine derivative of test substances and the concentration of free carnitine in the described solution in corium one side room.Described alkali and heat treated sample show the free carnitine of total and the concentration of carnitine derivative.Undressed sample shows the concentration of free carnitine.
The results are shown among Fig. 1.
Fig. 1 shows that L-carnitine 2-hexyldecanoic acid ester, L-carnitine 2-methyl palmitic acid ester and L-carnitine 2-butyl caprylate pass skin and reach with the suitable L-carnitine concentration that is obtained by L-carnitine cetylate or than its higher L-carnitine concentration.
[embodiment 2]
Stability
Test following 5 kinds of materials:
1) acetyl group L-carnitine hydrochloride (Sigma-Aldrich)
2) L-carnitine cetylate hydrochlorate (Sigma-Aldrich)
3) L-carnitine 2-hexyldecanoic acid ester hydrochloride (synthetic embodiment 1)
4) L-carnitine 2-methyl palmitic acid ester hydrochloride (synthetic embodiment 2)
5) L-carnitine 2-butyl caprylate hydrochlorate (synthetic embodiment 3)
Test substances (1) and (2) are markers.
Test substances is dissolved in separately contains 5 quality %1, among Dulbecco ' the s PBS (-) of 2-hexanediol, then add 1N NaOH and regulate pH to 7.As a result, make 0.3 quality % solution of described test substances.This solution compact package is controlled temperature at 80 ℃ in vial and in water-bath.
Through after the scheduled time, collect this solution and by RPHPLC (chromatographic column: ShodexC8-5B, elute soln: 70% acetonitrile, flow velocity: 1.0ml/min) analyze.Determine to come from the residual carnitine derivative of described test substances by the UV absorption intensity at 210nm place.The residual rate that Fig. 2 shows the carnitine derivative come from test substances over time.
Fig. 2 shows with the fatty acyl carnitine with straight chain acyl group and compares that have the carnitine derivative of alpha-branched acyl group: L-carnitine 2-hexyldecanoic acid ester, L-carnitine 2-methyl palmitic acid ester and L-carnitine 2-butyl caprylate demonstrate higher residual rate and be more stable extraordinarily in aqueous solution.
[embodiment 3]
Steatolysis promotes
Be inoculated in adipose cell before the mankind (from TOYOBO CO., LTD. obtains) on the 96 hole microplates and with adipose cell growth medium TAGM before human (from TOYOBO CO., LTD. obtains) at 37 ℃ and 5%CO 2This culture medium is every other day upgraded in following cultivation simultaneously.Change described growth medium into human adipose cell division culture medium TADM (from TOYOBO CO., LTD. obtains), and cultivated 5 days.Subsequently, described culture medium is changed into have in the following test substances of 50 μ M any or do not have its evaluation culture medium as shown in table 1 below.Cultivated 5 days.
Test following 5 kinds of materials:
1) L-carnitine hydrochloride (Sigma-Aldrich)
2) L-carnitine cetylate hydrochlorate (Sigma-Aldrich)
3) L-carnitine 2-hexyldecanoic acid ester hydrochloride (synthetic embodiment 1)
4) L-carnitine 2-methyl palmitic acid ester hydrochloride (synthetic embodiment 2)
5) L-carnitine 2-butyl caprylate hydrochlorate (synthetic embodiment 3)
Test substances (1) and (2) are markers.
Table 1
(evaluation culture medium)
Component Concentration (g/l)
Calcium chloride dihydrate 0.265
The ferric nitrate nonahydrate 0.0001
Magnesium sulfate 0.09767
Potassium chloride 0.4
Sodium carbonate 3.7
Sodium chloride 6.4
Sodium dihydrogen phosphate 0.109
The L-arginine monohydrochloride 0.084
The L-cystine hydrochloride 0.0626
L-glutaminate 0.584
Glycine 0.030
L-histidine hydrochloride hydrate 0.042
The L-isoleucine 0.105
The L-leucine 0.105
L-lysine hydrochloride 0.146
The L-methionine 0.030
The L-phenylalanine 0.066
The L-serine 0.042
The L-threonine 0.095
The L-tryptophan 0.016
L-tyrosine disodium dihydrate 0.10379
The L-valine 0.094
Lipotril 0.004
Folic acid 0.004
Inositol 0.0072
Nicotiamide 0.004
The D-calcium pantothenate 0.004
Pyridoxine hydrochloride 0.004
Riboflavin 0.0004
Thiamine hydrochloride 0.004
Phenol red sodium 0.0159
Sodium Pyruvate 0.11
pH 7.3
With described adipose cell Dulbecco ' s PBS (-) washing 3 times and carry out formalin fixed.Described adipose cell with oil red/water-isopropyl alcohol (1/1) solution-dyed, and is extracted with isopropyl alcohol.By cumulative triglyceride in the described adipose cell of colorimetric method for determining.Table 2 shows the triglyceride accumulation that is obtained by described test substances with respect to undressed adipose cell (100).
Table 2
Test substances The triglyceride accumulation
Do not add 100
The L-carnitine hydrochloride 98
L-carnitine cetylate hydrochlorate 87
L-carnitine 2-hexyldecanoic acid ester hydrochloride 89
L-carnitine 2-methyl palmitic acid ester hydrochloride 89
L-carnitine 2-butyl caprylate hydrochlorate 90
Table 2 demonstrates as fatty acyl carnitine, and L-carnitine 2-hexyldecanoic acid ester, L-carnitine 2-methyl palmitic acid ester and L-carnitine 2-butyl caprylate have the lipometabolic effect of good promotion.
