CN1186656A - Water-in-oil type cosmetic emulsions - Google Patents

Water-in-oil type cosmetic emulsions Download PDF

Info

Publication number
CN1186656A
CN1186656A CN97122692A CN97122692A CN1186656A CN 1186656 A CN1186656 A CN 1186656A CN 97122692 A CN97122692 A CN 97122692A CN 97122692 A CN97122692 A CN 97122692A CN 1186656 A CN1186656 A CN 1186656A
Authority
CN
China
Prior art keywords
water
amide derivatives
acid
component
polyoxyethylene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN97122692A
Other languages
Chinese (zh)
Inventor
山本知幸
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kao Corp
Original Assignee
Kao Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kao Corp filed Critical Kao Corp
Priority to CN97122692A priority Critical patent/CN1186656A/en
Publication of CN1186656A publication Critical patent/CN1186656A/en
Pending legal-status Critical Current

Links

Abstract

Described is a water-in-oil type cosmetic emulsion comprising (A) an amide compound having a melting point of 0 to 50 DEG C. and (B) a nonionic surfactant having an HLB smaller than 8. The cosmetic composition according to the present invention has excellent stability, can enhance the water-retaining ability of the stratum corneum and has excellent skin-roughness lessening effects.

Description

Water-in-oil type cosmetic emulsions
The present invention relates to water-in-oil type cosmetic emulsions, this emulsifying physical ability is promoted the water-retaining property of keratodermatitis, and has fabulous effect to alleviating pachylosis.
Reduction that it is generally acknowledged water content in the horny layer can cause various skin problems, as pachylosis, drying and aging.The known chemical compound (for example iuntercellular lipoid, particularly aphingolipid) that contains amido link can address these problems effectively.Attempted this chemical compound is added in the cosmetic composition, promoting cuticular water-retaining property, thereby alleviated or prevent pachylosis.
But, therefore still can't reach the enough effects that alleviate pachylosis so far owing to be difficult to make the chemical compound of this amide containing key in cosmetic composition (as the water-in-oil emulsion body), stably to add.
Therefore the purpose of this invention is to provide a kind of cosmetic composition, said composition can be promoted the water-retaining property of keratodermatitis, and therefore has fabulous effect to alleviating pachylosis.
The inventor has carried out extensive studies for this reason.Found that and a kind of specific amide compound and a kind of HLB value be lower than 8 non-ionic surface active agent is shared to provide a kind of water-in-oil type cosmetic emulsions, amide compound can be stablized adding in this emulsified body, and this emulsifying physical ability is promoted the water-retaining property of keratodermatitis, and have fabulous effect to alleviating pachylosis, thereby finished the present invention.
A kind of water-in-oil type cosmetic emulsions is provided among the present invention, and this emulsified body comprises following composition (A) and (B):
(A) fusing point is 0-50 ℃ a amide compound; With
(B) HLB is lower than 8 non-ionic surface active agent.
The fusing point that is applicable to the amide compound of component of the present invention (A) is 0-50 ℃, preferred 10-40 ℃.Fusing point exceeds the amide compound of this scope can not stablize adding in said composition.
By the way, can determine fusing point through extrapolation according to the initial fusing point that JIS-K-7121-1987-9-9.1 (2) are measured among the present invention.
The example of this amide compound comprises amide, as isostearoyl amine, 2-Methylpentadecane amide and different myristamide, acyl glutamic acid vegetable stearin alcohol ester, and as shown in the formula the amide derivatives shown in (1) to (3):
Figure A9712269200051
R wherein 1And R 2Be same to each other or different to each other, being respectively can hydroxylated C 1-40Alkyl, R 3Be C 1-6Straight or branched alkylidene or singly-bound, R 4Be hydrogen atom, C 1-12Straight or branched alkoxyl or 2,3-dihydroxy propoxyl group, condition is to work as R 3When being singly-bound, R 4It is hydrogen atom.
Figure A9712269200052
R wherein 1And R 2Definition as above, R 3aBe C 3-6The straight or branched alkylidene, R 4aBe C 1-12The straight or branched alkoxyl. R wherein 1, R 2And R 3Definition as above, R 4bBe hydrogen atom, C 1-12Straight or branched alkoxyl or 2, the 3-glycidoxy, condition is to work as R 3When being singly-bound, R 4bIt is hydrogen atom.
In the amide derivatives in these amide derivatives (1), R 1And R 2Be same to each other or different to each other, being respectively can hydroxylated C 1-40Straight or branched, saturated or unsaturated alkyl.R 1And R 2Example comprise methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl, nonadecyl, heneicosyl, docosyl, nonacosyl, melissyl, iso stearyl, different heptadecyl, the 2-ethylhexyl, 1-ethyl heptyl, the 8-heptadecyl, 8-heptadecene base, 8,11-17 carbon dialkylenes, 2-heptyl undecyl, 9-vaccenic acid base, 1-hydroxyl nonyl, 1-hydroxyl pentadecyl, 2-hydroxyl pentadecyl, 15-hydroxyl pentadecyl, 11-hydroxyl heptadecyl and 11-hydroxyl-8-heptadecene base.
Preferred R 1Be C 8-26Straight or branched alkyl or alkenyl, its instantiation comprises: octyl group, decyl, dodecyl, myristyl, cetyl, octadecyl, docosyl, melissyl, iso stearyl, 2-ethylhexyl, 2-heptyl undecyl and 9-vaccenic acid base.Preferred especially alkyl R 1Be C 12-22The straight or branched alkyl is as the iso stearyl of dodecyl, myristyl, cetyl, octadecyl, docosyl and methyl-branched.
Preferred R 2Be C 9-25Straight or branched alkyl or alkenyl, its instantiation comprises: nonyl, undecyl, tridecyl, pentadecyl, heptadecyl, heneicosyl, nonacosyl, different heptadecyl, 1-ethyl heptyl, 8-heptadecyl, 8-heptadecene base, 8,11-17 carbon dialkylenes, 1-hydroxyl nonyl, 1-hydroxyl pentadecyl, 2-hydroxyl pentadecyl, 15-hydroxyl pentadecyl, 11-hydroxyl heptadecyl and 11-hydroxyl-8-heptadecene base.Preferred especially alkyl R 2Be C 11-21The straight or branched alkyl is as the different heptadecyl of undecyl, tridecyl, pentadecyl, heptadecyl, heneicosyl and methyl-branched.
R 3Be C 1-6Straight or branched alkylidene or singly-bound.Concrete alkylidene comprises: methylene, ethylene, trimethylene, 1,4-butylidene, pentamethylene, hexamethylene, 1-methyl isophthalic acid, 2-ethylidene, 1-methyl isophthalic acid, 3-propylidene, 2-methyl isophthalic acid, 3-propylidene, 1,1-dimethyl-1,2-ethylidene, 1-ethyl-1,2-ethylidene, 1-methyl isophthalic acid, 4-butylidene, 2-ethyl-trimethylene.Preferred R 3Be C 1-6Straight-chain alkyl-sub-, preferred especially methylene, ethylene and trimethylene.
R 4Be hydrogen atom, C 1-12The straight or branched alkoxyl, or 2,3-dihydroxy propoxyl group.Concrete alkoxyl comprises: methoxyl group, ethyoxyl, propoxyl group, butoxy, hexyloxy, octyloxy, the last of the ten Heavenly stems oxygen base, 1-methyl ethoxy and 2-ethyl hexyl oxy.Preferred R 4Be hydrogen atom, C 1-8Alkoxyl and 2,3-dihydroxy propoxyl group, preferred especially hydrogen atom, methoxyl group, ethyoxyl, propoxyl group, butoxy, 1-methyl ethoxy, 2-ethyl hexyl oxy and 2,3-dihydroxy propoxyl group.
In the amide derivatives (1), R in the chemical compound of special preferred formula (1) 1, R 2, R 3, and R 4Combination is selected from above-mentioned special preferable range.
In the amide derivatives (2), R 1And R 2Definition as above, and preferably use identical group.R 3aExample and amide derivatives (1) in the alkylidene R that enumerates 3Similar, but do not comprise methylene and ethylene.Preferred R 3aBe C 3-6Straight-chain alkyl-sub-, preferred especially trimethylene.R 4aExample and amide derivatives (1) in the alkoxyl R that enumerates 4Similar.Its preferred embodiment also with (1) in R 4Preferred embodiment similar.
In the amide derivatives (3), R 1, R 2And R 3Definition as above.R 4bBe hydrogen atom, C 1-12The straight or branched alkoxyl, or 2, the 3-glycidoxy.R 1, R 2And R 3Instantiation and amide derivatives (1) in cited similar.Its preferred embodiment is also with aforesaid similar.C 1-12Straight or branched alkoxyl R 4bExample and amide derivatives (1) in the R that enumerates 4Similar.Preferred especially hydrogen atom and R 4Cited similar alkoxyl and 2, the 3-glycidoxy.
Amide derivatives (1) in (3), the amide derivatives shown in the special preferred formula (1).
For example can adopt following preparation method (1) or preparation method (2) to make amide derivatives (1).Preparation method 1
Figure A9712269200081
Figure A9712269200091
R wherein 1, R 2And R 3Definition as above, R 4fBe hydrogen atom, C 1-12Straight or branched alkoxyl, condition are to work as R 3When being singly-bound, R 4fIt is hydrogen atom.R 6, R 8, R 10And R 11Be respectively C 1-8Straight or branched, saturated or undersaturated alkyl, wherein preferred C 1-5The straight or branched alkyl, special preferable methyl.R 9Be hydrogen atom, alkali metal atom or COR 8, R 7And R 12Be respectively leave away atom or group, as halogen atom, methanesulfonates group or toluenesulfonic acid ester group.For the consideration of practicality etc., R 7Preferably chlorine atom or bromine atoms, preferred especially chlorine atom.For the consideration of practicality etc., R 12Preferably methanesulfonates group or toluenesulfonic acid ester group.Preparation method 2 R wherein 1, R 2And R 6-R 12Definition as above, R 3gIt is the straight or branched alkylidene that contains 1-6 carbon atom.
In preparation method (1) and the preparation method (2) respectively to go on foot reaction condition as follows: the 1st step:
Under room temperature to 150 ℃ by glycidyl ether (7) and amine (8F) or (8G) prepared in reaction aminoalcohol derivative (4F) or (4G), under not solvent-laden condition or at water, lower alcohol such as methanol, ethanol or isopropyl alcohol, ether solvents such as oxolane, diox or glycol dimethyl ether, hydrocarbon solvent such as hexane, benzene, toluene or dimethylbenzene, or carry out this reaction under the existence of the mixed solvent of two or more required solvents.The 2nd step:
In room temperature to 150 ℃, normal pressure to the reduced pressure of 0.01mmHg by aminoalcohol derivative (4F) or (4G) and fatty acid ester (9) prepared in reaction amide derivatives (2F) or (2G), this fatty acid ester (9) preferred fatty acid lower alkyl esters, as fatty acid methyl ester or fatty-acid ethyl ester, this is reflected under the base catalyst existence and carries out, for example, at alkali metal hydroxide, as potassium hydroxide or sodium hydroxide, alkaline earth metal hydroxide is as calcium hydroxide, alkali carbonate, as potassium carbonate, alkaline earth metal carbonate is as calcium carbonate, or alkali alcoholate, as Feldalat NM, Sodium ethylate or potassium tert-butoxide carry out under existing.With respect to aminoalcohol derivative (4F) or (4G), the consumption of base catalyst is preferably the 0.01-0.2 equivalent.Preferably in reaction, from system, derive the alcohol of gained, response speed is accelerated.The 3rd step:
