CN1307278C - Gellant - Google Patents
Gellant Download PDFInfo
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- CN1307278C CN1307278C CNB038128802A CN03812880A CN1307278C CN 1307278 C CN1307278 C CN 1307278C CN B038128802 A CNB038128802 A CN B038128802A CN 03812880 A CN03812880 A CN 03812880A CN 1307278 C CN1307278 C CN 1307278C
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- gel
- jelling agent
- oil
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L9/00—Disinfection, sterilisation or deodorisation of air
- A61L9/01—Deodorant compositions
- A61L9/012—Deodorant compositions characterised by being in a special form, e.g. gels, emulsions
Abstract
A gellant which, when used in preparing an oil-based gel-form composition, can be dissolved in a composition at a relatively low temperature and with which a gel-form composition stable at high temperatures can be prepared. The gellant for oily bases comprises at least one N-acyl-L-(acidic amino acid) dialkylamide represented by the following general formula (1): (1) (wherein R<1> and R<2> each independently represents a C1-26 hydrocarbon group; R<3> represents a C7-10 hydrocarbon group; and n is 1 or 2), e.g., N-2-ethylhexanoyl-L-glutamic acid dibutylamide, and at least one monohydric lower alcohol, e.g., 3-methoxy-3-methylbutanol. When used in preparing an oil-based gel-form composition, the gellant can be dissolved at a temperature as low as 100 DEG C or below. A stable gel-form composition which is free from syneresis even at high temperatures can be prepared. The gel-form composition obtained is excellent in appearance including transparency and is suitable for use in applications such as a fragrance.
Description
Technical field
The present invention relates to a kind of jelling agent.Especially, the present invention relates to a kind of jelling agent, it can be dissolved in composition under low relatively temperature when preparation oil base gelatinous composition, thereby can make stable gel composition under hot conditions.
Background technology
The gel fragrant substance of the routine of reporting so far comprises hydrated gel fragrant substance and the organophilic gel fragrant substance that has than low water content, and the two is all supplied on market as commodity.The hydrated gel fragrant substance is long ago just well known, and it comprises hydrated gel, and for example agar and carrageen also have polyvinyl and polyacrylate based polyalcohol hydrated gel also to be used recently.They little by little ooze out fragrance by the evaporation that is accompanied by moisture in gel surface, and are used as fragrant substance.But, these hydrated gel fragrant substances moisture of easily emanating out, particularly, the natural polymerization gel in freezing back in case melt a large amount of moisture of will emanating out, thereby the problem that causes economic worth obviously to reduce.In addition, the low gel strength of polymer hydration gel causes the relatively poor problem of shape-holding property energy.Therefore in addition, these hydrated gel fragrant substance heat resistanceheat resistant poor performance are not suitable for when the use that be exposed under the hot conditions, for example, are used on the automobile as fragrant substance etc.
On the other hand, because hydrophobic gel fragrant substance can easily make ethanol, ethylene glycol monoethyl ether, petroleum solvent and native hydrocarbon kind solvent etc. and higher fatty acid salt, particularly sodium stearate agglutination, they have been applied to commercial fragrant substance product (JP-B-S56-6783 and JP-B-S57-50502).Yet, according to these hydrophobic gel fragrant substances, solvent, for example water, glycol or alcohol become the neccessary composition of dissolving as the sodium stearate of gel former.Thereby the shortcoming of the gel fragrant substance that these are hydrophobic is, owing to the gel that produces after heat impedance difference and the preparation in resistates enrichment and outward appearance for example poor transparency reduced value as commerical prod.The example of other hydrophobic gel fragrant substance comprise with hydrogenated castor oil and hydrocarbon compound for example the preparation of d-limonene the solid gel fragrant substance and with 1 2-hydroxystearic acid and the hydrocarbon compound solid gel fragrant substance for preparing of d-limonene for example.Yet the shortcoming of the gel fragrant substance that these are hydrophobic is that to compare the heat resistanceheat resistant performance poorer with above-mentioned sodium stearate gel fragrant substance.
On the other hand, it is also disclosed that the amine salt of N-acylamino acid or its ester or amide derivatives have pectisation (JP-B-S53-13434) on oil base.In addition, JP-B-H03-80025 has disclosed the gelatinous composition that can obtain the properties of transparency excellence by amide derivatives and volatile terpene hydrocarbon.Yet according to these methods, the solid gelling of spices etc. needs a large amount of jelling agents, and the dissolving jelling agent needs 100 ℃ or higher high temperature.Therefore, they are unsatisfactory as the production method of the gelatinous composition that contains fragrant substance.