[embodiment 4]
Make the cosmetics that contain L-carnitine 2-hexyldecanoic acid ester hydrochloride according to table 3.These cosmetics were stored 3 months and were confirmed stable and do not have at 40 ℃ and separate and precipitate.
Table 3
Component ％
Sodium chloride 0.2
EDTA four sodium 0.2
1, the 2-hexanediol 4.0
Glycyrrhizic acid dipotassium 0.1
1% aqueous solution of sodium hyaluronate 4.0
L-carnitine 2-hexyldecanoic acid ester hydrochloride 0.3
Purify waste water Surplus
Annotate: numerical value is with respect to the quality % that amounts to 100%.
[embodiment 5]
The preparation of cosmetic water (skin toner)
Prepare cosmetic water according to following formulation Example 1-4, wherein the summation of component A and B is 100%.
(formulation Example 1)
A.
Glycyrrhizic acid dipotassium 0.2％
L-carnitine 2-hexyldecanoic acid ester hydrochloride 1.0％
Citric acid 0.1％
Sodium citrate 0.3％
Purify waste water Surplus
B.
Polyoxyethylene sorbitol four oleates 0.9％
Dehydrated sorbitol mono-fatty acid ester 0.1％
Olive oil 0.1％
Dipropylene glycol 5.0％
Methyl parahydroxybenzoate 0.1％
Ethanol 10.0％
(formulation Example 2)
A.
Sodium citrate 0.1％
Glycerol 8.0％
Pyrrolidone sodium carboxylate 1.0％
Trehalose 0.03％
1,3 butylene glycol 5.0％
Purify waste water Surplus
B.
Polyoxyethylene polyoxypropylene decyl myristyl ether 0.6％
Methyl parahydroxybenzoate 0.1％
Ethanol 10.0％
L-carnitine 2-hexyldecanoic acid ester hydrochloride 0.3％
(formulation Example 3)
A.
Polyvinyl alcohol 0.1％
CVP Carbopol ETD2050 0.2％
Glycerol 3.0％
Sodium versenate 0.1％
Sodium hydroxide 0.05％
2-amino-2-methyl-1-propanol 0.06％
Caffeine 0.1％
Purify waste water Surplus
B.
Ethanol 20.0％
Polyoxyethylene oleyl ether 0.3％
Methyl parahydroxybenzoate 0.1％
Methanol 0.1％
L-carnitine 2-methyl palmitic acid ester hydrochloride 0.1％
In formulation Example 1,2 and 3, respectively the composition of A and B is mixed and 50 ℃ of heating to obtain solution.Subsequently, stirring under the situation of A, joining the B of some fractions among the A and be dissolved in wherein.Under agitation cool off the solution of gained.When temperature is 30 ℃, stops stirring and place solution to obtain cosmetic water.
(formulation Example 4)
A.
1,3 butylene glycol 5.02％
Two (cholesteryl/Shan Yu base/octyl group dodecyl) lauroyl glutamate 0.5％
Trehalose 0.03％
Tricaprylin 0.03％
PEG-58 castor oil hydrogenated isostearate 1.5％
The PEG-60 castor oil hydrogenated 0.5％
Methyl parahydroxybenzoate 0.2％
Propyl p-hydroxybenzoate 0.01％
Tocopherol 0.05％
L-carnitine 2-butyl caprylate hydrochlorate 0.3％
B.
Natrium malicum 0.1％
Malic acid In right amount
Purify waste water Surplus
Respectively the composition of A and B is mixed and 60 ℃ of heating to obtain solution.Subsequently, stirring under the situation of A, B is mixed with A and cooling off this mixture to form uniform cosmetic water.
[embodiment 6]
The preparation of milk milky lotion
Prepare the milk milky lotion according to formulation Example 5-7.In formulation Example 5 and 6, the summation of component A and B is 100%.In formulation Example 7, the summation of component A to C is 100%.
(formulation Example 5)
A.
Squalane 10.0％
The polyoxyethylene iso stearic acid of glycerine ester 3.5％
Polyoxyethylene hydrogenated Oleum Ricini three isostearates 6.5％
Polyoxyethylene hydrogenated Oleum Ricini pyroglutamic acid isostearate 12.0％
Methyl parahydroxybenzoate 0.1％
B.
L-carnitine 2-hexyldecanoic acid ester hydrochloride 0.5％
Purify waste water Surplus
Composition with A and B mixes respectively, and with A and B respectively 70 ℃ and 50 ℃ of heating to obtain solution.Subsequently, stirring under the situation of A, the B of some small parts is being joined among the A to form emulsion.Under agitation cool off this emulsion to obtain the emulsifying product, this emulsifying product dilutes 10 times to produce the milk milky lotion with purifying waste water.
(formulation Example 6)
A.
Liquid paraffin 10.6％
Isopropyl myristate 0.6％
Oleyl alcohol 1.2％
Polyoxyethylene stearyl base ether 3.4％
The PEG distearate 1.9％
The polyoxyethylene polyoxypropylene myristyl ether 0.4％
L-carnitine 2-hexyldecanoic acid ester hydrochloride 0.3％
B.