Amide derivatives (2F) or (2G) also can be by the preparation of following method: under room temperature to 100 ℃, make aminoalcohol derivative (4F) or (4G) and fat acyl chloride (10) reaction, this reaction can be under not solvent-laden condition or at halogenated hydrocarbon solvent such as chloroform, dichloromethane or 1, the 2-dichloroethanes, ether solvents such as oxolane diox or glycol dimethyl ether, hydrocarbon solvent such as hexane, benzene, toluene or dimethylbenzene, or there is or do not exist alkali in the mixed solvent of two or more required solvents, tertiary amine for example, as carrying out under pyridine or the triethylamine so that aminoalcohol derivative (4F) or (4G) change into carboxylic acid amide esters derivant (11F) or (11G), then, the 4th step:
Its ester group of hydrolysis optionally under alkali condition, for example at alkali metal hydroxide, as potassium hydroxide or sodium hydroxide, alkaline earth metal hydroxide is as calcium hydroxide, alkali carbonate, as potassium carbonate, alkaline earth metal carbonate is as calcium carbonate, or alkali alcoholate, there is hydrolysis down as Feldalat NM, Sodium ethylate or potassium tert-butoxide.The 5th step:
Under room temperature to 150 ℃, by amide derivatives (2F) or (2G) and the normal epoxide of 1-20 (12) (preferred chloropropylene oxide) prepared in reaction amide derivatives (3F) or (3G), this reaction can be under not solvent-laden condition or at water, ether solvents such as oxolane diox or glycol dimethyl ether, hydrocarbon solvent such as hexane, benzene, toluene or dimethylbenzene, or in the mixed solvent of two or more required solvents at the normal alkali metal hydroxide of 1-10, as potassium hydroxide or sodium hydroxide, alkaline earth metal hydroxide, as calcium hydroxide, alkali carbonate, as potassium carbonate, alkaline earth metal carbonate is as carrying out under the calcium carbonate existence.For consideration to productive rate etc., preferably in the presence of phase transfer catalyst, react, for example quaternary ammonium salt such as tetrabutyl ammonium bromide, tetrabutylammonium chloride, hexadecyltrimethylammonium chloride, cetyl trimethyl ammonium bromide, stearyl trimethyl ammonium chloride or two four oxyethylene group stearyl ammonio methacrylates, or the ammonium lactone, as lauryl dimethyl carboxyl ammonium lactone.The 6th step:
Under room temperature to 300 ℃ condition, prepare amide derivatives (1F) or (1G) through hydration with amide derivatives (3F) or (3G), under alkali condition, for example at alkali metal hydroxide, as potassium hydroxide or sodium hydroxide, alkaline earth metal hydroxide, as calcium hydroxide, alkali carbonate is as potassium carbonate, alkaline earth metal carbonate, carry out this reaction under existing as calcium carbonate, or under acid condition, for example at mineral acid such as sulphuric acid or hydrochloric acid, lewis acid such as boron trifluoride or butter of tin, carboxylic acid such as acetic acid, tetradecanoic acid or hexadecanoic acid, or carry out this reaction under sulfonic acid such as the p-methyl benzenesulfonic acid existence, or under soda acid mixing condition, carry out this reaction.The 7th step:
Amide derivatives (1F) or (1G) also can be by the preparation of following method: make amide derivatives (3F) or (3G) and one or more carboxylic acid derivates (13) react alone or in combination, preferred lower fatty acid of this carboxylic acid derivates (13) such as acetic acid, the alkali metal salt of lower fatty acid such as sodium acetate, lower aliphatic anhydride such as acetic anhydride, can for example carry out this reaction in the presence of the tertiary amine (as triethylamine) or not at base catalyst, make amide derivatives (3F) or (3G) transform into ester-acid amide derivant (14F) or (14G), the 8th step then:
Its ester group of hydrolysis optionally under alkali condition, for example at alkali metal hydroxide, as potassium hydroxide or sodium hydroxide, alkaline earth metal hydroxide is as calcium hydroxide, alkali carbonate, as potassium carbonate, alkaline earth metal carbonate is as calcium carbonate, or alkali alcoholate, there is hydrolysis down as Feldalat NM, Sodium ethylate or potassium tert-butoxide.The 9th step:
Amide derivatives (1F) or (1G) also can be by the preparation of following method: make amide derivatives (3F) or (3G) react with carbonyl compound (15), this carbonyl compound is lower aliphatic ketone preferably, as acetone or butanone, this is reflected at acidic catalyst, for example at mineral acid such as sulphuric acid, hydrochloric acid or phosphoric acid, carboxylic acid such as acetic acid, lewis acid such as boron trifluoride or butter of tin carry out under existing, make amide derivatives (3F) or (3G) change into 1,3-dioxolanes-amide derivatives (16F) or (16G), then, the 10th step:
Under acid condition, make 1,3-dioxolanes-amide derivatives (16F) or (16G) carry out deketalization (deketalation), for example at mineral acid such as sulphuric acid, hydrochloric acid or phosphoric acid, carboxylic acid such as acetic acid, or there are reaction down in sulfonic acid such as p-methyl benzenesulfonic acid.The 11st step:
Also can be or (2G) and glycerol derivatives (17) prepared in reaction 1 by amide derivatives (2F), 3-dioxolanes-amide derivatives (16F) or (16G), in the presence of alkali, for example at alkali metal hydroxide, as potassium hydroxide or sodium hydroxide, alkaline earth metal hydroxide, as calcium hydroxide, alkali carbonate, as potassium carbonate, alkaline earth metal carbonate is as calcium carbonate, or alkali metal hydride, there are down not contain under the solvent condition or dinethylformamide or dimethyl sulfoxide, ether solvents such as oxolane diox or ethylene glycol diethyl ether at a non-proton transfering polarity solvent such as N as sodium hydride, hydrocarbon solvent such as hexane, benzene, toluene or dimethylbenzene, or carry out this reaction in the mixed solvent of two or more required solvents.
The amide derivatives (1) that is made by above method can carry out purification by in the art known method own.Among the present invention, the purity of the amide derivatives (1) that is suitable for can be 100%, or the purity that contains one or more intermediate products and/or one or more byproducts of reaction is more than 70% or 70% but is lower than 100% mixture, guarantee that simultaneously it has fabulous effect, and do not have safety issue.It should be noted that amide derivatives (1) comprises its solvate forms, is typically hydrate.
The example of the amide derivatives (1) that can be made by preparation method 1 comprises following chemical compound:
Figure A9712269200161
Wherein m and n are the numbers that its distribution concentrates on m=7 and n=7, and m+n is 10-16, and m is 4-10, and n is 4-10.
Figure A9712269200172
Wherein the definition of m and n as above.Wherein the definition of m and n as above.
Figure A9712269200173
The example of the amide derivatives (1) that can be made by preparation method 2 comprises following chemical compound:
Figure A9712269200181
Wherein m and n are the numbers that its distribution concentrates on m=7 and n=7, and m+n is 10-16, and m is 4-10, and n is 4-10.
Especially preferably the amide compound as component (A) is the N substituted amide chemical compound that contains at least 30 carbon atoms altogether.
In addition, as amide compound, preferably can be with 1% (weight) or higher, particularly 5% (weight) or higher amount keep those of bonded water.The bonded water content of institute can be by at room temperature adding water in the sample, will add maximum amount of water that water disappears up to homogeneous phase as the bonded water yield in sample, then by following equation calculate the total amount of bound water and sample total amount percentage ratio and determine:
Amide compound as component (A) can be used singly or in combination.The addition of preferred this amide compound is 0.02-20% (weight) based on total composition, preferred especially 0.02-10% (weight).Based on the consideration to stability, more preferably its addition is 0.02-5% (weight).
The HLB value that is applicable to the non-ionic surface active agent of component of the present invention (B) is lower than 8, preferably is no more than 5.When the HLB value is not less than 8, can not obtain excellent emulsified body stability.
By the way, term used herein " HLB value " is the index that characterizes hydrophilic-lipophilic balance (HLB), in the present invention, adopts following equation (Oda, people such as Tamura propose) to calculate this value:
Figure A9712269200191
The example that is suitable for the non-ionic surface active agent of making component (B) comprises: be added with polyoxyethylated surfactant, the derivant of polyoxyethylene castor oil and castor oil hydrogenated for example, as polyoxyethylene castor oil and polyoxyethylene hydrogenated Oleum Ricini, polyoxyethylene sorbitan fatty acid ester, as polyethenoxy sorbitan monostearate and polyethenoxy sorbitan four oleates, polyoxyethylene fatty acid glyceride such as polyoxyethylene glyceryl list isostearate and polyoxyethylene glyceryl three isostearates and polyoxyethylene alkyl ether and polyoxyethylene alkyl phenyl ether such as polyoxyethylene octyl group lauryl ether, polyoxyethylene lauryl ether, Polyoxyethylene cetyl ether, polyoxyethylene stearyl base ether and polyoxyethylene nonylplenyl ether; Polyglycerol alkyl ether; Polyglyceryl fatty acid ester; Sucrose fatty acid ester.
Preferred polyoxyethylene hydrogenated Oleum Ricini, polyoxyethylene alkyl ether and polyoxyethylene sorbitan fatty acid ester in these non-ionic surface active agents.
Enumerate more than that the surfactant of making component (B) can use separately or shared.For the consideration to stability, preferably its addition accounts for the 0.0002-10% (weight) of total composition, preferred 0.0002-5% (weight), more preferably 0.0002-3% (weight).
For the consideration to stability, preferred ingredient (A) and weight ratio (B) are 1: 0.01 to 1: 10, particularly 1: 0.4 to 1: 5.