[problem to be solved by this invention]
An object of the present invention is to provide a kind of jelling agent, it has overcome above-mentioned shortcoming.Especially, an object of the present invention is to provide a kind of jelling agent, it can be when preparation oil base gelatinous composition dissolves under 100 ℃ or lower low temperature, and available its makes in addition hot conditions under also stable, particularly, under hot conditions, can not cause the gelatinous composition of synersis.In addition, another object of the present invention provides a kind of jelling agent, and it is used to prepare for example gelatinous composition of transparency excellence of outward appearance.In addition, another object of the present invention provides a kind of gelatinous composition, and it can be used as fragrant substance, can not cause for example transparency excellence of synersis and outward appearance under hot conditions.
[method of dealing with problems]
The contriver researchs and solves the problems referred to above hardy; therefore the jelling agent of finding to contain specific N-acyl group-L-acidic amino acid dialkyl amide and lower alcohol has the excellent specific property as the oil base jelling agent; when preparation oil base gelatinous composition, can under 100 ℃ or lower low temperature, dissolve, and even under hot conditions, allow to make the stable gel composition.In addition, find that the gelatinous composition of gained is the composition with good transparency, and can be used as fragrant substance.The present invention is based on above-mentioned discovery finishes.
Summary of the invention
Therefore, the invention provides a kind of jelling agent, it contains the N-acyl group-L-acidic amino acid dialkyl amide shown in the general formula (I) below at least a:
(R wherein
1And R
2Represent alkyl respectively independently with 1-26 carbon atom; R
3Representative has the alkyl of 7-10 carbon atom; And n represents 1 or 2) and at least a monobasic lower alcohol.Jelling agent of the present invention can be used to make the oil base gelling.
According to the preferred embodiments of the invention, provide the above-mentioned jelling agent that is defined as follows, wherein R
1And R
2Be respectively straight or branched alkyl independently with 1-26 carbon atom, and R
3For having the straight or branched alkyl of 7-10 carbon atom; And wherein n is 2.
The preferred embodiment according to the present invention provides the above-mentioned jelling agent that is defined as follows, wherein R
1And R
2Respectively independently for having the straight or branched alkyl of 3-5 carbon atom; R
3For having the straight or branched alkyl of 7-9 carbon atom; And n is 2.
The also preferred embodiment according to the present invention, wherein above-mentioned jelling agent, wherein the ratio by the N-acyl group shown in the top general formula (the I)-gross weight of L-acidic amino acid dialkyl amide and the gross weight of lower alcohol is 1: 100 to 100: 1.According to particularly preferred embodiment of the present invention, the above-mentioned jelling agent that is defined as follows is provided, be N-2-ethyl hexanoyl base-L-L-glutamic acid dibutyl acid amides wherein by the N-acyl group shown in the top general formula (I)-L-acidic amino acid dialkyl amide.In addition, also providing lower alcohol wherein is that the above-mentioned jelling agent of 3-methoxyl group-3-methyl butanol or propylene glycol monomethyl ether is as the preferred embodiments of the invention.
On the other hand, the invention provides and contain (a) the above-mentioned jelling agent and (b) gelatinous composition of at least a oil base.According to this gelatinous composition embodiment preferred, providing wherein, oil base is the above-mentioned gelatinous composition of volatile terpene hydrocarbon; Above-mentioned gelatinous composition as fragrant substance is provided; Provide and be the above-mentioned gelatinous composition of substantial transparent composition; And provide the above-mentioned gelatinous composition that under hot conditions, can not cause synersis basically.
In addition, the present invention also provides the method that makes the oil base gelationization, comprises that the compound shown in the general formula (I) that will contain above at least a and the jelling agent of at least a lower alcohol mix with at least a oil base; Production contains the method for the gelatinous composition of oil base, and it comprises above-mentioned jelling agent is mixed with at least a oil base; And above-mentioned jelling agent contains purposes in the gelatinous composition of at least a oil base in production.
Implement best mode of the present invention
In general formula (I), R
1And R
2Represent alkyl respectively independently with 1-26 carbon atom.R
1And R
2The alkyl of representative can be straight chain, side chain, ring-type or its combination.Also can be used as alkyl although contain the alkyl of unsaturated link(age), more preferably use alkyl.Can use preferably to have 1-10 carbon atom, more preferably the straight or branched alkyl of 2-6 carbon atom can use the straight or branched alkyl that also more preferably has 3-5 carbon atom.Normal-butyl group most preferably.