The stearyl sodium glutamate 0.1％
Propylene glycol 1.4％
Methyl parahydroxybenzoate 0.1％
PEG-400 0.2％
Purify waste water Surplus
Composition with A and B mixes respectively, and with A and B respectively 70 ℃ and 75 ℃ of heating to obtain solution.Subsequently, stirring under the situation of B, the A of some small parts is being joined among the B to form emulsion.Under agitation cool off this emulsion to obtain the milk milky lotion.
(formulation Example 7)
A.
The polyoxyethylene sorbitan monostearate 1.0％
Polyoxyethylene sorbitol four oleates 0.5％
Sorbitan monostearate 1.0％
Stearic acid 0.5％
Behenyl alcohol 0.5％
Cera Flava 0.5％
Squalane 10.0％
Three-2 ethyl hexanoic acid glyceride 10.0％
Ten polyglycereol, ten oleates 3.0％
1,3 butylene glycol 7.0％
Methyl parahydroxybenzoate 0.1％
L-carnitine 2-methyl palmitic acid ester hydrochloride 0.3％
B.
Xanthan gum 0.04％
CVP Carbopol ETD2050 0.08％
Purify waste water Surplus
C.
Triethanolamine 0.05％
Purify waste water 4.95％
Composition with A, B and C mixes respectively, and with A and B 80 ℃ of heating to obtain solution C homogenize at room temperature.Subsequently, under the situation that stirs A, B is joined among the A to form emulsion, to wherein adding C.Cooling under agitation is in forming emulsion liquid near 40 ℃.With this emulsion liquid composition cools to room temperature to produce the milk milky lotion.
[embodiment 7]
The preparation of gel
8-13 prepares gel according to formulation Example.In formulation Example 8, the summation of component A and B is 100%.In formulation Example 9, the summation of component A to E is 100%.In formulation Example 10-13, the summation of component A to C is 100%.
(formulation Example 8)
A.
Agar 2.0％
Xanthan gum 0.2％
Caffeine 0.1％
Purify waste water 50.0％
B.
Glycerol 7.0％
PEG-1500 8.0％
Methyl parahydroxybenzoate 0.1％
L-carnitine 2-hexyldecanoic acid ester hydrochloride 0.8％
Purify waste water Surplus
Composition with A and B mixes respectively, and with A and B respectively 90 ℃ and 50 ℃ of heating to obtain dispersion.Subsequently, A is cooled to 50 ℃.Stirring under the situation of A, B is being joined among the A and be no more than 30 ℃ and make this mixture gelation by under agitation being cooled to.When described gel becomes when enough solidifying, use dispersal device that it is broken into microgel, then the degassing is to produce (translucent) gel uniformly.(formulation Example 9)
A.
CVP Carbopol ETD2050 0.35％
Purify waste water 50.0％
B.
Sodium hydroxide 0.1％
Purify waste water 10.0％
C.
1% aqueous solution of sodium hyaluronate 6.0％
Purify waste water Surplus
D.
The polyoxyethylene polyoxypropylene myristyl ether 0.3％
Ethanol 5.0％
Methyl parahydroxybenzoate 0.1％
L-carnitine 2-hexyldecanoic acid ester hydrochloride 0.3％
E.
PFPE 0.2％
Composition with A, B, C and D mixes respectively.Make A and B at room temperature form solution, with C and D respectively 50 ℃ and 40 ℃ of heating to obtain solution.Subsequently, stirring under the situation of A, joining B among the A and make this mixture gelation.After this, add C, D and be in the same place with E and by mixing in described gel, then the degassing is to produce (translucent) gel uniformly.
(formulation Example 10)
A.
CVP Carbopol ETD2050 0.5％
Purify waste water 40.0％
B.
Potassium hydroxide 0.1％
Purify waste water 10.0％
C.
Dipropylene glycol 10.0％
Methyl parahydroxybenzoate 0.1％
Glycyrrhizic acid dipotassium 0.05％
Hydrolytic collagen 0.05％
L-carnitine 2-methyl palmitic acid ester hydrochloride 0.5％
Purify waste water Surplus
Composition with A, B and C mixes respectively.Make A and B at room temperature form solution, and heat C to obtain solution at 50 ℃.Subsequently, stirring under the situation of A, joining B among the A and make this mixture gelation.After this, in described gel, add C and, follow the degassing to produce (translucent) gel uniformly by mixing together.
(formulation Example 11)
A.
Glycerol 10.0％
1,3 butylene glycol 6.0％
Polydimethylsiloxane 2.0％
The PEG-60 castor oil hydrogenated 0.6％
Laureth-2 (laureth-2) 0.1％
Laureth-21 (laureth-21) 0.1％
To the hydroxymethyl-benzoic acid methyl ester 0.26％
To the hydroxymethyl-benzoic acid propyl ester 0.1％
To the hydroxymethyl-benzoic acid ethyl ester 0.1％
Phenyl phenol 0.1％
Tocopherol acetas 0.1％
The chitosan succinamide 0.01％
Yeast extract 0.1％
Ethanol 0.01％
Spice 0.01％
L-carnitine 2-hexyldecanoic acid ester hydrochloride 0.3％
B.