Also can comprise oil ingredient in the cosmetic composition of the present invention.This oil ingredient there is not particular restriction.The example comprises: hydro carbons such as solid or liquid paraffin, vaseline, crystallite oil, ceresine, ceresin, montan wax, squalane and Squalene; Natural oils is as pressing tree oil, hydrogenated palm oil, Oleum Cocois, Oleum menthae, primrose oil, Cera Flava, sunflower oil, Oleum Arachidis hypogaeae semen, American Avocado Tree oil, Adeps Bovis seu Bubali, Adeps Sus domestica, horse fat, egg oil, olive oil, Carnauba wax, lanoline, hydrogenated lanolin, Jojoba oil; Ester oil class such as glyceryl monostearate, distearin, glyceryl monooleate, Palmic acid myristyl ester, the Palmic acid cetyl ester, 16-hydroxy-palmitic acid cetyl ester, the isooctyl acid cetyl ester, isopropyl palmitate, the Palmic acid isobutyl ester, isopropyl stearate, isobutyl stearate, stearic acid isocetyl ester, isopropyl myristate, tetradecanoic acid 2-octyl group dodecyl ester, lauric acid hexyl ester, isopropyl laurate, decyl oleate, different n-nonanoic acid isotridecyl ester, the neopentyl glycol dicaprate, diethyl phthalate, lactic acid myristyl ester, adipic acid hydrogen diisopropyl ester, the adipic acid cetyl ester, the tetradecanoic acid cetyl ester, malic acid two iso stearyl esters, diisopropyl adipate, the tetradecanoic acid cetyl ester, the lactic acid cetyl ester, single tetradecanoic acid list isostearic acid two glyceride, the 2 ethyl hexanoic acid cetyl ester, Palmic acid 2-Octyl Nitrite, tetradecanoic acid 2-octyl group dodecyl ester, neopentyl glycol two-2-ethylhexanoate, oleic acid 2-octyl group dodecyl ester, three glyceryl isostearates, two-p-methoxycinnamic acid list-2 ethyl hexanoic acid glyceride, tetramethylolmethane four esters, triglyceride, three-2 ethyl hexanoic acid glyceride; Higher fatty acids such as stearic acid, oleic acid, linoleic acid, isostearic acid, tetradecanoic acid, palmitoleic acid, castor oil acid, lauric acid, behenic acid, comprise the above fatty acid of enumerating and on the alkyl of above-mentioned fatty acid, have the hydroxy fatty acid of hydroxyl, and Palmic acid; Higher alcohol such as benzylalcohol, 2-Methylpentadecane alcohol, isooctadecanol, tadenan, hexadecanol, phenylethanol, hexadecanol, stearyl alcohol, oleyl alcohol, 2-octyldodecanol, butanols and 2-hexyldecanol; The aphingolipid of phospholipid, natural extract (sphingo) derivant and synthetic product thereof are as glycosyl ceramide, galactosylceramide and ceramide.They can be shared.
The preferred addition of this oil ingredient in cosmetic composition of the present invention is 0-70% (weight), more preferably 1-60% (weight), especially preferably 5-50% (weight).
Except that said components and water, also can add other component commonly used in cosmetic composition in the water-in-oil type cosmetic emulsions of the present invention, for example water-soluble alcohol such as ethanol, glycerol, sorbitol, propylene glycol, dipropylene glycol or 1,3-butanediol, water-soluble high-molecular substance, acid, alkali, salt, spice, coloring agent, antioxidant, UV absorbent, brightening agent, blood circulation accelerant, vitamin, chelating agen, lipoid controlling agent, powder class, astringent, skin soft agent and above-mentioned beyond surfactant.They can use in the degree that does not influence advantage of the present invention on demand.
Can adopt method commonly used to prepare water-in-oil type cosmetic emulsions of the present invention.It can be mixed with various dosage forms, for example skin care cosmetic compositions such as cream, cosmetic emulsion, foundation cream and skin cleansing composition.
Water-in-oil type cosmetic emulsions of the present invention stable containing has the good miscibility or the amide compound of mixed stability, thereby it has fabulous emulsified body stability, can promote the water-retaining property of keratodermatitis, and to alleviating or preventing pachylosis to have fabulous effect.
Will present invention is described by following examples.Yet should remember that the present invention is not limited only to following examples.In preparation embodiment 1-10, adopt preparation method 1 preparation amide derivatives (1).Preparation embodiment 1
In being housed, 2 liters of five mouthfuls of flasks of agitator, Dropping funnel, nitrogen ingress pipe and distilling apparatus add 743.2 gram (8.34mol) 3 methoxypropyl amine and 150 milliliters of ethanol, under 80 ℃ heating condition, in nitrogen atmosphere, stir the mixture of gained, in this mixture, dripped 165.9 gram (0.56mol) cetyl glycerin ethers through 3 hours.After dropwising, stirred this reactant mixture 12 hours down, under heating and decompression, steam ethanol and excessive 3 methoxypropyl amine at 80 ℃.Adopt the residue of silicagel column, thereby obtain 196.5 gram aminoalcohol derivatives (4a) (productive rate: based on the cetyl glycerin ether is 91%) (the 1st step) through the chromatography purification gained.
It below is the physical characteristic of this aminoalcohol derivative (4a) of gained.White solid.Fusing point: (v is pure, cm for 53 ℃ of IR -1): 3340,2930,2855,1470,1310,1120,
1065,955,?900,720。 1H-NMR(CDCl 3,δ):0.88(t,J=6.3Hz,3H),1.25-1.45
(m,26H),1.45-1.85(m,6H),2.57
-2.76(m,4H),3.32(s,3H),3.38-
3.48(m,6H),3.77-3.89(m,1H)。
As above gained (the 1st step) and fused chemical compound (4a) and 1.53 restrain the methanol solution of the Feldalat NM of (7.91mmol) 28% to add 61.3 grams (158.1mmo1) in 1 liter of five mouthfuls of flask of agitator, Dropping funnel, nitrogen ingress pipe and distilling apparatus are housed, in 60 ℃ and nitrogen atmosphere, stir the mixture 30 minutes of gained, under the same conditions, in this mixture, dripped 38.3 gram (158.1mmol) methyl myristates through 1 hour.After dropwising, under 60 ℃, decompression (80-100 torr) condition, stirred this reactant mixture 5 hours, reaction is carried out fully.Cool off this reactant mixture, adopt silicagel column then, thereby obtain 88.7 gram amide derivatives (2a) (productive rate: 94%) (the 2nd step) through this mixture of chromatography purification.
Figure A9712269200212
It below is the physical characteristic of this amide derivatives (2a) of gained.White solid.Fusing point: (v is pure, cm for 48 ℃ of IR -1): 3440,2930,2860,1650,1625,1470,
1225,1210,1110,950,720。 1H-NMR(CDCl 3,δ):0.88(brt,J=6.3Hz,6H),1.15-
1.95(m,53H),2.36(t,J=7.5Hz,2H),3.29??????????2H),3.29-3.55(m,10H),3.33(s,3H)
,3.85-3.95(m,1H)。
In being housed, 1 liter of five mouthfuls of flask of agitator, nitrogen ingress pipe and distilling apparatus add 94.5 grams (158.0mmol) as above gained (the 2nd step) chemical compound (2a), 1.53 gram (4.74mmol) tetrabutyl ammonium bromide, 32.2 gram (347.6mmol) chloropropylene oxides, 12.6 gram (315.0mmol) sodium hydroxide and 66 milliliters of toluene, under 45 ℃, in nitrogen atmosphere, stirred 10 hours then.After washing the reactant mixture of gained with water 3 times under 70 ℃, under heating and decompression, boil off toluene and excessive chloropropylene oxide, and adopt silicagel column, thereby obtain 94.9 gram amide derivatives (3a) (productive rate: 92%) (the 5th step) through this residue of chromatography purification.
It below is the physical characteristic of this amide derivatives (3a) of gained.White solid.(v is pure, cm for fusing point: 38-39 ℃ IR -1): 2930,2855,1650,1470,1425,1380,
1210,1120,905,840,720。 1H-NMR(CDCl 3,δ):0.88(brt,J=6.0Hz,6H),1.10-
1.45(m,46H),1.45-1.90(m,6H),2.25
-2.48(m,2H),2.50-2.68(m,1H),2.70
-2.85(m,1H),3.02-3.20(m,1H),3.20
-4.00(m,13H),3.32(s,3H)。
In being installed, 100 milliliters of autoclaves of agitator add 71.3 grams (109.0mmol) as above gained chemical compound (5a) (the 5th step) and 11.78 gram (654.1mmol) water, 0.087 gram (2.18mmol) sodium hydroxide and 0.87 gram (4.36mmol) tetradecanoic acid, under 160 ℃, in closed system, stirred 6 hours then.After the reaction mixture, 80 ℃ down with 2% NaCl solution washing 2 times, adopt silicagel column to carry out purification then, thereby obtain 68.3 gram target amide derivatives (1a) (productive rate: 93%) (the 6th goes on foot) through chromatography.
Figure A9712269200231
It below is the physical characteristic of this amide derivatives (1a) of gained.Colourless transparent liquid.(v is pure, cm for IR -1): 3445,2930,2860,1630,1470,1420,
1380,1305,1210,1120,720。 1H-NMR(CDCl 3,δ):0.88(brt,J=6.7Hz,6H),1.15-
1.44(m,46H),1.44-1.95(m,8H),2.25
-2.45(m,2H),3.20-3.90(m,16H),3.33
(s,3H)。
In being housed, 500 milliliters of four-hole boiling flasks of agitator, nitrogen ingress pipe and distilling apparatus add 31.0 grams (47.7mmol) as above gained chemical compound (3a) (the 5th step), 11.9 gram (663.7mmol) water, 13.6 gram (165.9mmol) sodium acetates and 104.9 gram (1746.8mmol) acetic acid, under 70 ℃, in nitrogen atmosphere, stirred 19 hours then.Under heating and decompression, steam excessive acetic acid, thereby obtain containing ester-acid amide derivant (14a-1), (14a-2) and mixture (14a-3) (the 7th step).
This mixture that contains these ester-acid amide derivants does not still take out in flask, adds sodium hydrate aqueous solution, 18 gram water and 200 milliliters of butanols of 59.3 gram (711.2mmo1) 48% then, stirs 3 hours down at 80 ℃.Under heating and decompression, boil off butanols.With 250 milliliters of dilution with toluene residues, under 70 ℃, wash gained solution with water 2 times.Under heating and decompression, boil off toluene, adopt silicagel column then, thereby obtain the required amide derivatives (1a) of 22.3 grams (productive rate: 70%) (the 8th step) through the chromatography purification residue.Preparation embodiment 2
In being housed, 10 liters of five mouthfuls of flasks of agitator, Dropping funnel, nitrogen ingress pipe and distilling apparatus add 4680 gram (52.5mol) 3 methoxypropyl amines and 900 gram ethanol, under 80 ℃ heating condition, in nitrogen atmosphere, stir the mixture of gained, in this mixture, dripped 1045 gram (3.50mol) cetyl glycerin ethers through 3 hours.After dropwising, stirred this reactant mixture 1 hour down, under heating and decompression, steam ethanol and excessive 3 methoxypropyl amine, make the product of main component (the 1st step) thereby obtain containing aminoalcohol derivative (4a) at 80 ℃.
Main component in the product of above-mentioned gained (l step) is chemical compound (4a), and is contained in five mouthfuls of flasks of 10 liters, to wherein adding 9.82 gram (0.175mol) potassium hydroxide.Feed circulating nitrogen gas, (60-100 torr) stirs the mixture 3 hours of gained under 80 ℃, reduced pressure, and the water of gained is removed in distillation simultaneously.Stir under the same conditions then,, in this reactant mixture, drip 882.3 gram (3.64mol) methyl myristates through 3 hours.When dripping, the methanol of gained is removed in distillation.Dropwise the back and feeding under the condition of nitrogen, stirred this mixture 10 hours down, steam the methanol of gained, reaction is carried out fully, thereby obtained the chemical compound that main component is amide derivatives (2a) (the 2nd step) at 60-45 ℃, decompression (60-10 torr).