R
3Representative has the alkyl of 7-10 carbon atom.R
3The alkyl of representative can be straight chain, side chain, ring-type or its combination.Also can be used as alkyl although contain the alkyl of unsaturated link(age), more preferably use alkyl.Alkyl is preferably the straight or branched alkyl.More preferably, R
3Representative has the straight or branched alkyl of 7-9 carbon atom.R
3The examples of groups of-CO-representative comprises, for example, and positive capryloyl, positive nonanoyl, positive decanoyl, n-undecane acyl group, 2-ethyl hexanoyl base or the like.Wherein, consider high gelling ability, preferred capryloyl, decanoyl and 2-ethyl hexanoyl base, most preferably 2-ethyl hexanoyl base.Work as R
3When the group of-CO-representative is 2-ethyl hexanoyl base, consider as the 2-ethyl hexanoyl chloro of raw material be easy to obtain, more preferably use 2-(R, S)-the ethyl hexanoyl base.
In general formula (I), the acidic amino acid residue in the molecule is the L-asparagicacid residue, and the n of this moment is 1, is the L-glutaminic acid residue and work as it, and the n of this moment is 2.N is 2 in the preferred formula (I).Depend on R
1, R
2And/or R
3Kind; N-acyl group shown in the general formula (I)-L-acidic amino acid dialkyl amide can have one or more unsymmetrical carbons; and, also can use steric isomer for example to revolve isomer or diastereomer, stereoisomer mixture or racemic modification arbitrarily based on such unsymmetrical carbon for jelling agent of the present invention.In addition, work as R
1, R
2And/or R
3When having olefinic double bond, its configuration can be Z or E.For jelling agent of the present invention, also can use the pure geometrical isomer or the mixture of geometrical isomer arbitrarily.In addition, for jelling agent of the present invention, also can use the hydrate or the solvate of the N-acyl group-L-acidic amino acid dialkyl amide shown in the top arbitrarily general formula (I).
N-acyl group shown in the general formula (I)-L-acidic amino acid dialkyl amide can pass through; for example; Schotten baumann reaction takes place and makes N-acidylate L-glutamic acid or N-acidylate aspartic acid in fatty acid halide by making long-chain under the condition that exists at basic catalyst and L-L-glutamic acid or L-aspartic acid; make subsequently sulfonamide derivatives for example alkylamine prepare at acid catalyst or do not have to carry out reacting by heating under the catalyzer existence condition.Optionally; its can by with acylating agent for example fatty acid halide glutamyl ammonia or aspartyl ammonia N-acyl group are made, wherein glutamyl ammonia or aspartyl ammonia can by L-glutamic acid or aspartic acid with sulfonamide derivatives for example alkylamine at acid catalyst or the reaction that does not have to carry out under the catalyzer existence condition obtain.
Because having in the embodiment of this paper at length, explains the preparation example of the N-acyl group shown in the general formula (I)-L-acidic amino acid dialkyl amide; those skilled in the art can choose raw material, reagent, reaction conditions or the like and prepare the N-acyl group shown in the general formula (I)-L-acidic amino acid dialkyl amide arbitrarily by as required these methods being carried out random modification or replacement with reference to the preparation example.
In jelling agent of the present invention, a kind of compound can be used as the N-acyl group shown in the general formula (I)-L-acidic amino acid dialkyl amide, yet two or more compounds that are selected from compound shown in the general formula (I) can be used in combination.Although the amount of the N-acyl group-L-acidic amino acid dialkyl amide shown in the used general formula (I) is not particularly limited in the jelling agent of the present invention; as long as its amount can be so that the oil base gelling; but its amount is generally almost 0.1-15 weight part; preferred 0.5-10 weight part is 100 parts by the weight of wanting the agglomerative oil base.When its amount during less than 0.1 weight part, can not reach enough gel strengths, and when it measured greater than 15 weight parts, compound can not be dissolved in oil base, this can cause the outward appearance of the gelling oil base that obtained relatively poor.
The kind that can be used as the low-level alcohol compound of jelling agent composition among the present invention does not have special restriction.Although a kind of compound can be used as low-level alcohol compound, also can use two or more low-level alcohol compounds.What term " rudimentary " typically referred to the carbon atom that comprised in the compound molecule here adds up to 10 or still less.In addition, " alkylol cpd " is meant the monohydroxy-alcohol compound, do not comprise polyvalent alcohol for example binary or trivalent alcohol.Low-level alcohol compound can have functional group arbitrarily.Although the position of the kind of functional group, quantity, replacement does not have special restriction, for example can comprise one or two or a plurality of alkoxyl group, aryl, oxo base or the like.In the molecule the total number of carbon atoms be 11 or more alkylol cpd volatility poor, therefore, when gelinite composition during as fragrant substance, higher alcohols can remain residual components in use or after using.