CVP Carbopol ETD2050 0.5％
Carbamide 0.02％
Glucosamine hydrochloride 0.01％
Disodiumedetate 0.01％
Purify waste water 50.0％
C.
Arginine 0.63％
Purify waste water Surplus
Composition with A, B and C mixes respectively.To obtain solution, make B and C at room temperature form solution at 60 ℃ of heating A.Subsequently, stirring under the situation of A, joining B among the A and make this mixture gelation.After this, in described gel, add C and, then be cooled to room temperature to produce (translucent) gel uniformly by mixing together.
(formulation Example 12)
A.
Glycerol 50.0％
L-carnitine 2-hexyldecanoic acid ester hydrochloride 0.5％
Tourmaline 5.0％
Olive oil 1.0％
PEG-12 28.0％
PEG-75 7.5％
The polyglycereol laurate 1.0％
Ethanol 0.49％
(acrylic acid/acrylic acid (C10-30) Arrcostab) copolymer 0.11％
Methyl parahydroxybenzoate 0.11％
Propyl p-hydroxybenzoate 0.02％
Semen Ginkgo extrac 0.02％
Folium Camelliae sinensis extract 0.02％
The Aesculus chinensis Bunge extract 0.02％
Brown alga extract 0.02％
B.
CVP Carbopol ETD2050 0.07％
Purify waste water 3.0％
C.
Sodium hydroxide 0.01％
Purify waste water Surplus
Composition with A, B and C mixes respectively.To obtain solution, make B and C at room temperature form solution at 60 ℃ of heating A.Subsequently, stirring under the situation of A, joining B among the A and make this mixture gelation.After this, in described gel, add C and, then be cooled to room temperature to produce (translucent) gel uniformly by mixing together.
(formulation Example 13)
A.
Decamethylcyclopentaandoxane 20.0％
Potassium ascorbate 3.0％
L-carnitine 2-butyl caprylate hydrochlorate 0.3％
B.
Squalane 50.0％
Liquid paraffin,light Surplus
The dextrin cetylate 8.0％
C.
P-methoxycinnamic acid octyl group ester 1.0％
Phenyl phenol 0.5％
Alpha-tocopherol 0.1％
Weigh the respectively composition of A, B and C.At room temperature mediate the composition of A with ball mill.The composition of heating B is to obtain uniform solution.Make the composition of C at room temperature form solution.Subsequently, under the situation that stirs B, C is joined among the B.This mixture of homogenize also under agitation is cooled to room temperature.After this, add A and fully stir this mixture to produce (translucent) gel uniformly.
[embodiment 8]
The preparation of essence (serum)
14-16 prepares essence according to formulation Example.In formulation Example 14, the summation of component A to D is 100%.In formulation Example 15, the summation of component A and B is 100%.In formulation Example 16, the summation of component A to C is 100%.
(formulation Example 14)
A.
Xanthan gum 0.4％
Hydroxyethyl-cellulose 0.1％
CVP Carbopol ETD2050 0.1％
1,3 butylene glycol 5.0％
L-carnitine 2-hexyldecanoic acid ester hydrochloride 0.3％
Purify waste water 50.0％
B.
Potassium hydroxide (1% aqueous solution) 2.5％
Purify waste water 10.0％
C.
Caffeine 1.0％
Purify waste water Surplus
D.
Methyl parahydroxybenzoate 0.1％
Ethanol 3.0％
Composition with A, B, C and D mixes respectively.Make A, B and D at room temperature form solution, heat C to obtain solution at 50 ℃.Subsequently, under the situation that stirs A, B is joined among the A to form thick liquid.After this, to wherein adding C and D and by mixing together to produce uniform liquid (essence).
(formulation Example 15)
A.
1,3 butylene glycol 10.0％
Glycerol 5.0％
Hyaluronate sodium 0.2％
Xanthan gum 0.2％
Glycyrrhizic acid dipotassium 0.02％
L-carnitine 2-methyl palmitic acid ester hydrochloride 0.3％
Purify waste water Surplus
B.
Ethanol 3.0％
Hydrolecithin 0.5％
Tricaprylin 0.3％
The diphenyl polydimethylsiloxane 0.2％
Methyl parahydroxybenzoate 0.22％
Phenyl phenol 0.08％
The PEG-50 castor oil hydrogenated 0.1％
The PEG-60 castor oil hydrogenated 0.1％
Alpha-tocopherol 0.01％
Polyglycereol-10 myristinate 0.05％
Composition with A and B mixes respectively, and at 50 ℃ of heating A and B to obtain solution.Subsequently, under the situation that stirs A, B is under agitation mixed with A, under agitation cool off this mixture to produce uniform liquid (essence).
(formulation Example 16)
A.
Xanthan gum 0.4％
Hydroxyethyl-cellulose 0.4％
1,3 butylene glycol 3.0％
Glycerol 3.0％
Methyl parahydroxybenzoate 0.1％
Purify waste water Surplus
B.
L-carnitine 2-butyl caprylate hydrochlorate 0.3％
1, the 2-hexanediol 4.0％
Purify waste water 50.0％
C.