Be chemical compound (2a) and be contained in the as above products obtained therefrom (the 2nd step) in five mouthfuls of flasks of 10 liters and add 33.9 gram (0.105mol) tetrabutyl ammonium bromide, 712.5 gram (7.70mol) chloropropylene oxides and 2100 gram toluene to main component.Feed nitrogen, under 45 ℃, decompression (150-50 torr) and stirring condition, dripped 1750.0 and restrain (21.0mol) 48% sodium hydrate aqueous solutions through 2 hours.After dropwising, stir the mixture 10 hours of gained under the same conditions, so that reaction is carried out fully.After washing this reactant mixture with water 4 times under 70 ℃, toluene and excessive chloropropylene oxide are removed in distillation under heating and decompression, thereby obtain the product that main component is amide derivatives (3a) (the 5th step).
Be chemical compound (3a) and be contained in the as above products obtained therefrom (the 5th step) in five mouthfuls of flasks of 10 liters and add 378.2 gram (21.0mol) water, 5.83 gram (0.070mol) 48% sodium hydrate aqueous solutions and 32.0 gram (0.14mol) tetradecanoic acids to main component, under 100 ℃, nitrogen atmosphere, stirred 2.5 days then.Under 80 ℃ with this reactant mixture with 2% sodium-chloride water solution washing 3 times after, under heating and decompression, remove and anhydrate, thereby obtain the product that 2261.5 gram main components are target compound (1a) (the 6th step).The content of chemical compound in the product (1a) is 70%, wherein also contains intermediate product, byproduct of reaction etc., as following various shown in: Wherein n is the integer of 2-10.
Figure A9712269200271
Preparation embodiment 3
According to the 1st step among the preparation embodiment 1 and the 2nd step preparation amide derivatives (2b), but wherein be to substitute above-mentioned methyl myristate (the 1st step and the 2nd step) in the 2nd step of preparation embodiment 1 with methyl palmitate.
Figure A9712269200272
It below is the physical characteristic of this amide derivatives (2b) of gained.White solid.Fusing point: (v is pure, cm for 55 ℃ of IR -1): 3430,2930,2855,1620,1470,1205,
1110,950,720。 1H-NMR(CDCl 3,δ):0.88(brt,J=6.4Hz,6H),1.26-
1.89(m,57H),2.36(t,J=7.6Hz,2H),3.29
-3.52(m,10H),3.33(s,3H),3.88-3.95
(m,1H)。
Go on foot preparation amide derivatives (3b) according to the 5th among the preparation embodiment 1, but wherein be chemical compound (2b) (the 2nd step) alternative compounds (2a) (the 5th goes on foot) in the 5th step of preparation embodiment 1 by above gained.
It below is the physical characteristic of this amide derivatives (3b) of gained.White solid.(v is pure, cm for fusing point: 44-45 ℃ IR -1): 2930,2860,1650,1470,1425,1380,
1210,1120,910,845,755,720。 1H-NMR(CDCl 3,δ):0.88(brt,J=6.7Hz,6H),1.15-
1.45(m,50H),1.45-1.73(m,4H),1.73
-1.90(m,2H),2.25-2.48(m,2H),2.50
-2.68(m,1H),2.70-2.85(m,1H),3.00-
3.18(m,1H),3.18-4.00(m,13H),3.32(s,
3H)。
According to the 6th step preparation target amide derivatives (1b) among the preparation embodiment 1, but wherein be chemical compound (3b) (the 5th step) alternative compounds (3a) in the 6th step of preparation embodiment 1, and substitute tetradecanoic acid (the 6th step) with hexadecanoic acid by above gained.
It below is the physical characteristic of this amide derivatives (1b) of gained.White solid.Fusing point: (v is pure, cm for 33 ℃ of IR -1): 3445,2930,2860,1650,1630,1470,
1420,1380,1305,1210,1120,1080。 1H-NMR(CDCl 3,δ):0.88(brt,J=6.4Hz,6H),1.15-1.45
(m,50H),1.45-1.95(m,7H),2.25-2.55
(m,3H),3.20-3.92(m,16H),3.33(s,
3H)。
In being installed, 500 milliliters of four-hole boiling flasks of agitator and nitrogen ingress pipe add 34.1 grams (50.0mmol) above-mentioned (the 5th step) gained chemical compound (3b), 25.5 gram (250.0mmol) acetic anhydrides and 25.3 gram (250.0mmol) triethylamines, under 100 ℃, in nitrogen atmosphere, stirred 10 hours then.Reactant mixture is concentrated under heating and decompression, and adopt the residue of silicagel column, thereby obtain 34.9 gram ester-acid amide derivants (14b) (productive rate: 89%) (the 7th step) through the chromatography purification gained.
Figure A9712269200291
It below is the physical characteristic of this ester-acid amide derivant (14b) of gained.The brown transparency liquid. 1H-NMR(CDCl 3,δ):0.88(brt,J=6.4Hz,6H),1.26-
1.83(m,56H),2.03-2.20(m,6H),2.33
(t,J=7.1Hz,2H),3.12-4.35(m,15H),3.32
(s,3H)5.04-5.43(m,1H)。
The methanol solution and 200 ml methanol that in 200 milliliters of four-hole boiling flasks of agitator and nitrogen ingress pipe are installed, add the Feldalat NM of 33.9 grams (43.2mmol) above-mentioned (the 7th step) gained chemical compound (14b), 0.42 gram (2.16mmol) 28%, then at room temperature, in nitrogen atmosphere, stirred 3.5 hours.Under heating and decompression, concentrate this reactant mixture, and adopt the residue of silicagel column, thereby obtain 16.0 gram target amide derivatives (1b) (productive rate: 53%) (the 8th step) through the chromatography purification gained.
In being installed, 3 liters of four-hole boiling flasks of agitator and nitrogen ingress pipe add 45.2 grams (72.0mmol) above-mentioned (the 2nd step) gained chemical compound (2b), 2.86 gram (119.2mmol) sodium hydride and 800 milliliters of toluene, under 55 ℃, in nitrogen atmosphere, stirred 30 minutes then.Add 34.8 gram (121.5mmol) 1 then in the mixture of gained, 2-isopropylidene dioxy base-3-tosyl oxygen base propane stirred 18 hours down at 100 ℃ then.In this reactant mixture, adding 20 milliliters of 2-propanol under the ice-cooled condition so that unreacted sodium hydride inactivation, under heating and decompression, concentrate this reactant mixture then, and the employing silicagel column is through the residue of chromatography purification gained, thereby obtain 51.0 grams 1,3-dioxolanes-amide derivatives (16b) (productive rate: 96%) (the 11st step).
Figure A9712269200301
Below be gained this 1, the physical characteristic of 3-dioxolanes-amide derivatives (16b).Colourless transparent liquid. 1H-NMR(CDCl 3,δ):0.88(brt,J=6.4Hz,6H),1.20-
1.90(m,62H),2.36(t,J=
7.0Hz,2H),3.30-4.25(m,19H)。
In being installed, 2 liters of four-hole boiling flasks of agitator and nitrogen ingress pipe add 51.0 grams (68.9mmol) above-mentioned (the 11st step) gained chemical compound (16b), 0.50 gram (2.63mmol) hydration toluenesulfonic acid and 500 ml methanol, then at room temperature, in nitrogen atmosphere, stirred 12 hours.Under heating and decompression, concentrate this reactant mixture then, and adopt the residue of silicagel column, thereby obtain 41.0 gram target amide derivatives (1b) (productive rate: 85%) (the 10th step) through the chromatography purification gained.Preparation embodiment 4
According to the 1st step among the preparation embodiment 1 and the 2nd step preparation amide derivatives (2c), but wherein be in the 2nd step of preparation embodiment 1 by substitute methyl myristate (the 1st step and the 2nd step) with methyl laurate.
Figure A9712269200302
It below is the physical characteristic of this amide derivatives (2c) of gained.Colourless transparent liquid.(v is pure, cm for IR -1): 3435,2930,2855,1620,1470,1220,
1110,720。 1H-NMR(CDCl 3,δ):0.88(br?t,J=6.4Hz,6H),1.20-1.90
(m,49H),2.36(t,J=7.6Hz,2H),3.25
-3.52(m,10H),3.33(s,3H),3.88-3.95
(m,1H)。
Go on foot preparation amide derivatives (3c) according to the 5th among the preparation embodiment 1, but wherein be chemical compound (2c) (the 2nd step) alternative compounds (2a) (the 5th goes on foot) in the 5th step of preparation embodiment 1 by above gained.
It below is the physical characteristic of this amide derivatives (3c) of gained.Weak yellow liquid.(v is pure, cm for IR -1): 2940,2875,1750,1650,1470,1380,
1210,1120,910,845。 1H-NMR(CDCl 3,δ):0.88(brt,J=6.4Hz,6H),1.15-
1.45(m,42H),1.45-1.75(m,4H),
1.75-1.90(m,2H),2.25-2.50(m,2H),
2.50-2.68(m,1H),2.70-2.85
(m,1H),3.00-3.18(m,1H),3.18-4.00
(m,13H),3.32(s,3H)。
Among the embodiment 1 the 7th goes on foot and the 8th step preparation target amide derivatives (1c) according to preparing, but wherein is chemical compound (3c) (the 5th goes on foot) alternative compounds (3a) (the 7th step and the 8th step) by above gained in the 7th of preparation embodiment 1 goes on foot.
It below is the physical characteristic of this amide derivatives (1c) of gained.Colourless transparent liquid.(v is pure, cm for IR -1): 3430,2930,2860,1650,1630,1470,
1380,1260,1210,1115,1080,795,720。 1H-NMR(CDCl 3,δ):0.88(brt,J=6.7Hz,6H),1.15-1.45
(m,42H),1.45-1.97(m,8H),2.25-2.45
(m,2H),3.15-3.92(m,16H),3.33(s,3H)。Preparation embodiment 5
Go on foot and the 2nd step preparation amide derivatives (2d) according to the 1st among the preparation embodiment 1, but wherein be that (" Lunac P-70 " is that weight ratio is the mixture of 3: 70: 27 tetradecanoic acid, hexadecanoic acid and octadecanoid acid by the alternative methyl myristate of the methyl ester of " Lunac P-70 " (the 1st step and the 2nd step) in the 2nd step of preparation embodiment 1; Produce by KAO. Corp. SA), described methyl ester is in the presence of sulfuric acid catalyst, is obtained by " Lunac P-70 " and methanol reaction through reflux.
Figure A9712269200321
Wherein A represents C 13H 27, H 15H 31And C 17H 35Mixture.
It below is the physical characteristic of this amide derivatives (2d) of gained.White solid.Fusing point: (v is pure, cm for 50 ℃ of IR -1): 3430,2930,2860,1620,1470,1205,
1110,950,720。
According to the 11st step among the preparation embodiment 3 and the 10th step preparation target amide derivatives (1d), but wherein in the 11st step of preparation embodiment 3 chemical compound (2d) (the 2nd step) alternative compounds (2b) by above gained, and in ensuing the 10th step, not to 1 of gained, 3-dioxolanes-amide derivatives (16d) carries out purification (the 11st step and the 10th step). Wherein A represents C 13H 27, C 15H 31And C 17H 35Mixture.
It below is the physical characteristic of this amide derivatives (1d) of gained.White solid.Fusing point: (v is pure, cm for 32 ℃ of IR -1): 3445,2930,2860,1650,1630,1470,
1380,1210,1120,1080,720。Preparation embodiment 6
According to the prepared in reaction aminoalcohol derivative (4e) in the 1st step among the preparation embodiment 1, but wherein be to substitute cetyl glycerin ether (the 1st step) in the 1st step of preparation embodiment 1 by batiolum.
Figure A9712269200332
It below is the physical characteristic of this aminoalcohol derivative (4e) of gained.White solid.(v is pure, cm for fusing point: 57-58 ℃ IR -1): 3340,2930,2855,1470,1120,960,
900,840,720。 1H-NMR(CDCl 3,δ):0.88(brt,J=6.3Hz,3H),1.25-1.45
(m,30H),1.45-1.85(m,6H),2.55-2.75
(m,4H),3.32(s,3H),3.35-3.50(m,6H),
3.77-3.89(m,1H)。
Go on foot preparation amide derivatives (2e) according to the 2nd among the preparation embodiment 1, but wherein be chemical compound (4e) (the 1st step) alternative compounds (4a) (the 2nd goes on foot) in the 2nd step of preparation embodiment 1 by above gained.
Figure A9712269200341
It below is the physical characteristic of this amide derivatives (2e) of gained.The white solid fusing point: (v is pure, cm for 49 ℃ of IR -1): 3440,2930,2860,1650,1625,1470,
1225,1210,1110,950,720。 1H-NMR(CDCl 3,δ):0.88(brt,J=6.3Hz,6H),1.15-
1.95(m,57H),2.36(t,J=
7.5Hz,2H),3.30-3.55(m,10H),3.33(s,3H),
3.85-3.95(m,1H)。