The example of lower alcohol comprises, for example methyl alcohol, ethanol, Virahol, propyl carbinol, 2-butanols, the trimethyl carbinol, 3-methoxybutanol, 3-methoxyl group-3-methyl butanol, amylalcohol, hexanol, hexalin, cis-3-hexenol, linalool, β-styroyl alcohol, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol methyl ether, propylene glycol methyl ether acetate or the like.Wherein, preferred 3-methoxybutanol, 3-methoxyl group-3-methyl butanol, hexanol, hexalin, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol methyl ether and propylene glycol methyl ether acetate.The example of preferred low-level alcohol compound comprises, 3-methoxyl group-3-methyl butanol, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether and dipropylene glycol methyl ether.Wherein, the gelling ability that the temperature when considering possible reduction dissolving and keeping suits, preferred especially 3-methoxyl group-3-methyl butanol or propylene glycol monomethyl ether.Although there is no particular limitation for the amount of employed low-level alcohol compound, for example, the amount that this compound uses is about 0.1-50 weight part, and more preferably 1-20 weight part is 100 parts by the weight of the oil base of wanting gel.When it measured less than 0.1 weight part, the solvent temperature of jelling agent can improve, and when it measures greater than 50 weight parts, can not reach enough gel strengths.
Jelling agent of the present invention contains one or both or the multiple compound that is selected from the N-acyl group shown in the general formula (I)-L-acidic amino acid dialkyl amide and one or both or multiple low-level alcohol compound.When using this jelling agent, can make gelatinous composition with high gel strength and transparency, it is stable and even also can cause synersis at high temperature.Although (" gross weight " here is meant the gross weight of the N-acyl group shown in the general formula (I)-L-acidic amino acid dialkyl amide; when using a kind of compound; the weight of this compound; and when using two or more compounds; the weight sum of these compounds) and the ratio of the gross weight of low-level alcohol compound can be preferably 1: 100 to 100: 1 usually according to the random selection of desired characteristics.
There is no particular limitation to prepare the employed oil of gelatinous composition of the present invention, as long as above-mentioned jelling agent can dissolve when heating fully, and it is just passable to form gel when being cooled to room temperature, yet special therein example comprises silicone oil for example cyclomethicone and dimethicone; Higher alcohols is hexadecanol, isooctadecanol, lauryl alcohol, hexadecanol and octyl dodecanol for example; Lipid acid is Unimac 5680, undecylenic acid and oleic acid for example; Ester is Tetradecyl tetradecanoate, lauric acid hexyl ester, decyl oleate, Isopropyl myristate, the sad hexyl of dimethyl ester in the last of the ten Heavenly stems, Zerol, diethyl phthalate, ethylene glycol monostearate and octyl hydroxystearate for example; Hydrocarbon is d-limonene, α-Pai Xi, whiteruss, Vaseline and squalane for example; Wax is lanolin, reduction lanolin and carnauba wax for example; Fat and oil is ermine oil, cocoa seed oil, Oleum Cocois, palm-kernel oil, Camellia oil, sesame oil, Viscotrol C and olive wet goods for example.Wherein, preferred hydrocarbon ils, the outward appearance of considering final oil base gelatinous composition is transparency, more preferably terpene hydrocarbon for example.Further, preferred especially volatile terpene hydrocarbon.The example of volatile terpene hydrocarbon for example comprises, phellandrene, terpinolene, myrcene, α-Pai Xi, d-limonene or its mixture, perhaps contain main component and be the natural oil of these compounds arbitrarily, for example contain turps that main component is a α-Pai Xi, contain the orange oil etc. that main component is the d-limonene.
The part by weight of preferred used oil base is the about 10-99% that accounts for the gross weight of gel composition.When the weight percent of the oil base that contains less than 10 weight %, or during greater than 99 weight %, may not obtain enough gel strengths.For oil base, two or more oil base can be used in combination.
Although there is no particular limitation for the preparation method of gelatinous composition of the present invention; the gel composition of expection can obtain like this; for example; the stirring in about 50-100 ℃ of heating of N-acyl group-L-acidic amino acid dialkyl amide, low-level alcohol compound and oil base is formed uniform solution up to mixture, be cooled to room temperature subsequently.In order to dissolve jelling agent at low temperatures, N-acyl group-L-acidic amino acid dialkyl amide and lower alcohol need heating in advance to dissolve, and add oil when forming uniform solution, are cooled to room temperature subsequently.Optionally, heating N-acyl group-L-acidic amino acid dialkyl amide and lower alcohol are to dissolving, and the mixture solution of gained can add and makes its gelation in the oil thus.
For gel preparation of compositions of the present invention,, can use other jelling agent except above-mentioned jelling agent.For example, as the polyamide resin of oily jelling agent, jelling agent for example 12-oxystearic acid, sodium stearate, aluminium octoate, dibenzylidene-D-Sorbitol Powder or N-lauroyl-L-L-glutamic acid dibutyl acid amides can use.1,2-polyhutadiene etc. also can be used as auxiliary jelling agent.