Ascorbic acid-2-magnesium phosphate 1.5％
Ascorbic acid-2-sodium phosphate 1.5％
Sodium citrate 0.5％
Tetrasodium ethylenediamine tetraacetate 0.1％
Purify waste water 9.4％
Composition with A, B and C mixes respectively.Make A and C at room temperature form solution, heat B to obtain solution at 50 ℃.Subsequently, under the situation that stirs A, B is joined among the A to form viscous liquid.After this, under agitation mixed C to produce uniform liquid (essence).
[embodiment 9]
The preparation of cream
17-19 prepares cream according to formulation Example, and wherein the summation of component A and B is 100%.
(formulation Example 17)
A.
Hydrogenated rapeseed oil alcohol 4.2％
Isononyl isononanoate 6.0％
Squalane 9.6％
Myristic acid octyl group dodecyl ester 4.8％
The polyglycereol monostearate 2.0％
Glyceryl stearate 1.0％
Propyl p-hydroxybenzoate 0.05％
Xanthan gum 0.1％
Alpha-tocopherol 0.5％
B.
1,3 butylene glycol 4.8％
Glycerol 4.8％
L-carnitine 2-hexyldecanoic acid ester hydrochloride 0.8％
Ascorbic acid-2-phosphoric acid-6-sodium palmitate 1.0％
Methyl parahydroxybenzoate 0.1％
Purify waste water Surplus
Composition with A and B mixes respectively, and at 85 ℃ of heating A and B to obtain solution.Subsequently, under the situation that stirs A, B is joined among the A to produce emulsion.Under agitation cool off this emulsion.When temperature is about 40 ℃, stops stirring and make this emulsion degassing to produce cream.
(formulation Example 18)
Except replace L-carnitine 2-hexyldecanoic acid ester hydrochloride by L-carnitine 2-methyl palmitic acid ester hydrochloride, according to formulation Example 17 preparation cream.
(formulation Example 19)
Except replace L-carnitine 2-hexyldecanoic acid ester hydrochloride by L-carnitine 2-butyl caprylate hydrochlorate, according to formulation Example 17 preparation cream.
[embodiment 10]
The preparation of lamellar beauty mask (cosmetic pack)
Prepare the lamellar beauty mask according to formulation Example 20-23, wherein the summation of component A and B is 100%.
(formulation Example 20)
A.
Glycerol 30.0％
Aluminum magnesium hydroxide 1.0％
B.
Diisopropanolamine (DIPA) 1.0％
Sodium polyacrylate 2.0％
Acrylic acid/sodium acrylate copolymer (50/50 mol ratio) 2.0％
L-carnitine 2-hexyldecanoic acid ester hydrochloride 0.3％
Ascorbic acid-2-magnesium phosphate 3.0％
Purify waste water Surplus
(formulation Example 21)
A.
1,3 butylene glycol 30.0％
Gel aluminum hydroxide/sodium bicarbonate coprecipitate 0.05％
B.
Sodium acrylate/acrylic acid copolymer (70/30 mol ratio) 1.0％
Polyacrylic acid 1.0％
N-vinyl acetamide/sodium acrylate copolymer (9/1 weight ratio) 3.0％
Aluctyl. 0.05％
10% ammonia spirit 0.01％
L-carnitine 2-hexyldecanoic acid ester hydrochloride 2.0％
Ascorbic acid-2-magnesium phosphate 0.01％
Purify waste water Surplus
In above-mentioned formulation Example, the composition with A and B mixes respectively.Make A at room temperature form dispersion and 50 ℃ the heating B to obtain solution.Subsequently, under agitation cool off B, and under mediating, A is joined among the B gradually to room temperature.With the gap of knife type coater gained colloidal sol is applied on the polypropylene lined with 0.5mm.After this, be attached to adhesive-bonded fabric on the described colloidal sol and place it in the aluminum lamination bag, then with its heat-sealing.After the ripening 3 days, obtain the lamellar beauty mask.
(formulation Example 22)
Except replace L-carnitine 2-hexyldecanoic acid ester hydrochloride by L-carnitine 2-methyl palmitic acid ester hydrochloride, according to formulation Example 20 preparation lamellar beauty masks.
(formulation Example 23)
Except replace L-carnitine 2-hexyldecanoic acid ester hydrochloride by L-carnitine 2-butyl caprylate hydrochlorate, according to formulation Example 20 preparation lamellar beauty masks.
[embodiment 11]
The preparation of facial film (pack)
Prepare facial film (peel off pack) according to formulation Example 24-26, wherein the summation of component A and B is 100%.
(formulation Example 24)
A.
Polyvinyl alcohol 13.0％
Carrageenin 0.5％
Purify waste water Surplus
B.
1,3 butylene glycol 3.0％
Methyl parahydroxybenzoate 0.1％
Ethanol 8.0％
L-carnitine 2-hexyldecanoic acid ester hydrochloride 1.0％
Composition with A and B mixes respectively.By making the A swelling and make B at room temperature form solution 50 ℃ of heating.Subsequently, stirring under the situation of A, joining B among the A gradually and mix.Under agitation cool off this mixture.When temperature is about 30 ℃, stops stirring and place mixture to produce peel off pack.
(formulation Example 25)
Except replace L-carnitine 2-hexyldecanoic acid ester hydrochloride by L-carnitine 2-methyl palmitic acid ester hydrochloride, according to formulation Example 24 preparation peels off pack.