Go on foot preparation amide compound (3e) according to the 5th among the preparation embodiment 1, but wherein be chemical compound (2e) (the 2nd step) alternative compounds (2a) (the 5th goes on foot) in the 5th step of preparation embodiment 1 by above gained.
It below is the physical characteristic of this amide derivatives (3e) of gained.Colourless transparent liquid.(v is pure, cm for IR -1): 2930,2860,1650,1425,1380,1260,
1210,1120,910,720。 1H-NMR(CDCl 3,δ):0.88(brt,J=6.0Hz,6H),1.10-1.45
(m,50H),1.45-1.90(m,6H),2.25-2.50
(m,2H),2.50-2.68(m,1H),2.70-2.85
(m,1H),3.01-3.20(m,1H),3.20-4.00
(m,13H),3.32(s,3H)。
Among the embodiment 1 the 7th goes on foot and the 8th step preparation target amide derivatives (1e) according to preparing, but wherein is chemical compound (3e) (the 5th goes on foot) alternative compounds (3a) (the 7th step and the 8th step) by above gained in the 7th of preparation embodiment 1 goes on foot.
It below is the physical characteristic of this amide derivatives (1e) of gained.White solid.Fusing point: (v is pure, cm for 23 ℃ of IR -1): 3425,2930,2860,1650,1630,1470,
1380,1220,1210,1120,720。 1H-NMR(CDCl 3,δ):0.88(brt,J=6.7Hz,6H),1.17-1.45
(m,49H),1.45-1.92(m,8H),2.22-2.45
(m,2H),3.20-3.90(m,17H),3.33(s,3H)。Preparation embodiment 7
According to the 2nd step preparation amide derivatives (2f) among the preparation embodiment 1, but wherein be chemical compound (4e) alternative compounds (4a) in the 2nd step of preparation embodiment 1, and substitute methyl myristate (the 1st step and the 2nd step) with methyl palmitate by the 1st step gained among the preparation embodiment 6.
Figure A9712269200352
It below is the physical characteristic of this amide derivatives (2f) of gained.White solid.(v is pure, cm for fusing point: 54-55 ℃ IR -1): 3430,2930,2855,1620,1470,1220,
1205,1110,950,885,720。 1H-NMR(CDCl 3,δ):0.88(brt,J=6.4Hz,6H),1.25-1.95
(m,61H),2.36(t,J=7.6Hz,2H),3.29
-3.52(m,10H),3.33(s,3H),3.88-3.95
(m,1H)。
According to the 5th step preparation amide derivatives (3f) among the preparation embodiment 1, but wherein be in the 5th step of preparation embodiment 1 by chemical compound (2f) alternative compounds (2a) (the 5th step).
It below is the physical characteristic of this amide derivatives (3f) of gained.White solid.(v is pure, cm for fusing point: 45-47 ℃ IR -1): 2930,2860,1650,1470,1425,1380,
1210,1120,910,845,755,720。 1H-NMR(CDCl 3,δ):0.88(brt,J=6.7Hz,6H),1.15-
1.45(m,54H),1.45-1.73(m,4H),
1.73-1.90(m,2H),2.25-2.48(m,2H),
2.50-2.68(m,1H),2.70-2.85
(m,1H),3.00-3.18(m,1H),3.18-4.00
(m,13H),3.32(s,3H)。
Among the embodiment 1 the 7th goes on foot and the 8th step preparation target amide derivatives (1f) according to preparing, but wherein is chemical compound (3f) (the 5th goes on foot) alternative compounds (3a) (the 7th step and the 8th step) by above gained in the 7th of preparation embodiment 1 goes on foot.
Figure A9712269200371
It below is the physical characteristic of this amide derivatives (1f) of gained.White solid.Fusing point: (v is pure, cm for 35 ℃ of IR -1): 3445,2930,2860,1650,1630,1470,
1420,1380,1305,1210,1120,1080。 1H-NMR(CDCl 3,δ):0.88(brt,J=6.4Hz,6H),1.15-1.45
(m,54H),1.45-1.95(m,7H),2.25-2.55
(m,3H),3.20-3.95(m,16H),3.33(s,3H)。Preparation embodiment 8
According to the prepared in reaction aminoalcohol derivative (4g) in the 1st step among the preparation embodiment 1, but wherein be to substitute cetyl glycerin ether (the 1st step) in the 1st step of preparation embodiment 1 by the myristyl glycerin ether.
Figure A9712269200372
It below is the physical characteristic of this aminoalcohol derivative (4g) of gained.White solid.Fusing point: (v is pure, cm for 47 ℃ of IR -1): 3340,2930,2855,1470,1310,1120,
1065,995,900,720。 1H-NMR(CDCl 3,δ):0.88(t,J=6.3Hz,3H),1.25-1.45
(m,26H),1.45-1.85(m,6H),2.55-2.75
(m,4H),3.32(s,3H),3.38-3.48(m,6H),
3.75-3.88(m,1H)。
According to the 2nd step preparation amide derivatives (2g) among the preparation embodiment 1, but wherein be chemical compound (4g) (the 1st step) alternative compounds (4a) in the 2nd step of preparation embodiment 1, and wherein substitute methyl myristate (the 2nd step) with methyl palmitate by above gained.
Figure A9712269200381
It below is the physical characteristic of this amide derivatives (2g) of gained.White solid.Fusing point: (v is pure, cm for 47 ℃ of IR -1): 3440,2930,2855,1620,1470,1205,
1110,950,720。 1H-NMR(CDCl 3,δ):0.88(brt,J=6.4Hz,6H),1.26-
1.89(m,52H),2.36(t,J=
7.6Hz,2H),3.29-3.52(m,11H),3.33
(s,3H),3.88-3.95(m,1H)。
Go on foot preparation amide compound (3g) according to the 5th among the preparation embodiment 1, but wherein be chemical compound (2g) (the 2nd step) alternative compounds (2a) (the 5th goes on foot) in the 5th step of preparation embodiment 1 by above gained.
It below is the physical characteristic of this amide derivatives (3g) of gained.Colourless transparent liquid.(v is pure, cm for IR -1): 2930,2860,1650,1470,1425,1380,
1210,1120,910,845,755,720。 1H-NMR(CDCl 3,δ):0.88(brt,J=6.7Hz,6H),1.15-1.45
(m,46H),1.45-1.73(m,4H),1.73-
1.90(m,2H),2.25-2.50(m,2H),2.50-
2.68(m,1H),2.70-2.85(m,1H),3.00-3.18
(m,1H),3.18-4.00(m,13H),3.32(s,3H)。
Among the embodiment 1 the 7th goes on foot and the 8th step preparation target amide derivatives (1g) according to preparing, but wherein is chemical compound (3g) (the 5th goes on foot) alternative compounds (3a) (the 7th step and the 8th step) by above gained in the 7th of preparation embodiment 1 goes on foot.
It below is the physical characteristic of this amide derivatives (1g) of gained.White solid.Fusing point: (v is pure, cm for 27 ℃ of IR -1): 3445,2930,2860,1650,1630,1470,
1420,1380,1305,1210,1120,1080,720。 1H-NMR(CDCl 3,δ):0.88(brt,J=6.4Hz,6H),1.15-1.45
(m,45H),1.45-1.93(m,7H),2.20-2.60
(m,3H),3.20-3.90(m,17H),3.33(s,3H)。Preparation embodiment 9
According to the prepared in reaction aminoalcohol derivative (4h) in the 1st step among the preparation embodiment 1, but be by 1 in the 1st step of preparation embodiment 1 wherein, the 2-dimethoxy-ethylamine substitutes 3 methoxypropyl amine (the 1st step).
It below is the physical characteristic of this aminoalcohol derivative (4h) of gained.White solid.(v is pure, cm for fusing point: 54-55 ℃ IR -1): 3430,2920,2855,1470,1120,1065,
900,720。 1H-NMR(CDCl 3,δ):0.88(t,J=6.3Hz,3H),1.25-1.70
(m,30H),2.57-2.76(m,4H),3.32(s,3H),
3.38-3.48(m,6H),3.77-3.89(m,1H)。
According to the 2nd step preparation amide derivatives (2h) among the preparation embodiment 1, but wherein be chemical compound (4h) (the 1st step) alternative compounds (4a) in the 2nd step of preparation embodiment 1, and wherein substitute methyl myristate (the 2nd step) with methyl palmitate by above gained.
It below is the physical characteristic of this amide derivatives (2h) of gained.White solid.(v is pure, cm for fusing point: 51-52 ℃ IR -1): 3420,2920,2855,1620,1470,1110,
720。 1H-NMR(CDCl 3,δ):0.87(t,J=6.4Hz,6H),1.15-1.70
(m,55H),2.25-2.50(m,2H),3.20-
4.00(m,11H),3.34(s,3H)。
Go on foot preparation amide derivatives (3h) according to the 5th among the preparation embodiment 1, but wherein be chemical compound (2h) (the 2nd step) alternative compounds (2a) (the 5th goes on foot) in the 5th step of preparation embodiment 1 by above gained.
It below is the physical characteristic of this amide derivatives (3h) of gained.Colourless transparent liquid.(v is pure, cm for IR -1): 2930,2855,1650,1470,1420,1380,
1310,1250,1190,1120,910,850,720。 1H-NMR(CDCl 3,δ):0.88(brt,J=6.4Hz,6H),1.13-1.45
(m,50H),1.45-1.70(m,4H),2.30-2.50
(m,2H),2.50-2.70(m,1H),2.70-2.85
(m,1H),3.00-3.20(m,1H),3.20-4.00
(m,13H),3.32(s,3H)。
Go on foot preparation target amide derivatives (1h) according to the 6th among the preparation embodiment 1, but wherein be chemical compound (3h) (the 5th step) alternative compounds (3a) (the 6th goes on foot) in the 6th step of preparation embodiment 1 by above gained.
Figure A9712269200411
It below is the physical characteristic of this amide derivatives (1h) of gained.White solid.(v is pure, cm for fusing point: 31-32 ℃ IR -1): 3450,2930,2860,1630,1470,1380,
1300,1190,1160,720。 1H-NMR(CDCl 3,δ):0.88(t,J=6.4Hz,6H),1.15-1.75
(m,54H),2.20-2.45(m,3H),3.20-3.90
(m,17H),3.33(s,3H)。
According to preparation the 11st among embodiment 3 step preparation 1,3-dioxolanes-amide derivatives (16h), but wherein be chemical compound (2h) (the 2nd step) alternative compounds (2b) (the 11st step) by above gained in the 11st step of preparation embodiment 3.
Below be gained this 1, the physical characteristic of 3-dioxolanes-amide derivatives (16h).Colourless transparent liquid. 1H-NMR(CDCl 3,δ):0.88(t,J=6.4Hz,6H),1.15-1.70
(m,54H),1.34(s,3H),1.40(s,3H),
2.36(t,J=7.0Hz,2H),3.25-4.30
(m,19H)。
Go on foot preparation target amide derivatives (1h) according to the 11st among the preparation embodiment 3, but wherein be chemical compound (16h) (the 11st step) alternative compounds (16b) (the 10th goes on foot) in the 10th step of preparation embodiment 3 by above gained.Preparation embodiment 10
According to the prepared in reaction aminoalcohol derivative (4i) in the 1st step among the preparation embodiment 1, but wherein be to substitute 3 methoxypropyl amine (the 1st step) in the 1st step of preparation embodiment 1 by ethamine.
Figure A9712269200422
It below is the physical characteristic of this aminoalcohol derivative (4i) of gained.White solid.(v is pure, cm for fusing point: 60-61 ℃ IR -1): 3400,2930,2855,1470,1310,1110,
995,720。 1H-NMR(CDCl 3,δ):0.88(t,J=6.4Hz,3H),1.11(t,J
=7.2Hz,3H),1.15-1.70(m,30H),
2.55-2.80(m,4H),3.35-3.53(m,4H),
3.79-3.93(m,1H)。
According to the 2nd step preparation amide derivatives (2i) among the preparation embodiment 1, but wherein be chemical compound (4i) (the 1st step) alternative compounds (4a) in the 2nd step of preparation embodiment 1, and wherein substitute methyl myristate (the 2nd step) with methyl palmitate by above gained.
Figure A9712269200431
It below is the physical characteristic of this amide derivatives (2i) of gained.White solid.Fusing point: (v is pure, cm for 56 ℃ of IR -1): 3410,2930,2860,1625,1470,1380,
1305,1245,1210,1110,950,855,720。 1H-NMR(CDCl 3,δ):0.88(t,J=6.4Hz,6H),1.15-1.75
(m,57H),2.34(t,J=7.6Hz,2H),3.30
-3.55(m,9H),3.85-4.00(m,1H)。
Go on foot preparation amide compound (3i) according to the 5th among the preparation embodiment 1, but wherein be chemical compound (2i) (the 2nd step) alternative compounds (2a) (the 5th goes on foot) in the 5th step of preparation embodiment 1 by above gained.
Figure A9712269200432
It below is the physical characteristic of this amide derivatives (3i) of gained.Colourless transparent liquid.(v is pure, cm for IR -1): 2930,2855,1650,1470,1425,1380,
1210,1120,905,840,720。 1H-NMR(CDCl 3,δ):0.88(brt,J=6.4Hz,6H),1.10-1.75
(m,57H),2.25-2.50(m,2H),2.50-2.70
(m,1H),2.70-2.85(m,1H),3.00-4.00
(m,12H)
Go on foot preparation target amide derivatives (li) according to the 6th among the preparation embodiment 1, but wherein be chemical compound (3i) (the 5th step) alternative compounds (3a) (the 6th goes on foot) in the 6th step of preparation embodiment 1 by above gained.