Gelatinous composition of the present invention can be mixed with any spices, tensio-active agent, various additive, various powder etc. if desired.There is no particular limitation for the kind of these compositions, and it can choose at random according to the application and the desired characteristics of gelatinous composition.Two or more these compositions can be used in combination.
The example of spices comprises that for example, vegetable source natural spices is rose oil, jasmine oil, orange flower oil and oleum lavendulae for example; The animal source natural perfume is Moschus oil, civetta sesame oil and castoreum oil for example; The synthetic hydrocarbon polymer is Limonene and β-caryophyllene for example; Synthol is cis-3-hexenol and linalool for example; Synthetic aldehyde for example 2,6-nonadienal and citral; Synthetic ketone is β-ionone and exaltone for example; Synthetic ester is linalyl acetate for example; Synthetic lactone is γ-undecalactone for example; Synthesizing phenol is oxymethoxyallylbenzene for example; Synthesis oxide is rose oxide (roseoxide) for example; Synthetic nitrogenous compound is indoles for example; Synthetic acetal is the phenylacetic aldehyde dimethyl acetal for example; Synthetic Schiff's base is aurantiol for example.
The example of tensio-active agent comprises, for example, anion surfactant is for example N-long acyl acidic amino acid salt and N-long acyl neutral amino acids salt of N-long acyl amino acid salts for example, N-longer chain fatty acid acyl group-N methyl taurine salt, alkyl-sulphate and alkylene oxide adducts thereof, fatty acid amide ether sulfate, the metal-salt of lipid acid and weak base salt, the sulfo-succinic acid tensio-active agent, alkylphosphonic and alkylene oxide adducts thereof, alkyl ether carboxylic acid or the like; Nonionogenic tenside is for example glyceryl ether and alkylene oxide adducts thereof of ether type tensio-active agent for example, esters surface active agent is glyceryl ester and alkylene oxide adducts thereof for example, ether-ether class tensio-active agent is sorbitan ester and alkylene oxide adducts thereof for example, esters surface active agent is polyoxyalkylene fatty acid ester, glyceryl ester, fatty acid polyglycerol ester, sorbitol ester and sucrose fatty ester for example, alkyl glucoside, hard Viscotrol C Pyrrolidonecarboxylic acid diester and alkylene oxide adducts thereof and nitrogenous nonionogenic tenside be Marlamid for example; The for example aliphatic amine salt of cats product is alkyl ammomium chloride and dialkylammonium chloride for example, and quaternary ammonium salt, and the aromatic series quaternary ammonium salt is phenylmethane ammonium salt and fatty acid acyl arginine ester for example; With amphoterics trimethyl-glycine formula tensio-active agent carboxybetaine for example for example, aminocarboxylic acid tensio-active agent and imidazoline surfactant or the like.
The example of various additives comprises that for example, amino acid is Padil, L-Ala, Serine, Threonine, arginine, L-glutamic acid, aspartic acid, leucine and Xie Ansuan for example; Polyvalent alcohol is glycerine, ethylene glycol, 1,3 butylene glycol, propylene glycol and isoprenediol (isopreneglycol) for example; Water-soluble polymers for example polyamino acid comprises polyglutamic acid and poly aspartic acid and salt thereof, polyoxyethylene glycol, gum arabic, alginate, xanthan gum, hyaluronic acid, hyaluronate, chitin, chitosan, the water soluble shells polysaccharide, carboxyvinyl polymer, carboxymethyl cellulose, Natvosol, the hydroxypropyl trimethyl ammonium chloride, many chlorinations dimethylated methylene phenylpiperidines , Polyvinylpyrolidone (PVP) deutero-quaternary ammonium, cationization protein, collagen degradation product and derivative thereof, acylated protein and Polyglycerine; Sugar alcohol is N.F,USP MANNITOL and alkylene oxide adducts thereof for example, also has the animal or plant extract, nucleic acid, VITAMIN, enzyme, antiphlogistic, sterilant, sanitas, antioxidant, UV light absorber, sequestrant, antiperspirant, pigment, dyestuff, oxidation dye, organic and inorganic powder, the pH regulator agent, pearling agent, wetting agent or the like.