(formulation Example 26)
Except replace L-carnitine 2-hexyldecanoic acid ester hydrochloride by L-carnitine 2-butyl caprylate hydrochlorate, according to formulation Example 24 preparation peels off pack.
[embodiment 12]
The preparation of bath shampoo
According to formulation Example 27 and 28 preparation bath shampoos, wherein the summation of each composition is 100%.
(formulation Example 27)
Polyoxyethylene sorbitol four oleates 14.0％
Polyoxyethylene oleyl ether 3.0％
NOFABLE SO-992 NOFABLE SO-902 3.0％
Squalane 10.0％
Jojoba oil 20.0％
American Avocado Tree oil 5.0％
Propyl p-hydroxybenzoate 0.1％
L-carnitine 2-hexyldecanoic acid ester hydrochloride 1.0％
Liquid paraffin Surplus
(formulation Example 28)
Sodium bicarbonate 35.5％
Citric acid 37.1％
Polyethylene Glycol 2.1％
Magnesium oxide 1.1％
Alpha-tocopherol 1.2％
Ascorbic acid-2-sodium phosphate 1.5％
Ascorbic acid-2-glucoside 1.5％
L-carnitine 2-methyl palmitic acid ester hydrochloride 0.5％
In above-mentioned formulation Example, at room temperature stir each composition to evenly producing bath shampoo.
[embodiment 13]
The preparation of facial cleansing agent
Prepare the facial cleansing agent according to formulation Example 29-31.In formulation Example 29 and 30, the summation of component A to C is 100%.In formulation Example 31, the summation of component A and B is 100%.
(formulation Example 29)
A.
Myristic acid 15.0％
Palmic acid 5.0％
Stearic acid 3.0％
Cera Flava 3.0％
PEG-6000 2.0％
Glycol distearate 2.0％
The fatty acid distribution of coconut oil diglycollic amide 3.0％
Spissated glycerol 15.0％
L-carnitine 2-hexyldecanoic acid ester hydrochloride 0.5％
B.
Potassium hydroxide 5.5％
Purify waste water 14.5％
C.
The N-sodium lauroyl sarcosine 10.0％
Purify waste water Surplus
Composition with A, B and C mixes respectively.To obtain solution, make C at room temperature form solution at 80 ℃ of heating A and B.Subsequently, under the situation that stirs A, B is joined among the A gradually, after this add C.Under agitation cool off this mixture.When temperature is about 30 ℃, stop to stir and placing this solution.As a result, obtain the facial cleansing agent.
(formulation Example 30)
Except replace L-carnitine 2-hexyldecanoic acid ester hydrochloride by L-carnitine 2-methyl palmitic acid ester hydrochloride, according to formulation Example 29 preparation facial cleansing agent.
(formulation Example 31)
A.
Lauric acid 2.0％
Myristic acid 17.0％
Palmic acid 4.0％
Stearic acid 4.0％
Fatty acid distribution of coconut oil potassium 8.0％
The fatty acid distribution of coconut oil diglycollic amide 3.0％
N-cocoyl N-methyltaurine sodium 10.0％
Concentrated glycerin 10.0％
1,3 butylene glycol 10.0％
L-carnitine 2-butyl caprylate hydrochlorate 1.0％
B.
Potassium hydroxide 5.5％
Tetrasodium ethylenediamine tetraacetate 0.2％
Purify waste water Surplus
Composition with A and B mixes respectively.To obtain solution, make B at room temperature form solution at 80 ℃ of heating A.Subsequently, under the situation that stirs A, B is joined among the A gradually.Under agitation cool off this mixture.When temperature is about 30 ℃, stop to stir and placing this solution.As a result, obtain the facial cleansing agent.
[embodiment 14]
The preparation of shampoo
32-34 prepares shampoo according to formulation Example, and wherein the summation of each composition is 100%.
(formulation Example 32)
POE (2) sodium laureth sulfate 30.0％
POE (2) Zetesol AP 20.0％
Betanin lauryl dimethyl aminoacetate 6.0％
O-[2-hydroxyl-3-(trimethyl ammonium) propyl group] the hydroxyethyl-cellulose chloride 0.25％
The fatty acid distribution of coconut oil diglycollic amide 4.0％
Glycol distearate 2.0％
1,3 butylene glycol 3.0％
Disodiumedetate 0.2％
L-carnitine 2-hexyldecanoic acid ester hydrochloride 1.0％
Purify waste water Surplus
Each composition is mixed and then stir to obtain emulsion 80 ℃ of heating.Under agitation cool off this emulsion.When temperature is about 30 ℃, stop to stir and placing this emulsion.As a result, obtain shampoo.
(formulation Example 33)
Except replace L-carnitine 2-hexyldecanoic acid ester hydrochloride by L-carnitine 2-methyl palmitic acid ester hydrochloride, according to formulation Example 32 preparation shampoos.
(formulation Example 34)
Except replace L-carnitine 2-hexyldecanoic acid ester hydrochloride by L-carnitine 2-butyl caprylate hydrochlorate, according to formulation Example 32 preparation shampoos.
[embodiment 15]
The preparation of hair oil
35-37 prepares hair oil according to formulation Example, and wherein the summation of each composition is 100%.