It below is the physical characteristic of this amide derivatives (li) of gained.White solid.(v is pure, cm for fusing point: 35-36 ℃ IR -1): 3445,2930,2860,1630,1470,1420,
1380,1305,1210,1120,720。 1H-NMR(CDCl 3,δ):0.88(brt,J=6.4Hz,6H),1.1?-1.75
(m,57H),2.31(t,J=7.5Hz,2H),3.20
-3.90(m,16H)。Embodiment 1
1-5 prepares cosmetic emulsions according to table, and the effect of measuring its stability and alleviating pachylosis.The results are shown in Table 1-5.
By the way, about 1 milligram of sample is added Differential Scanning Calorimeter (DSC; 5 μ l; Seiko Electron Industry product) in the test cabinet, and heat under 100-200 ℃ scanning temperature, firing rate is 2 ℃/minute, to measure listed fusing point in the table.Be this fusing point according to JIS-K-7121-1987-9-9.1 (2) by the fusing point that initial fusing point extrapolation obtains.(preparation method)
With component 1-21 heating and dissolving, be heated to the component 22-29 of uniform temp then.Reaction mixture obtains each cosmetic emulsions then.(assay method) (1) stability
Be to store a week under 75% the condition with each cosmetic emulsions, estimate its state at 40 ℃, humidity.It is compared with the emulsified body compositions that has just prepared, do not find that being decided to be of outward appearance and characteristic variations is good, being decided to be of generation significant change is poor.(2) alleviate the effect of pachylosis
The measured is the female volunteers in ten age 20-50 years, and their buccal is because of becoming coarse winter.Each measured is coated in different cosmetic emulsions 2 weeks on the buccal of the left and right sides respectively.After applying for 2 weeks, measure the conductivity of skin at once.Particularly, after washing one's face with 37 ℃ warm water, each measured is that 20 ℃, humidity are undisturbedly to stay 20 minutes in 40% the room in temperature.Adopt skin conductivity instrument (IBS company product) to measure the water content in its horny layer.Conductivity values is lower than 20 explanation pachylosiies, i.e. the effect of emulsified body is not enough, is chosen as height and be at least effect in 20 o'clock in conductivity.
Table 1
Component (weight %) Product of the present invention
??1 ??2 ??3 ??4 ??5
??1 Polyoxyethylene iso stearyl ether (10E.O.) (HLB10)
??2 Polyoxyethylene hexyl decyl ethers (10E.O.) (HLB11)
??3 Polyoxyethylene octyl group lauryl ether (5E.O.) (HLB6)
??4 Polyoxyethylene hydrogenated Oleum Ricini (5E.O.) (HLB3) ??2 ??2 ??2 ??2 ??2
??5 Three isostearic acid polyoxyethylene hydrogenated Oleum Ricini (15E.O.) (HLB3)
??6 Polyoxyethylene cetyl ether (3E.O.) (HLB5)
??7 Amide derivatives (1a) (25 ℃ of fusing points) ??2
??8 Amide derivatives (1b) (33 ℃ of fusing points) ??2
??9 Amide derivatives (1c) (25 ℃ of fusing points) ??2
?10 Amide derivatives (1d) (32 ℃ of fusing points) ??2
?11 Amide derivatives (1e) (23 ℃ of fusing points) ??2
?12 Amide derivatives (1f) (35 ℃ of fusing points)
Component (weight %) Product of the present invention
????1 ????2 ????3 ????4 ????5
?13 Amide derivatives (1g) (27 ℃ of fusing points)
?14 Amide derivatives (1h) (31 ℃ of fusing points)
?15 Amide derivatives (li) (35 ℃ of fusing points)
?16 Natural ceramide (105 ℃ of fusing points)
?17 Stearmide (100 ℃ of fusing points)
?18 Different n-nonanoic acid isotridecyl ester ????10 ????10 ????10 ????10 ????10
?19 Single tetradecanoic acid list isostearic acid two glyceride
?20 Stearic acid
?21 Stearyl alcohol
?22 Citric acid
?23 Sodium citrate
?24 Succinic acid
?25 Sodium hydrogen phosphate
?26 86% glycerol ????30 ????30 ????30 ????30 ????30
?27 1,3 butylene glycol ????5 ????5 ????5 ????5 ????5
?28 Ethanol
?29 Water Surplus Surplus Surplus Surplus Surplus
Character Paste Paste Paste Paste Paste
Stability Well Well Well Well Well
Alleviate the effect of pachylosis High High High High High
Table 2
Component (weight %) Product of the present invention
??6 ??7 ??8 ??9 ??10
??1 Polyoxyethylene iso stearyl ether (10E.O.) (HLB10)
??2 Polyoxyethylene hexyl decyl ethers (10E.O.) (HLB11)
??3 Polyoxyethylene octyl group lauryl ether (5E.O.) (HLB6)
??4 Polyoxyethylene hydrogenated Oleum Ricini (5E.O.) (HLB3) ??2 ??2 ??2 ??2
??5 Three isostearic acid polyoxyethylene hydrogenated Oleum Ricini (15E.O.) (HLB3) ??1
??6 Polyoxyethylene cetyl ether (3E.O.) (HLB5) ??1
??7 Amide derivatives (1a) (25 ℃ of fusing points) ??5
??8 Amide derivatives (1b) (33 ℃ of fusing points)
??9 Amide derivatives (1c) (25 ℃ of fusing points)
??10 Amide derivatives (1d) (32 ℃ of fusing points)
??11 Amide derivatives (1e) (23 ℃ of fusing points)
??12 Amide derivatives (1f) (35 ℃ of fusing points) ??2
Component (weight %) Product of the present invention
????6 ????7 ????8 ????9 ????10
??13 Amide derivatives (1g) (27 ℃ of fusing points) ????2
??14 Amide derivatives (1h) (31 ℃ of fusing points) ????2
??15 Amide derivatives (1i) (35 ℃ of fusing points) ????2
??16 Natural ceramide (105 ℃ of fusing points)
??17 Stearmide (100 ℃ of fusing points)
??18 N-nonanoic acid isotridecyl ester ????10 ????10 ????10 ????10 ????10
??19 Single tetradecanoic acid list isostearic acid two glyceride
??20 Stearic acid
??21 Stearyl alcohol
??22 Citric acid
??23 Sodium citrate
??24 Succinic acid
??25 Sodium hydrogen phosphate
??26 86% glycerol ????30 ????30 ????30 ????30 ????30
??27 1,3 butylene glycol ????5 ????5 ????5 ????5 ????5
??28 Ethanol
??29 Water Surplus Surplus Surplus Surplus Surplus
Character Paste Paste Paste Paste Paste
Stability Well Well Well Well Well
Alleviate the effect of pachylosis High High High High High
Table 3
Component (weight %) Product of the present invention
??11 ??12 ??13 ??14 ??15
??1 Polyoxyethylene iso stearyl ether (10E.O.) (HLB10)
??2 Polyoxyethylene hexyl decyl ethers (10E.O.) (HLB11)
??3 Polyoxyethylene octyl group lauryl ether (5E.O.) (HLB6) ??3
??4 Polyoxyethylene hydrogenated Oleum Ricini (5E.O.) (HLB3) ??3 ??3 ??1
??5 Three isostearic acid polyoxyethylene hydrogenated Oleum Ricini (15E.O.) (HLB3) ??2 ??1
??6 Polyoxyethylene cetyl ether (3E.O.) (HLB5) ??1
??7 Amide derivatives (1a) (25 ℃ of fusing points)
??8 Amide derivatives (1b) (33 ℃ of fusing points) ??5
??9 Amide derivatives (1c) (25 ℃ of fusing points) ??5
?10 Amide derivatives (1d) (32 ℃ of fusing points) ??5
?11 Amide derivatives (1e) (23 ℃ of fusing points) ??5
?12 Amide derivatives (1f) (35 ℃ of fusing points) ??5
Component (weight %) Product of the present invention
???11?? ???12 ???13 ???14 ????15
??13 Amide derivatives (1g) (27 ℃ of fusing points)
??14 Amide derivatives (1h) (31 ℃ of fusing points)
??15 Amide derivatives (li) (35 ℃ of fusing points)
??16 Natural ceramide (105 ℃ of fusing points)
??17 Stearmide (100 ℃ of fusing points)
??18 Different n-nonanoic acid isotridecyl ester ????1 ????1 ????1 ????5
??19 Single tetradecanoic acid list isostearic acid two glyceride ????1
??20 Stearic acid ????2
??21 Stearyl alcohol ????2
??22 Citric acid ????0.5 ????0.2
??23 Sodium citrate ????0.5 ????0.2
??24 Succinic acid ????0.5 ????0.2
??25 Sodium hydrogen phosphate ????1 ????0.5
??26 86% glycerol ????5 ????10 ???10 ????20 ????10
??27 1,3 butylene glycol ????20 ????30 ????5 ????2 ????3
??28 Ethanol ????5 ????2 ????3
??29 Water Surplus Surplus Surplus Surplus Surplus
Character Paste Paste Paste Paste Paste
Stability Well Well Well Well Well
Alleviate the effect of pachylosis High High High High High
Table 4
Component (weight %) Product of the present invention Contrast product
???16 ???1 ???2 ??3 ??4
??1 Polyoxyethylene iso stearyl ether (10E.O.) (HLB10)
??2 Polyoxyethylene hexyl decyl ethers (10E.O.) (HLB11) ??3
??3 Polyoxyethylene octyl group lauryl ether (5E.O.) (HLB6) ???3
??4 Polyoxyethylene hydrogenated Oleum Ricini (5E.O.) (HLB3) ??1
??5 Three isostearic acid polyoxyethylene hydrogenated Oleum Ricini (15E.O.) (HLB3) ????1 ??2 ??1
??6 Polyoxyethylene cetyl ether (3E.O.) (HLB5) ??1
??7 Amide derivatives (1a) (25 ℃ of fusing points) ????1
??8 Amide derivatives (1b) (33 ℃ of fusing points)
??9 Amide derivatives (1c) (25 ℃ of fusing points)
?10 Amide derivatives (1d) (32 ℃ of fusing points)
?11 Amide derivatives (1e) (23 ℃ of fusing points)
?12 Amide derivatives (1f) (35 ℃ of fusing points)
Component (weight %) Product of the present invention Contrast product
????16 ????1 ????2 ????3 ????4
??13 Amide derivatives (1g) (27 ℃ of fusing points) ????5
??14 Amide derivatives (1h) (31 ℃ of fusing points)
??15 Amide derivatives (li) (35 ℃ of fusing points)
??16 Natural ceramide (105 ℃ of fusing points) ????5 ????5
??17 Stearmide (100 ℃ of fusing points) ????5 ????5
??18 Different n-nonanoic acid isotridecyl ester ????5 ????5 ????5 ????5
??19 Single tetradecanoic acid list isostearic acid two glyceride ????2 ????1
??20 Stearic acid ????0.5 ????2
??21 Stearyl alcohol ????0.5 ????2
??22 Citric acid ????0.1 ????0.5
??23 Sodium citrate ????0.1 ????0.5
??24 Succinic acid ????0.1 ???0.5
??25 Sodium hydrogen phosphate ????0.1 ???1
??26 86% glycerol ????5 ???20 ???10 ????5 ????10
??27 1,3 butylene glycol ????1 ???2 ???30 ????10 ????5
??28 Ethanol ????1 ???2 ????5
??29 Water Surplus Surplus Surplus Surplus Surplus
Character Paste Paste Paste Paste Paste
Stability Well Well Well Well Well
Alleviate the effect of pachylosis High High High High High
Table 5
Component (weight %) Contrast product
??5 ????6
??1 Polyoxyethylene iso stearyl ether (10E.O.) (HLB10) ??1
??2 Polyoxyethylene hexyl decyl ethers (10E.O.) (HLB11)
??3 Polyoxyethylene octyl group lauryl ether (5E.O.) (HLB6)
??4 Polyoxyethylene hydrogenated Oleum Ricini (5E.O.) (HLB3)
??5 Three isostearic acid polyoxyethylene hydrogenated Oleum Ricini (15E.O.) (HLB3)
??6 Polyoxyethylene cetyl ether (3E.O.) (HLB5)
??7 Amide derivatives (1a) (25 ℃ of fusing points) ????5
??8 Amide derivatives (1b) (33 ℃ of fusing points)
??9 Amide derivatives (1c) (25 ℃ of fusing points)
??10 Amide derivatives (1d) (32 ℃ of fusing points)
??11 Amide derivatives (1e) (23 ℃ of fusing points)
??12 Amide derivatives (1f) (35 ℃ of fusing points)
Component (weight %) Contrast product
????5 ????6
??13 Amide derivatives (1g) (27 ℃ of fusing points) ????5
??14 Amide derivatives (1h) (31 ℃ of fusing points)
??15 Amide derivatives (li) (35 ℃ of fusing points)
??16 Natural ceramide (105 ℃ of fusing points)
??17 Stearmide (100 ℃ of fusing points)
??18 Different n-nonanoic acid isotridecyl ester
??19 Single tetradecanoic acid list isostearic acid two glyceride ????2
??20 Stearic acid ????0.5
??21 Stearyl alcohol ????0.5
??22 Citric acid ????0.1
??23 Sodium citrate ????0.1
??24 Succinic acid ????0.1
??25 Sodium hydrogen phosphate ????0.1
??26 86% glycerol ????5
??27 1,3 butylene glycol ????1
??28 Ethanol ????1
??29 Water Surplus Surplus
Character The emulsifying shape Separate shape
Stability Difference Difference
Alleviate the effect of pachylosis Low Low
The result of table 1-5 shows that each cosmetic emulsions of the present invention has stability, and has the effect that alleviates pachylosis.