The example of various powder comprises that for example, toner is nylon microballon and silicone microballon for example, nylon powder; the fatty acid metal soap, Zh 1, red iron oxide, black iron oxide; chromic oxide, cobalt oxide, carbon black, ultramarine blue pigment; iron blue pigment, zinc oxide, titanium oxide; zirconium white, silicon-dioxide, aluminum oxide; cerium oxide, mica titanium, boron nitride; barium sulfate, lime carbonate, magnesiumcarbonate; pure aluminium silicate, Magnesium Silicate q-agent, silicon carbide; pigment, color lake, sericite; mica, talcum, kaolin; dish shape barium sulfate, butterfly barium sulfate, titanium oxide microparticle; zinc oxide fine particles, ferric oxide particles, acylamino acid is acyl-lysine for example; acyl glutamic acid; acyl group arginine and acyl amino acetate.In addition, they can for example silicone-treated, fluorine cpd processing, silane coupling agent processing, silane treatment, organic titanate processing, the processing of acidylate Methionin, fatty acid treatment, metallic soap be handled, oil solution is handled and amino acid is handled through surface treatment.
Although there is no particular limitation in the use of gelatinous composition of the present invention, for example can be used as fragrant substance, gel cosmetic products, parcel makeup, granular makeup, wax or the like, can also be used to prepare composition according to final purpose with appropriate form.
[embodiment]
Hereinafter, illustrate in greater detail the present invention by embodiment, still, scope of the present invention not only is confined to the following examples.The lauroyl glutamate dibutylamine that uses among the comparative example is by Ajinomoto Co., the amino acid jelling agent " GP-1 " of Inc. preparation.
Embodiment 1:N-2-(R, S)-preparation of ethyl hexanoyl base-L-L-glutamic acid dialkyl amide
The Sodium Glutamate monohydrate of 110g is dissolved in the water of 140g and 27% aqueous sodium hydroxide solution of 78g, is cooled to 10 ℃ then.After adding 110g acetone, to 27% aqueous sodium hydroxide solution of 2-ethyl hexanoyl chloro that wherein drips 87g and 78g.Acylation reaction liquid is with the dilution of 100g water, thereby and neutralizes with 95% the sulfuric acid of 63g and to make its layering in oil.Remove water layer, oil reservoir obtains oily matter through vacuum concentration.This oily matter is dissolved in the methyl alcohol of 742g, refluxes 9 hours after then adding 95% the sulfuric acid of 6.2g.By the time after reaction liquid was cooled to 35 ℃, the n-Butyl Amine 99 neutralization with 8.8g distilled out methyl alcohol and obtains oily matter.The n-Butyl Amine 99 that adds the toluene of 643g and 271g in this oily matter, in the time of stirring 90 ℃ of heating 10 hours.Sulfuric acid to warm water that wherein adds 506g and 130g makes its layering in oil, removes water layer.The warm water that adds 1200g under atmospheric pressure obtains the slurries of white solid except that desolvating subsequently to oil reservoir.Leach solid and obtain 2-ethyl hexanoyl base L-glutamic acid dibutyl acid amides 50 ℃ of following vacuum-dryings.
(a)
13C-NMR peak (solvent: CDCl
3): 12.04,12.07,13.74,13.96,13.99,20.08,20.11,22.70,22.74,26.01,29.83,31.56,31.60,32.37,33.05,39.29,39.53,49.37,52.53,52.56,171.29,173.03,176.66 (ppm)
(b)
1H-NMR peak (solvent: CDCl
3) δ: 3.248 (m, 4H), 4.373 (m, 1H), 6.199 (brs, 1H), 7.079 (brs, 1H), 7.169 (brs, 1H)
(c) wave number of infrared absorption spectrum: 3291.7,2961.0,2932.5,1638.2,1551.2,1452.6 (cm
-1)
(d) MS spectrum: 382.3 (M-H)
-
Embodiment 2:N-2-(R, S)-preparation of ethyl hexanoyl base-L-L-glutamic acid dibutyl acid amides
57.6g the Sodium Glutamate monohydrate be dissolved in the water of 92.6g, the IPA of 72.9g and 27% aqueous sodium hydroxide solution of 41g, be cooled to 10 ℃ then.When keeping pH11 (± 0.2) and 10 (± 5) ℃ humidity, with the 2-ethyl hexanoyl chloro of 1.5 hours Dropwise 5 0.1g in this solution and 27% aqueous sodium hydroxide solution of 49.6g, after this, be warming up to 30 ℃, stirred subsequently 1 hour.Keep 40 ℃ or more low temperature the time with 75% the sulfuric acid of 41.2g this acylation reaction liquid that neutralizes, regulate the pH value then and be 1.9 and make its layering in oil.Remove water layer, oil reservoir obtains oily matter through vacuum concentration (50 ℃, decompression).Add the water of 151.9g, the propyl carbinol of 91.3g and the toluene of 496.1g and in this oily matter, make its layering in oil in 40 ℃.Add the boron oxide of 21.4g and 61.9 butylamine in the gained oil reservoir, then reflux (bathe temperature: 135 ℃) so that gained water was carried out azeotropic dehydration above 13 hours with oil bath.Make its layering in oil to the dilute sulphuric acid that wherein adds 444g (about 6%) in 85 ℃.After the oil reservoir of gained adds the water of 419g, its layering in oil once more.When dripping the water of 1000g gradually with the oil reservoir decompression azeotropic of gained.In case remove propyl carbinol and toluene, promptly can obtain the slurries of white solid.Leach solid and through drying under reduced pressure obtain 105g N-2-(R, S)-ethyl hexanoyl base-L-L-glutamic acid dibutyl acid amides (productive rate: 89%).