(formulation Example 35)
Salicylic acid 0.3％
Menthol 0.2％
Ethanol 60.0％
Glycerol 5.0％
L-carnitine 2-hexyldecanoic acid ester hydrochloride 1.0％
Purify waste water Surplus
Each composition is mixed and the feasible solution that at room temperature obtains.As a result, obtain hair oil.
(formulation Example 36)
Except replace L-carnitine 2-hexyldecanoic acid ester hydrochloride by L-carnitine 2-methyl palmitic acid ester hydrochloride, according to formulation Example 35 preparation hair oils.
(formulation Example 37)
Except replace L-carnitine 2-hexyldecanoic acid ester hydrochloride by L-carnitine 2-butyl caprylate hydrochlorate, according to formulation Example 35 preparation hair oils.

Claims (26)

1. preparation for external application to skin, it comprises by the carnitine derivative of formula (1) expression and/or by the salt of the carnitine derivative of formula (2) expression:
R wherein 1And R 2Each can have the saturated or undersaturated aliphatic hydrocarbyl of 1-18 carbon atom of side chain naturally;
R wherein 1And R 2Suc as formula defined in (1), X -Be that cationic moiety with described carnitine derivative keeps electroneutral inorganic or organic anion, and Y +Be that anionicsite with described carnitine derivative keeps electroneutral inorganic or organic cation.
2. the preparation for external application to skin of claim 1, the R in its Chinese style (1) and (2) 1And R 2Each can have the saturated or undersaturated aliphatic hydrocarbyl of 3-16 carbon atom of side chain naturally.
3. the preparation for external application to skin of claim 1, the R in its Chinese style (1) and (2) 1And R 2One of be the linear alkyl of 6 carbon atoms, and another is the linear alkyl of 8 carbon atoms.
4. the preparation for external application to skin of claim 1, the R in its Chinese style (1) and (2) 1And R 2One of be the linear alkyl of 4 carbon atoms, and another is the linear alkyl of 6 carbon atoms.
5. the preparation for external application to skin of claim 1, the R in its Chinese style (1) and (2) 1And R 2One of be methyl, and another is the linear alkyl of 14 carbon atoms.
6. each preparation for external application to skin among the claim 1-5, the X in its Chinese style (2) -It is to be selected from following anion: hydroxide ion, nitrate ion, sulfate ion, carbanion, bicarbonate ion, halide ion, formate ion, acetate ion, citrate ion, the tartrate anion ion, oxalate denominationby, fumarate ion, saturated or the undersaturated fatty acid anion that can have 3-20 carbon atom of side chain, the carnitine anion, the carnitine derivative anion, ascorbic acid root anion, Ascorbic acid 2-phosphate anion and ascorbic acid phosphoric acid esters derivant anion.
7. each preparation for external application to skin among the claim 1-6, the Y in its Chinese style (2) +Be to be selected from following cation: hydrion, sodium ion, potassium ion, calcium ion, magnesium ion, zinc ion, ammonium ion, carnitine cation and carnitine derivative cation.
8. each described preparation for external application to skin among the claim 1-7, wherein said by formula (1) expression carnitine derivative and/or account for the 0.01-20 quality % of described preparation for external application to skin by the salt of the carnitine derivative of formula (2) expression.
9. cosmetics, it comprises the salt of each described carnitine derivative among the claim 1-7 of 0.01-20 quality % and/or carnitine derivative.
10. the cosmetics of claim 9, it is the cosmetics that are used to promote lipid metabolism.
11. carnitine derivative by formula (3) expression:
Figure A20068003614500031
R wherein 3And R 4One of be the radical of saturated aliphatic alkyl that can have 1-16 carbon atom of side chain, and another is the radical of saturated aliphatic alkyl that can have 8-16 carbon atom of side chain.
12. salt by the carnitine derivative of formula (4) expression:
R wherein 3And R 4One of be the radical of saturated aliphatic alkyl that can have 1-16 carbon atom of side chain, and another is the radical of saturated aliphatic alkyl that can have 8-16 carbon atom of side chain, X -Be that cationic moiety with described carnitine derivative keeps electroneutral inorganic or organic anion, and Y +Be that anionicsite with described carnitine derivative keeps electroneutral inorganic or organic cation.
13. carnitine derivative by formula (5) expression:
Figure A20068003614500042
R wherein 5And R 6One of be the radical of saturated aliphatic alkyl that can have 2-7 carbon atom of side chain, and another is the radical of saturated aliphatic alkyl that can have 3-7 carbon atom of side chain.
14. salt by the carnitine derivative of formula (6) expression:
Figure A20068003614500051
R wherein 5And R 6One of be the radical of saturated aliphatic alkyl that can have 2-7 carbon atom of side chain, and another is the radical of saturated aliphatic alkyl that can have 3-7 carbon atom of side chain, X -Be that cationic moiety with described carnitine derivative keeps electroneutral inorganic or organic anion, and Y +Be that anionicsite with described carnitine derivative keeps electroneutral inorganic or organic cation.
15. carnitine derivative by formula (7) expression:
Figure A20068003614500052
16. salt by the carnitine derivative of formula (8) expression:
Figure A20068003614500053
X wherein -Be that cationic moiety with described carnitine derivative keeps electroneutral inorganic or organic anion, and Y +Be that anionicsite with described carnitine derivative keeps electroneutral inorganic or organic cation.