Claims (9)

1. water-in-oil type cosmetic emulsions comprises following component (A) and (B):
(A) a kind of fusing point be 0-50 ℃ amide compound and
(B) a kind of HLB value is lower than 8 non-ionic surface active agent.
2. according to the water-in-oil type cosmetic emulsions of claim 1, wherein component (A) is the N substituted amide chemical compound that has at least 30 carbon atoms altogether.
3. according to the water-in-oil type cosmetic emulsions of claim 1 or 2, wherein component (A) is selected from the amide derivatives shown in the following formula (1) to (3):
Figure A9712269200021
R wherein 1And R 2Be same to each other or different to each other, being respectively can hydroxylated C 1-40Alkyl, R 3Be C 1-6Straight or branched alkylidene or singly-bound, R 4Be hydrogen atom, C 1-12Straight or branched alkoxyl or 2,3-dihydroxy propoxyl group, condition is to work as R 3When being singly-bound, R 4Be hydrogen atom, R wherein 1And R 2Definition as above, R 3aBe C 3-6The straight or branched alkylidene, R 4aBe C 1-12The straight or branched alkoxyl,
Figure A9712269200023
R wherein 1, R 2And R 3Definition as above, R 4bBe hydrogen atom, C 1-12The straight or branched alkoxyl, or 2, the 3-glycidoxy, condition is to work as R 3When being singly-bound, R 4bIt is hydrogen atom.
4. according to each water-in-oil type cosmetic emulsions among the claim 1-3, wherein component (A) is the amide compound that can keep bonded water with 1% (weight) or higher amount.
5. according to each water-in-oil type cosmetic emulsions among the claim 1-4, wherein the consumption of component (A) is 0.02-20% (weight).
6. according to each water-in-oil type cosmetic emulsions among the claim 1-5, wherein component (B) comprises at least a following surfactant that is selected from: castor oil derivatives, the polyoxyethylene hydrogenated Oleum Ricini derivant, polyoxyethylene sorbitan fatty acid ester, the polyoxyethylene fatty acid glyceride, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyglycerol alkyl ether, polyglyceryl fatty acid ester and sucrose fatty acid ester.
7. according to each water-in-oil type cosmetic emulsions among the claim 1-5, wherein component (B) is at least a following surfactant that is selected from: polyoxyethylene hydrogenated Oleum Ricini, polyoxyethylene alkyl ether and polyoxyethylene sorbitan fatty acid ester.
8. according to each water-in-oil type cosmetic emulsions among the claim 1-7, wherein component (A) and amount ratio (B) are 1: 0.1 to 1: 10.
9. according to each water-in-oil type cosmetic emulsions among the claim 1-8, wherein the consumption of component (A) is 0.02-20% (weight), and the consumption of component (B) is 0.0002-10% (weight), and the consumption of oil ingredient is 0-70% (weight).
CN97122692A 1996-11-14 1997-11-13 Water-in-oil type cosmetic emulsions Pending CN1186656A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN97122692A CN1186656A (en) 1996-11-14 1997-11-13 Water-in-oil type cosmetic emulsions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP303101/96 1996-11-14
CN97122692A CN1186656A (en) 1996-11-14 1997-11-13 Water-in-oil type cosmetic emulsions