Embodiment 3: the preparation of gelatinous composition
According to the composition shown in the table 1, the N-acyl glutamic acid dibutyl acid amides of the 0.1g of gained is inserted in the oil in embodiment 1.Oil bath is heated this mixture to dissolving, and placement subsequently is cooled to room temperature and obtains gelatinous composition.In addition, the gelatinous composition of gained is in 0 ℃, room temperature and 50 ℃ storage one month down, and its profile detects by an unaided eye respectively.Table 1 has been listed and has been dissolved the required temperature of jelling agent and the profile of gelatinous composition.About the profile of gelatinous composition, transparent solid gel indicates with zero; Transparent gel but with indicating that partial dehydration shrinks with △; Muddy gel or the usefulness * sign that liquefies fully.
[table 1]
| (% weight) | Composition 1 | Composition 2 | Composition 3 | Composition 4 | Composition 5 | Composition 6 |
| N-2-(R, S)-ethyl hexanoyl base-L-L-glutamic acid dibutyl acid amides | 1 | 1 | 1 | 1 | ||
| N-lauroyl glutamate dibutyl acid amides | 1 | 1 | ||||
| The d-limonene | 89.1 | 99 | 89.1 | 89.1 | 99 | 89.1 |
| 3-methoxyl group-3-methyl butanol | 9.9 | 9.9 | ||||
| Octyl dodecanol | 9.9 | |||||
| Glycerine | 9.9 | |||||
| The jelling agent solvent temperature (℃) | 95 ℃ or lower | 125 ℃ or higher | 95 ℃ or lower | 125 ℃ or higher | 110-115 ℃ | 80 ℃ or lower |
| Be stored in the outward appearance of sample under 0 ℃ of condition | ○ | ○ | △ | △ | × | |
| Store the outward appearance of sample at ambient temperature | ○ | ○ | △ | * (layering) | △ | × |
| Be stored in the outward appearance of sample under 50 ℃ of conditions | ○ | ○ | × | △ | × |
From the result shown in the table 1, prove that jelling agent of the present invention can be dissolved in oil base under low relatively temperature when preparation oil base gelatinous composition, and the gel composition of gained even also be stable and do not cause synersis under hot conditions.In addition, the gelatinous composition of gained also has fabulous transparency, has shown good surface appearance (composition 1).On the other hand, when not using low-level alcohol compound, the solvent temperature of jelling agent is higher than 100 ℃ (compositions 2), and when using higher alcohols to substitute lower alcohol, especially obviously (composition 3) that outward appearance degenerates in the storage process under hot conditions.And, when using triatomic glycerine to substitute low-level alcohol compound, find gelatinous composition layering (composition 4).In addition, when the N-lauroyl glutamate dibutyl acyl of use is not a compound shown in the general formula (I), the outward appearance of finding gelatinous composition degenerate (composition 5 and 6).
Industrial applicibility
Gelling agent of the present invention can dissolve under 100 ℃ or lower temperature when preparation oil base gel combination, can prepare stable composition and does not cause syneresis even under hot conditions. And the gel combination of gained has for example transparency of fabulous outward appearance, and is applicable to for example aromatic substance.
Claims (7)
1. jelling agent, it contains the N-acyl group-L-acidic amino acid dialkyl amide shown in the general formula (I) below at least a:
R wherein
1And R
2Represent alkyl respectively independently with 1-26 carbon atom; R
3Representative has the alkyl of 7-10 carbon atom; And n represents 1 or 2,
With at least a the total number of carbon atoms be 10 or still less monohydroxy-alcohol.
2. jelling agent as claimed in claim 1, wherein R
1And R
2Respectively independently for having the straight or branched alkyl of 3-5 carbon atom, R
3For having the straight or branched alkyl of 7-9 carbon atom; And n is 2.
3. jelling agent as claimed in claim 1, wherein the N-acyl group shown in Shang Mian the general formula (I)-L-acidic amino acid dialkyl amide is N-2-ethyl hexanoyl base-L-L-glutamic acid dibutyl acid amides.
4. as the described jelling agent of arbitrary claim in the claim 1 to 3, wherein said alcohol is 3-methoxyl group-3-methyl butanol or propylene glycol monomethyl ether.
5. gelatinous composition, it contains described jelling agent of arbitrary claim and at least a oil base in the claim 1 to 4.
6. gelatinous composition as claimed in claim 5, wherein said oil base are volatile terpene hydrocarbon.
As fragrant substance as claim 5 or 6 described gelatinous compositions.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP161757/2002 | 2002-06-03 | ||
| JP2002161757 | 2002-06-03 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1659251A CN1659251A (en) | 2005-08-24 |
| CN1307278C true CN1307278C (en) | 2007-03-28 |
Family
ID=29706588
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB038128802A Expired - Lifetime CN1307278C (en) | 2002-06-03 | 2003-05-29 | Gellant |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4462035B2 (en) |
| CN (1) | CN1307278C (en) |
| AU (1) | AU2003241933A1 (en) |
| WO (1) | WO2003102104A1 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005298635A (en) * | 2004-04-09 | 2005-10-27 | Shiseido Co Ltd | Gel composition and its manufacturing process |
| JP5071996B2 (en) * | 2004-08-18 | 2012-11-14 | 長谷川香料株式会社 | Oily gel composition |
| JP5092753B2 (en) * | 2006-01-06 | 2012-12-05 | 味の素株式会社 | Gelling agent |
| JP4872356B2 (en) | 2006-01-18 | 2012-02-08 | 味の素株式会社 | Underwater capsule oil type emulsion composition |
| WO2011067732A1 (en) * | 2009-12-04 | 2011-06-09 | Firmenich Sa | Gel air freshener |
| PL2570474T3 (en) * | 2011-09-13 | 2015-04-30 | Procter & Gamble | Stable water-soluble unit dose articles |
| WO2013118921A1 (en) * | 2012-02-08 | 2013-08-15 | 味の素株式会社 | Gelling agent |
| KR102181705B1 (en) | 2013-05-20 | 2020-11-23 | 아지노모토 가부시키가이샤 | Gellant |
| EP3530711B1 (en) | 2016-10-24 | 2022-08-17 | Ajinomoto Co., Inc. | Gel composition |
| CA3118158A1 (en) | 2018-12-18 | 2020-06-25 | The Procter & Gamble Company | Personal care composition with increased vapor release |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55124583A (en) * | 1979-03-20 | 1980-09-25 | Ajinomoto Co Inc | Solidfying treatment agent for hydrophobic combustible organic medium |
| CN1245421A (en) * | 1996-12-20 | 2000-02-23 | 普罗克特和甘保尔公司 | Gel compositions containing gellants in form of alkyl amides of tri-carboxylic acids |
| CN1288721A (en) * | 1999-09-22 | 2001-03-28 | 莱雅公司 | Gel composition and use thereof in cosmetic compositions and the like |
| CN1294121A (en) * | 1999-10-20 | 2001-05-09 | 味之素株式会社 | N-acyl amino-acid amide prodn. process |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS525530B2 (en) * | 1974-03-01 | 1977-02-15 | ||
| JPS5266885A (en) * | 1975-12-01 | 1977-06-02 | Ajinomoto Co Inc | Gel composition containing water soluble organic medium |
-
2003
- 2003-05-29 JP JP2004510346A patent/JP4462035B2/en not_active Expired - Lifetime
- 2003-05-29 WO PCT/JP2003/006789 patent/WO2003102104A1/en active Application Filing
- 2003-05-29 CN CNB038128802A patent/CN1307278C/en not_active Expired - Lifetime
- 2003-05-29 AU AU2003241933A patent/AU2003241933A1/en not_active Abandoned
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55124583A (en) * | 1979-03-20 | 1980-09-25 | Ajinomoto Co Inc | Solidfying treatment agent for hydrophobic combustible organic medium |
| CN1245421A (en) * | 1996-12-20 | 2000-02-23 | 普罗克特和甘保尔公司 | Gel compositions containing gellants in form of alkyl amides of tri-carboxylic acids |
| CN1288721A (en) * | 1999-09-22 | 2001-03-28 | 莱雅公司 | Gel composition and use thereof in cosmetic compositions and the like |
| CN1294121A (en) * | 1999-10-20 | 2001-05-09 | 味之素株式会社 | N-acyl amino-acid amide prodn. process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1659251A (en) | 2005-08-24 |
| WO2003102104A1 (en) | 2003-12-11 |
| JP4462035B2 (en) | 2010-05-12 |
| JPWO2003102104A1 (en) | 2005-09-29 |
| AU2003241933A1 (en) | 2003-12-19 |
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