17. the salt of the carnitine derivative of claim 16, the X in its Chinese style (8) -It is to be selected from following anion: hydroxide ion, nitrate ion, sulfate ion, carbanion, bicarbonate ion, halide ion, formate ion, acetate ion, citrate ion, the tartrate anion ion, oxalate denominationby, fumarate ion, saturated or the undersaturated fatty acid anion that can have 3-20 carbon atom of side chain, the carnitine anion, the carnitine derivative anion, ascorbic acid root anion, Ascorbic acid 2-phosphate anion and ascorbic acid phosphoric acid esters derivant anion.
18. the salt of the carnitine derivative of claim 16 or 17, the Y in its Chinese style (8) +Be to be selected from following cation: hydrion, sodium ion, potassium ion, calcium ion, magnesium ion, zinc ion, ammonium ion, carnitine cation and carnitine derivative cation.
19. carnitine derivative by formula (9) expression:
Figure A20068003614500061
20. salt by the carnitine derivative of formula (10) expression:
Figure A20068003614500062
X wherein -Be that cationic moiety with described carnitine derivative keeps electroneutral inorganic or organic anion, and Y +Be that anionicsite with described carnitine derivative keeps electroneutral inorganic or organic cation.
21. the salt of the carnitine derivative of claim 20, the X in its Chinese style (10) -It is to be selected from following anion: hydroxide ion, nitrate ion, sulfate ion, carbanion, bicarbonate ion, halide ion, formate ion, acetate ion, citrate ion, the tartrate anion ion, oxalate denominationby, fumarate ion, saturated or the undersaturated fatty acid anion that can have 3-20 carbon atom of side chain, the carnitine anion, the carnitine derivative anion, ascorbic acid root anion, Ascorbic acid 2-phosphate anion and ascorbic acid phosphoric acid esters derivant anion.
22. the salt of the carnitine derivative of claim 20 or 21, the Y in its Chinese style (10) +Be to be selected from following cation: hydrion, sodium ion, potassium ion, calcium ion, magnesium ion, zinc ion, ammonium ion, carnitine cation and carnitine derivative cation.
23. carnitine derivative by formula (11) expression:
Figure A20068003614500071
24. salt by the carnitine derivative of formula (12) expression:
Figure A20068003614500072
X wherein -Be that cationic moiety with described carnitine derivative keeps electroneutral inorganic or organic anion, and Y +Be that anionicsite with described carnitine derivative keeps electroneutral inorganic or organic cation.
25. the salt of the carnitine derivative of claim 24, the X in its Chinese style (12) -It is to be selected from following anion: hydroxide ion, nitrate ion, sulfate ion, carbanion, bicarbonate ion, halide ion, formate ion, acetate ion, citrate ion, the tartrate anion ion, oxalate denominationby, fumarate ion, saturated or the undersaturated fatty acid anion that can have 3-20 carbon atom of side chain, the carnitine anion, the carnitine derivative anion, ascorbic acid root anion, Ascorbic acid 2-phosphate anion and ascorbic acid phosphoric acid esters derivant anion.
26. the salt of the carnitine derivative of claim 24 or 25, the Y in its Chinese style (12) +Be to be selected from following cation: hydrion, sodium ion, potassium ion, calcium ion, magnesium ion, zinc ion, ammonium ion, carnitine cation and carnitine derivative cation.
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* Cited by examiner, † Cited by third party
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CN104703583A (en) * 2012-10-09 2015-06-10 希格马托制药工业公司 Modified hyaluronic acid derivatives and use thereof
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Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100280111A1 (en) * 2007-12-28 2010-11-04 Showa Denko K.K. Skin external preparations and cosmetics
EP2238970A1 (en) 2007-12-28 2010-10-13 Showa Denko K.K. Emulsion preparation for external application to skin and cosmetic preparation
EP2216321A1 (en) * 2009-02-05 2010-08-11 Lonza Ltd. Process for the production of a fatty acid/carnitine derivative
DE102010028365A1 (en) 2010-04-29 2011-11-03 Lichtblick Gmbh Use of a phospholipid-containing composition for the removal of subcutaneous fat accumulations
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Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1156840B (en) * 1978-06-27 1987-02-04 Sigma Tau Ind Farmaceuti ACIL DERIVATIVES OF CARNITINE
IT1224842B (en) * 1988-12-27 1990-10-24 Sigma Tau Ind Farmaceuti USE OF L-CARNITINE DERIVATIVES IN THE THERAPEUTIC TREATMENT OF DEGENERATIVE ALTERATIONS OF THE NERVOUS SYSTEM
US6149924A (en) * 1998-07-20 2000-11-21 Biomed Research & Technologies, Inc. Composition for enhancing lipid production, barrier function, hydrogen peroxide neutralization, and moisturization of the skin
JP2002187821A (en) * 2000-12-21 2002-07-05 Noevir Co Ltd Hair cosmetic
JP2002201491A (en) * 2000-12-28 2002-07-19 Noevir Co Ltd Detergent composition

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CN103876950A (en) * 2014-03-12 2014-06-25 珀莱雅化妆品股份有限公司 Moisturizing nano light-screening agent for toning lotion and preparation method of light-screening agent
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CN112545956A (en) * 2020-12-18 2021-03-26 广西大学 Polyphenol-rich brown sugar moisturizing mask and preparation method thereof

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