Publications (1)

Publication Number Publication Date
CN1186656A true CN1186656A (en) 1998-07-08

Family

ID=5176875

Family Applications (1)

Application Number Title Priority Date Filing Date
CN97122692A Pending CN1186656A (en) 1996-11-14 1997-11-13 Water-in-oil type cosmetic emulsions

Country Status (1)

Country Link
CN (1) CN1186656A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104470612A (en) * 2012-06-06 2015-03-25 海茂株式会社 Flocculation treatment agent
CN110023280A (en) * 2016-09-27 2019-07-16 株式会社爱茉莉太平洋 Questamide H compound and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104470612A (en) * 2012-06-06 2015-03-25 海茂株式会社 Flocculation treatment agent
CN104470612B (en) * 2012-06-06 2017-04-19 海茂株式会社 Flocculation treatment agent
CN110023280A (en) * 2016-09-27 2019-07-16 株式会社爱茉莉太平洋 Questamide H compound and preparation method thereof

Similar Documents

Publication Publication Date Title
CN1162144C (en) Ultraviolet absorbing composition
CN1112910C (en) Acid composition using fatty foaming material as main ingredient and its use on local application
CN1094734C (en) Enteral formula or nutritional supplement containing arachidonic and docosahexaenoic acid
CN1200688C (en) Use of sophorolipids and cosmetic and dermatological compositions
CN1137086C (en) 2-aminopropane-1,3-diol compounds medicinal use thereof and intermediates in synthesizing the same
CN1043227C (en) Ceramide, preparation and application in cosmetic and dermatological pharmaceutical of same
CN1220483C (en) Use of nanodispersions in pharmaceutical end formulations
CN1158560A (en) Biodegradable quaternary hair and skin conditioners
CN1241536C (en) Humectant and cosmetics and external prepan. contg. same
CN1176264C (en) Preparation of high content (alkyl fatty ester) dihyamine compound from trihydroxy ethylamine
CN1097453C (en) Crystalline hydroxy waxes as oil in water stabilizers for skin cleansing lqiuid composition
CN1665478A (en) Vesicle dispersion and cosmetic containing the same
CN1072206C (en) Amide derivatives an external skin or Hair care prepn.
CN1088089A (en) Personal cleanser with humidizer
CN1033086C (en) Phenylalkyl acid derivetives, process for preparing same and process for separating optical isomeride
CN1668270A (en) Powder-containing oil-in-water emulsified composition
CN1925838A (en) Shower oil gels
CN1946770A (en) Aqueous dispersions of silicone polyether block copolymers
CN1045589C (en) N-acylaminoglutaricamide derivative
CN1539006A (en) Lanolin substitute, production method thereof and application of same
CN1511189A (en) Process for preparing vegetable oil fractions rich in non-tocolic high-melting, unsaponifiable matter
CN1243759C (en) Modified phospholipid of poly alkyl oxygen and its producing process
CN1310900C (en) Bi-aromatic compounds and pharmaceutical and cosmetic compositions containing the same
CN1081876A (en) Whitening embellisher
CN1747746A (en) Invert emulsion type composition containing at least one active agent sensitive to the presence of water, and its uses in cosmetics and in dermatology

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication