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CN1220693A - Betaine ester compound of active alcohols - Google Patents

Betaine ester compound of active alcohols Download PDF

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Publication number
CN1220693A
CN1220693A CN97195159A CN97195159A CN1220693A CN 1220693 A CN1220693 A CN 1220693A CN 97195159 A CN97195159 A CN 97195159A CN 97195159 A CN97195159 A CN 97195159A CN 1220693 A CN1220693 A CN 1220693A
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CN
China
Prior art keywords
ester
glycine
oxygen base
oxoethyl
composition
Prior art date
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Pending
Application number
CN97195159A
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Chinese (zh)
Inventor
M·J·德克莱克
H·J·M·德梅耶雷
A·P·斯特瑞罗
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Procter and Gamble Co
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Procter and Gamble Co
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Publication of CN1220693A publication Critical patent/CN1220693A/en
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • C11D3/0015—Softening compositions liquid
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/46—Esters of carboxylic acids with amino alcohols; Esters of amino carboxylic acids with alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/65—Mixtures of anionic with cationic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0094—Process for making liquid detergent compositions, e.g. slurries, pastes or gels
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes
    • C11D3/502—Protected perfumes
    • C11D3/507—Compounds releasing perfumes by thermal or chemical activation

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention relates to a composition and process for preparing such a composition which provides stabilised betaine ester compounds of active alcohols in an acidic environment. In particular, it relates to an aqueous acidic composition comprising: a) a betaine ester of an active alcohol which, at a concentration of from 0.01% to 10% by weight in said composition, is predominantly in the form of micelles and/ or is capable of being incorporated into micelles, b) a surfactant, said composition comprising an acidic material in sufficient amount to render the pH of the composition of less than 7.

Description

The betaine ester compound of reactive alcohols
Field of the present invention
The present invention relates to the betaine ester compound of reactive alcohols.Relate in particular to sour environment, for example stable reactive alcohols betaine ester compound in the fabric softener composition.
Background of the present invention
Washing and laundry product are known in the art.Yet the customer's approval of washing and laundry product is not only determined by the performance of these products, and is determined by relative aesthetic factors.Therefore perfume composition is an important component of successfully filling a prescription in this type of commercially available prod.
Therefore, the someone provides fragrance slowly to discharge, and Billy uses the compound formulas of spices energy last much longer itself.The disclosure of this compounds can and not find among the examination of appeal EP 95303762.9 at WO 95/04809, WO 95/08976.Examination of appeal EP95303762.9 has not described the betaine ester compound that the perfume alcohol that but perfume composition discharges when continuing length is provided.
Though the betaine ester compound is effective in the slow release of fragrance, but find now at sour environment, for example in the acidic products, described compound hydrolyzable when storing discharges their perfume composition, thereby has reduced the amount that discharges perfume alcohol after washing or cleaning process neutralization.Sour environment refers to the pH value less than 7.0.
Thereby the formulator of laundry and/or cleaning composition to face the preparation sour environment down stable, and the challenge that after washing or cleaning process neutralization, still produces the slow delivery formulations of reactive alcohols (for example spices).
The applicant finds that now the measure that the betaine ester compound of reactive alcohols uses with tensio-active agent has overcome this problem, and wherein the concentration of this betaine ester is 0.01～10wt%, mainly is the micellar form, and/or can introduces in the micella.Preferred this betaine ester has at least one long alkyl chain.
Therefore, the present invention includes acidic composition, said composition contains the betaine ester compound component and the tensio-active agent of reactive alcohols, this betaine ester compound has long alkyl chain, concentration is 0.01～10wt%, mainly is the micellar form, and/or can introduces in the micella.In order to reach package stability and washing or the cleaning process neutralization slow optimum benefit that discharges of reactive alcohols afterwards, preferred cationic tensio-active agent.
Without being limited by theory; it is believed that and use betaine ester compound that the betaine ester with hydrophobic property is provided with at least one long alkyl chain; they can be reset with micelle form, and/or be incorporated in the micella, thereby the protection ester bond can be in hydrolysis under the sour environment.
For purposes of the invention, term " acidic aqueous compositions " comprises that the pH value is less than or equal to 7.0 composition, and wherein pH measures in 20 ℃ of pure liquid products.
" slowly discharging " release to birth ratio that refers to active ingredient (for example spices) only uses active ingredient (for example spices) suction release itself will continue the longer time.
Thereby, the advantage of slow release principle of the present invention and package stability can be applied to other reactive alcohols component, for example flavouring agent alkoxide component, medicine alcohol actives or biological control alcohol reagent, and any other reactive alcohols component that other any need slowly discharge the actives component is essential.
The present invention's general introduction
The present invention relates to the aqueous acidic composition, comprise
A) betaine ester of reactive alcohols, concentration is 0.01～10wt%, mainly is the micellar form, and/or can introduce in the micella and
B) tensio-active agent,
Said composition comprises and presents in an amount at least sufficient to make the pH value of composition less than 7 acidic substance.
In a preferred embodiment of the invention, betaine ester is the hydrophobicity betaine ester of following formula:
Figure A9719515900081
R wherein 1, R 2, R 3Be selected from hydrogen, alkyl, aryl independently of one another,
Figure A9719515900082
With
Figure A9719515900083
Condition is R wherein 1, R 2And R 3Only be selected from hydrogen, aryl or alkyl independently of one another, and R 1, R 2Or R 3In be alkyl or aryl one of at least with at least 8 carbon atoms,
R wherein 4Be alkyl with 7～19 carbon atoms,
R wherein 1', R 2' be selected from independently of one another hydrogen, alkyl, aryl ,-CH 2-COOH ,-CH 2-COOR ,-CH 2-CH 2-COOH and-CH 2-CH 2-COOR,
Wherein n, n 1Be independently of one another 1～20 integer and
N wherein 2Be 0～20 integer,
N wherein 3Be 1～3 integer independently of one another, and wherein R is the organic chain of reactive alcohols independently of one another.
Another aspect of the present invention provides the method for preparing this acidic composition, and this method has further been improved the influence that betaine ester is avoided sour environment.The general method that preparation contains the composition of tensio-active agent comprises following step:
-mixed surfactant and optional components (if containing optional components) under the temperature that is higher than the tensio-active agent fusing point,
-prepare water base material (waterseat),
-mixture for preparing above is dispersed in the above-mentioned water base material and
-at random cool off resulting dispersion.
By this betaine ester is introduced with the melted surface promoting agent; or before the melted surface promoting agent is scattered in the water base material, betaine ester is introduced; or introduce with this surfactant dispersion; but this moment, this dispersion was on the Krafft temperature of mixture of tensio-active agent or above-mentioned any component, thus betaine ester was protected.
Detailed description of the present invention
The betaine ester compound of reactive alcohols
Necessary component of the present invention is the betaine ester of reactive alcohols, concentration is 0.01～10wt% of said composition, mainly be the micellar form, and/or can be incorporated in the micella that for example micella can be made up of 100% betaine ester or blended betaine ester/tensio-active agent.The betaine ester compound of preferred reactive alcohols has following general formula:
Figure A9719515900091
R wherein 1, R 2, R 3Be selected from hydrogen, alkyl, aryl independently of one another,
Figure A9719515900092
With
Figure A9719515900101
Condition is R wherein 1, R 2And R 3Only be selected from hydrogen, aryl or alkyl, R independently of one another 1, R 2Or R 3In be alkyl or aryl one of at least with at least 8 carbon atoms,
R wherein 4Be alkyl with 7～19 carbon atoms,
R wherein 1', R 2' be selected from independently of one another hydrogen, alkyl, aryl ,-CH 2-COOH ,-CH 2-COOR ,-CH 2-CH 2-COOH and-CH 2-CH 2-COOR,
Wherein n, n 1Be independently of one another 1～20 integer and
N wherein 2Be 0～20 integer,
Each n wherein 3Be independently from 1～3 integer and
Wherein each R is the organic chain of reactive alcohols independently.
Preferably, each n 2Be 0～6 integer independently.
Preferably, each n 3Be 1 or 2 integer independently, more preferably 1.
Preferred R 1, R 2, R 3Each is selected from H independently, has the alkyl chain of 1～20 carbon atom, and condition is R 1, R 2Or R 3In be alkyl one of at least with at least 8 carbon atoms.
Preferred R 1', R 2' be selected from hydrogen independently of one another, have alkyl chain, the phenyl of 1～3 carbon atom.
For above-mentioned compound, hydrophobic in fact R group is the organic chain of reactive alcohols, and this reactive alcohols is selected from flavouring agent alkoxide component, medicine alcohol actives, biological control alcohol reagent, perfume alcohol component and composition thereof.The flavouring agent component comprises the contributive seasonings of the whole sense of taste, odorant.Pharmaceutical actives comprises medicine.Biocontrol agent comprises biocide, anti-support one's family agent, bactericide, mycocide, algicide, fungicide, sterilizing agent, sanitas, sterilant, wormer, plant growth hormones.The perfume alcohol component comprises the component with aroma properties.
For above-claimed cpd, the R group is the organic chain of perfume alcohol preferably, this alcohol is selected from 2-phenoxyethyl alcohol, phenylethyl alcohol, Geraniol, geraniol, 3-methyl-5-phenyl-1-amylalcohol, 2,4-dimethyl-3-tetrahydrobenzene-1-methyl alcohol, phantol, tetrahydrolinalool, 1,2-dihydromyrcenol, hydroxycitronellol, farnesol, menthol, oxymethoxyallylbenzene, Vanillin, suitable-the 3-hexenol, terpinol and composition thereof.
For the present invention, preferred R group is selected from the organic chain of perfume alcohol, and this alcohol is selected from Geraniol, geraniol, phantol, dihydromyrcenol and composition thereof.
For the present invention, preferably compound is selected from bromination or chlorination spiceleaf oxygen base carbonyl-N, N-dimethyl-N-dodecyl methyl ammonium; Bromination or chlorination lemongrass oxygen base carbonyl-N, N-dimethyl-N-dodecyl methyl ammonium; Bromination or chlorination virtue camphor tree oxygen base carbonyl-N, N-dimethyl-N-dodecyl methyl ammonium; Bromination or chlorination dihydromyrcene oxygen base carbonyl-N, N-dimethyl-N-dodecyl methyl ammonium.
Other preferred compound is selected from N-dodecyl glycine geranyl ester hydrobromate or hydrogen chlorate; N-dodecyl glycine citronellyl ester hydrobromate or hydrogen chlorate; N-dodecyl glycine linalyl ester hydrobromate or hydrogen chlorate; N-dodecyl glycine dihydromyrcene base ester hydrobromate or hydrogen chlorate.
Other preferred compound is selected from N, N-dioctyl glycine geranyl ester hydrobromate or hydrogen chlorate; N, N-dioctyl glycine citronellyl ester hydrobromate or hydrogen chlorate; N, N-dioctyl glycine linalyl ester hydrobromate or hydrogen chlorate; N, N-dioctyl glycine dihydromyrcene base ester hydrobromate or hydrogen chlorate.
Other preferred compound is selected from N, N-two-dodecyl glycine geranyl ester hydrobromate or hydrogen chlorate; N, N-two-dodecyl glycine citronellyl ester hydrobromate or hydrogen chlorate; N, N-two-dodecyl glycine linalyl ester hydrobromate or hydrogen chlorate; N, N-two-dodecyl glycine dihydromyrcene base ester hydrobromate or hydrogen chlorate.
Other preferred compound is selected from bromination or chlorination N-(2-spiceleaf oxygen base-2-oxoethyl)-N, N-dimethyl-2-spiceleaf oxygen base-2-oxoethyl ammonium; Bromination or chlorination N-(2-lemongrass oxygen base-2-oxoethyl)-N, N-dimethyl-2-lemongrass oxygen base-2-oxoethyl ammonium; Bromination or chlorination N-(2-virtue camphor tree oxygen base-2-oxoethyl)-N, N-dimethyl-2-virtue camphor tree oxygen base-2-oxoethyl ammonium; Bromination or chlorination N-(2-dihydromyrcene oxygen base-2-oxoethyl)-N, N-dimethyl-2-dihydromyrcene oxygen base-2-oxoethyl ammonium.
Other preferred compound is selected from N-butyl-N-(2-spiceleaf oxygen base-2-oxoethyl) glycine geranyl ester hydrobromate or hydrogen chlorate; N-butyl-N-(2-lemongrass oxygen base-2-oxoethyl) glycine citronellyl ester hydrobromate or hydrogen chlorate; N-butyl-N-(2-virtue camphor tree oxygen base-2-oxoethyl) glycine linalyl ester hydrobromate or hydrogen chlorate; N-butyl-N-(2-dihydromyrcene oxygen base-2-oxoethyl) glycine dihydromyrcene base ester hydrobromate or hydrogen chlorate.
Other preferred compound is selected from N-dodecyl-N-(2-spiceleaf oxygen base-2-oxoethyl) glycine geranyl ester hydrobromate or hydrogen chlorate; N-dodecyl-N-(2-lemongrass oxygen base-2-oxoethyl) glycine citronellyl ester hydrobromate or hydrogen chlorate; N-dodecyl-N-(2-virtue camphor tree oxygen base-2-oxoethyl) glycine linalyl ester hydrobromate or hydrogen chlorate; N-dodecyl-N-(2-dihydromyrcene oxygen base-2-oxoethyl) glycine dihydromyrcene base ester hydrobromate or hydrogen chlorate.
Other preferred compound is selected from N, two (2-spiceleaf oxygen base-2-oxoethyl) glycine geranyl ester hydrobromate or the hydrogen chlorates of N-; N, two (2-lemongrass oxygen base-2-oxoethyl) glycine citronellyl ester hydrobromate or the hydrogen chlorates of N-; N, N-two (2-virtue camphor tree oxygen base-2-oxoethyl) glycine linalyl ester hydrobromate or hydrogen chlorate; N, two (2-dihydromyrcene oxygen base-2-oxoethyl) glycine dihydromyrcene base ester hydrobromate or the hydrogen chlorates of N-.
In the present composition in the betaine ester used herein arbitrarily above the mixture of component all can use.
Amount in this reactive alcohols betaine ester compound introducing acidic composition is 0.01～8wt% of total composition, more preferably 0.05～5wt%, most preferably 0.1～2wt% preferably.
Tensio-active agent
Other main ingredient of the present invention is a tensio-active agent.This type of tensio-active agent is selected from negatively charged ion, nonionic, positively charged ion, amphoteric and zwitterionic tensio-active agent.
Anion surfactant
Can comprise any main anion surfactant that is used to wash purpose in the composition.These tensio-active agents can comprise anionic vitriol, sulfonate, carboxylate salt and sarcosinate surfactant salt (comprise for example ammonium salt of sodium, potassium, ammonium and replacement, for example single, two and triethanolamine salt).
Other anion surfactant comprises isethionate, for example the monoesters of fatty acid amide, alkyl succinate and the sulfosuccinate of acyl-hydroxyethyl sulfonate, N-acyl group ox sulphur hydrochloric acid, N-methyltaurine, sulfo-succinic acid (particularly saturated and undersaturated C 12-C 18Monoesters), the diester of sulfo-succinic acid (particularly saturated and undersaturated C 6-C 14Diester), the N-acyl sarcosinate.Resinous acid and hydrogenant resinous acid also are suitable, for example rosin, staybelite and be present in or come from the resinous acid and the hydrogenated resin acid of tallow oil.
The anion sulfate tensio-active agent that herein be fit to use comprises straight chain and chain primary alkyl sulfate, alkyl ethoxy sulfate, fatty oil base glycerol vitriol, alkylphenol oxyethane ether sulfate, C 5-C 17Acyl group-N-(C 1-C 4Alkyl) and-N-(C 1-C 2Hydroxyalkyl) vitriol of glucosamine sulfate and alkyl polysaccharide APG (described herein is the compound of nonionic non-sulfuric acidization) for example.
Alkyl ethoxy sulfate surfactant is preferably selected from the C with the about 0.5～about 20 moles of ethylene oxide ethoxylations of per molecule 6-C 18Alkyl-sulphate.Alkyl ethoxy sulfate surfactant is more preferably the C with about 0.5～about 20 moles of per molecule, preferred about 0.5～about 5 moles of ethylene oxide ethoxylations 6-C 18Alkyl-sulphate.
The anionic sulphonate tensio-active agent that herein is fit to use comprises C 5-C 20Linear alkylbenzene sulfonate, alkyl ester sulfonate, C 6-C 22Uncle or secondary chain alkyl sulfonate, C 6-C 24Alkenyl sulphonate, sulfonated poly carboxylic acid, alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, fatty oil base glycerol sulfonate and any mixture thereof.
The anionic carboxylate tensio-active agent that herein is fit to use comprises alkyl ethoxy carboxylate, alkyl polyethoxye multi-carboxylate's tensio-active agent and soap (' alkyl carboxylic acid thing '), general secondary soap particularly described herein.The preferred alkyl ethoxy carboxylate of Shi Yonging comprises having general formula R O (CH herein 2CH 2O) xCH 2COO -M +Those, wherein R is C 6～C 18Alkyl, the x scope is 0～10, ethoxylate distributes and to be: when x was 0, amount of substance by weight was less than about 20%, and when x greater than 7 the time, amount of substance by weight is less than about 25%, when R on average is C 13Or still less the time, x on average is about 2～4, when R on average greater than C 13The time, x on average is about 3～10, and M is positively charged ion, is preferably selected from basic metal, alkaline-earth metal, ammonium, list, two and trolamine, most preferably be selected from sodium, potassium, ammonium and with the mixture of magnesium ion.Preferred alkyl ethoxy carboxylate is that R is C 12～C 18Those of alkyl.
The poly-many oxyethyl groups multi-carboxylate tensio-active agent of alkane that herein is fit to use comprises having general formula R O-(CHR 1-CHR 2-O)-R 3Those, wherein R is C 6～C 18Alkyl, x is 1～25, R 1And R 2Be selected from hydrogen, formyloxy, amber acidic group, hydroxy succinic acid base and composition thereof, wherein R 1Or R 2At least one is amber acidic group or hydroxy succinic acid base, R 3Be selected from alkyl hydrogen, replacement or unsubstituted 1～8 carbon atom and composition thereof.
Preferred soap surfactant is to contain the unitary secondary soap surfactant of the carboxyl that is connected in secondary carbon.Secondary carbon can be ring texture, for example to the octyl group phenylformic acid, or the cyclohexane carboxylic acid salt of alkyl replacement.Secondary soap surfactant should preferably not contain ehter bond, do not contain ester bond and hydroxyl.Should preferably there be nitrogen-atoms at headgroup (amphiphilic moieties).Secondary soap surfactant contains 11-15 carbon atom usually altogether, though many slightly (for example as many as 16) also tolerable, for example to the octyl group phenylformic acid.
Below general structure further illustrate some preferred secondary soap surfactants:
A. the secondary soap of a class very preferably comprises general formula R 3CH (R 4) the secondary carbon carboxyl material of COOM, wherein R 3Be CH 3(CH 2) x, R 4Be CH 3(CH 2) y, wherein y can be 0 or 1～4 integer, x is 4～10 integer, and summation (x+y) is 6-10, preferred 7-9, most preferably 8.
B. another kind of preferred secondary soap comprises the carboxylic compound of carboxyl substituent on the cyclic hydrocarbon radical unit, and promptly general formula is R 5-R 6The secondary soap of-COOM, wherein R 5Be C 7-C 10, preferred C 8-C 9Alkyl or alkenyl, and R 6Be ring structure, for example benzene, pentamethylene and hexanaphthene.(annotate: R 5Can with respect to the ring on carboxyl the neighbour, or contraposition on).
C. another kind of preferred secondary soap comprises general formula CH 3(CHR) k-(CH 2) m-(CHR) n-CH (COOM) (CHR) o-(CH 2) p-(CHR) q-CH 3The secondary carboxylic ester compound, wherein each R is C 1-C 4Alkyl, wherein k, n, o, q are 0～8 integers, condition is that the total scope of carbon atom (comprising carboxylate salt) is 10～18.
On each among general formula A, B and the C, material M can be any suitable, water-soluble counterion particularly.
The particularly preferred secondary soap surfactant of Shi Yonging is water-soluble material herein, is selected from 2-methyl isophthalic acid-undecanoic acid, 2-ethyl-1-capric acid, 2-propyl group-1-n-nonanoic acid, 2-butyl-1-is sad and the water-soluble salt of 2-amyl group-1-enanthic acid.
Other suitable anion surfactant is general formula R-CON (R 1) CH 2The basic metal sarcosinate of COOM, wherein R is C 5-C 17Straight or branched alkyl or alkenyl, R 1Be C 1-C 4Alkyl and M be alkalimetal ion.Preferred example is the tetradecyl and the oil base methyl sarcosinate of sodium-salt form.
Nonionogenic tenside
Can comprise the main any nonionogenic tenside that is used to wash purpose in the composition.Below the useful nonionogenic tenside of typical non-limiting class is listed in.
The polyhydroxy fatty acid amide of Shi Yonging is to have formula R herein 2CONR 1Those of Z, wherein: R 1Be H, C 1-C 4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture, preferred C 1-C 4Alkyl, more preferably C 1Or C 2Alkyl, most preferably C 1Alkyl (being methyl); R 2Be C 5-C 31Alkyl, preferred straight chain C 5-C 19Alkyl or alkenyl, more preferably straight chain C 9-C 17Alkyl or alkenyl, most preferably straight chain C 11-C 17Alkyl or alkenyl or its mixture; And Z is the polyhydroxy alkyl with straight-chain alkyl chain of at least 3 hydroxyls that are directly connected on the chain, or its oxyalkylated derivative (preferred ethoxylation or propenoxylated).The reducing sugar that Z preferably reacts derived from reductive amination; Z is sugar alcohol base (glycityl) more preferably.
The polyethylene oxide of alkylphenol, poly(propylene oxide) and polybutylene oxide condenses are suitable for herein.General polyethylene oxide condensation compound is preferred.These compounds comprise the alkylphenol of alkyl of the straight or branched structure that contains 6～about 18 carbon atoms of having an appointment and the condensation product of alkylene oxide.
The alkyl ethoxylated condensation product of fatty alcohol and about 1～about 25 moles of ethylene oxide is suitable for herein.The alkyl chain of fatty alcohol can be the uncle of straight or branched or secondary and generally contain 6～22 carbon atoms.Particularly preferably be the alcohol with 8～20 carbon atom alkyls and the condensation product of about 2～about 10 moles of ethylene oxide of every mol of alcohol.
The C of ethoxylation 6-C 18Fatty alcohol and C 6-C 18The fatty alcohol of blended ethoxylated/propoxylated is to be fit to the tensio-active agent of use herein, and is particularly wherein water miscible.The fatty alcohol of ethoxylation preferably ethoxylation degree is 3～50 C 10-C 18Ethoxylized fatty alcohol, most preferably ethoxylation degree is 3～40 C 12-C 18Ethoxylized fatty alcohol.Blended ethoxylated/propoxylated fatty alcohol preferably has 10～18 carbon atoms of alkyl chain length, ethoxylation degree 3～30, propoxylation degree 1～10.
Oxyethane is fit to use with the condensation product of the hydrophobic group that is generated by propylene oxide and propylene glycol condensation herein.The hydrophobic part of these compounds preferably has molecular weight about 1500～about 1800 and shows water-insoluble.The example of this type compound comprises some commercially available Pluronic that sold by BASF TMTensio-active agent.
Oxyethane is fit to use with the condensation product of the product that is obtained by propylene oxide and reacting ethylenediamine herein.The hydrophobic parts of these products is made up of the reaction product of quadrol and excessive propylene oxide, and generally has molecular weight about 2500～about 3000.The example of this type nonionogenic tenside comprises the commercially available Tetronic that is sold by BASF TMCompound.
The U.S. Pat 4 of the Llenado that issues on January 21st, 1986,565, disclose in 647 and be fit to the alkyl polysaccharide of use herein, have to contain and have an appointment 6～hydrophobic group and for example many glycosides of polysaccharide of about 30, preferred about 10～about 16 carbon atoms, hydrophilic group contains has an appointment 1.3～about 10, preferred about 1.3～3,1.3～2.7 saccharide unit most preferably from about.Can use any reducing sugar that contains 5 or 6 carbon atoms, for example glucose, semi-lactosi and galactosyl part can replace the glucosyl part.(hydrophobic group at random is connected on the positions such as 2-, 3-, 4-, so generation glucose or the semi-lactosi relative with glucoside or galactoside).Key can be between the position of position of for example other saccharide unit and the unitary 2-of aforementioned sugars, 3-, 4-and/or 6-between sugar.
Preferred alkyl polyglycoside has general formula
R 2O (c nH 2nO) t(glucoside) x
R wherein 2Be selected from alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and composition thereof, wherein alkyl contain 10～18, preferred 12～14 carbon atoms; N is 2 or 3; T is 0～10, and is preferred 0, and x is 1.3～8, preferred 1.3～3, most preferably 1.3～2.7.Glycosyl preferably is derived from glucose.
The fatty acid amide surfactant that herein is fit to use is to have general formula R 6CON (R 7) 2Those, R wherein 6Be contain 7～21, the alkyl of preferred 9～17 carbon atoms, each R 7Be selected from hydrogen, C 1-C 4Alkyl, C 1-C 4Hydroxyalkyl and-(C 2H 4O) xH, wherein x is 1～3 integer.
Cats product
The typical cationic surfactants that is used for the object of the invention is those of usually said cationic fabric softener actives.This type of cationic fabric softening component comprises that water-insoluble quaternary ammonium fabric softens actives, and the most frequently used is the ammonium chloride with two long alkyl chains.
Below preferred cation softening agent comprises in these:
1) ditallow dimethyl ammonium chloride (DTDMAC);
2) dihydro tallow alkyl dimethyl ammonium chloride;
3) dihydro tallow dimethyl methyl ammonium sulfate;
4) VARISOFT TA100;
5) two oil base alkyl dimethyl ammonium chlorides;
6) two palmityl hydroxyethyl ammonio methacrylates;
7) stearyl benzyl dimethyl ammonium chloride;
8) tallow trimethyl ammonium chloride;
9) h-tallow base trimethyl ammonium chloride;
10) C 12-C 14Alkyl hydroxyethyl dimethyl ammonium chloride;
11) C 12-C 18Alkyl dihydroxy ethyl ammonio methacrylate;
12) two (stearoyl-oxy ethyl) alkyl dimethyl ammonium chlorides (DSOEDMAC);
13) two (butter acyloxy ethyl) alkyl dimethyl ammonium chloride;
14) ditallow tetrahydroglyoxaline Methylsulfate;
15) 1-(2-butter amido-ethyl)-2-tallow tetrahydroglyoxaline Methylsulfate
16) ditallow tetrahydroglyoxaline
17) ditallow imidazoline ester
But be also included within the cationic fabric softening component scope is the quaternary ammonium compound of the fast degraded biologically that exists of the surrogate of two long-chain ammonium chlorides using to the more friendly material of environment with tradition.This type of quaternary ammonium compound contains introduces for example chain alkyl of carboxyl (or alkenyl) of functional group.Described material and fabric softening compositions be at open source literature EP-A-O for example, describes in 040,562 and EP-A-O, 239,910.
Quaternary ammonium compound herein and amine precursor have following logical formula I or (II):
Figure A9719515900171
Wherein Q be selected from-O-C (O)-,-C (O)-O-,-O-C (O)-O-,-NR 4-C (O)-,-C (O)-NR 4-; R 1Be (CH 2) n-Q-T 2Or T 3R 2Be (CH 2) m-Q-T 4Or T 5Or R 3R 3Be C 1-C 4Alkyl or C 1-C 4Hydroxyalkyl or H; R 4Be H or C 1-C 4Alkyl or C 1-C 4Hydroxyalkyl; T 1, T 2, T 3, T 4, T 5Be C independently 11-C 22Alkyl or alkenyl; N and m are 1～4 integers; And X -It is the compatible negatively charged ion of softening agent.
The compatible anionic infinite example of softening agent comprises muriate or methylsulfuric acid thing.
Alkyl or alkenyl, chain T 1, T 2, T 3, T 4T 5Must contain at least 11 carbon atoms, preferably at least 16 carbon atoms.Chain can be a straight or branched.
Butter are habitual and cheap sources of chain alkyl and alkenyl material.T wherein 1, T 2, T 3, T 4, T 5The compound of the mixture of the peculiar long-chain material of expression butter is particularly preferred.
The object lesson that is suitable for the quaternary ammonium compound in the aqueous fabric softening compositio herein comprises:
1) N, N-two (butter oxygen base-ethyl)-N, N-alkyl dimethyl ammonium chloride;
2) N, N-two (butter oxygen base-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium chloride;
3) N, N-two (2-butter oxygen base-2-oxo-ethyl)-N, N-alkyl dimethyl ammonium chloride;
4) N, N-two (2-butter oxygen base-ethyl carbonyl-oxo-ethyl)-N, N-alkyl dimethyl ammonium chloride;
5) N-(2-butter oxygen base-2-ethyl)-N-(2-butter oxygen base-2-oxo-ethyl)-N, the N-alkyl dimethyl ammonium chloride;
6) N, N, N-three (butter oxygen base-ethyl)-N-ammonio methacrylate;
7) N-(2-butter oxygen base-2-oxo-ethyl)-N-tallow-N, the N-alkyl dimethyl ammonium chloride; With
8) 1,2-two butter oxygen bases-3-trimethylammonium ammonium propane chloride;
Mixture with any above-mentioned substance.
In these materials, compound 1-7 is the example of logical formula I compound; Compound 8 is examples of logical formula II compound.Particularly preferably be N, N-two (butter oxygen base-ethyl)-N, the N-alkyl dimethyl ammonium chloride, it is undersaturated that wherein the tallow chain is at least part.The degree of unsaturation of tallow chain can the iodine number (IV) by corresponding lipid acid be measured, and in this example should preferred 5～100, two compounds difference has IV and is below or above 25.In fact, for the logical formula I compound that makes by IV 5～25, preferred 15～20 tallow fatty acid, found weight ratio greater than 30/70, be preferably greater than 50/50, the suitable/trans isomer more preferably greater than 70/30 provides best concentrating capacity.For by IV greater than the logical formula I compound that 25 tallow fatty acid makes, found that the ratio of cis-trans-isomer is little of the limit, unless need very high concentration.
Other example of the suitable quaternary ammonium of logical formula I and (II) obtains by for example following method:
-usefulness is coco group, palmityl, lauryl, oil base, castor-oil plant base, stearyl, palmityl for example
Deng " tallow " in the compound above replacing, this fatty acyl chain or saturated fully, or preferred fractional saturation at least;
-use " methyl " in ethyl, oxyethyl group, propyl group, propoxy-, sec.-propyl, butyl, isobutyl-or the tertiary butyl replacement above-claimed cpd;
-use " muriate " in the replacement above-claimed cpds such as bromide, Methylsulfate, formate, vitriol, nitrate.
In fact, negatively charged ion exists as just the counterion of positively charged quaternary ammonium compound.Performance for counterion in the actually operating of the present invention does not have strict requirement.Scope of the present invention can not be considered to only limit to some specific negatively charged ion.
" amine precursor " means corresponding to the second month in a season of above-mentioned quaternary ammonium compound or tertiary amine, this amine since the requirement of pH value aspect in this composition substantially by protonated.
Except above-mentioned cats product with fabric-softening performance, also can add other cats product, perhaps replace above-mentioned tensio-active agent with it.Described other ionic surface active agent comprises for example trimethylalkyl ammonium halogenide (R ＇-N of monoalkyl ammonium halogenide +(Me) 3X-) for example C16 trimethylammonium bromide or C14 trimethylammonium bromide; N-alkyl N, N-dimethyl-N (2-hydroxyethyl) ammonium (R '-N +(Me) 2CH 2CH 2OHX -) and composition thereof, wherein R ' is the alkyl chain with at least 8 carbon atoms, X -It is counterion defined above.
Cats product preferably in these tensio-active agents, most preferably above-mentioned cats product with fabric-softening performance.
The general content of this tensio-active agent is 0.1～80wt% of composition.
Acidic substance
Acidic substance are essential for the stability of the present composition.Acidity can be provided by above-mentioned betaine ester, particularly is selected from N-dodecyl glycine geranyl ester hydrobromate or hydrogen chlorate; N, N-dioctyl glycine geranyl ester hydrobromate or hydrogen chlorate; N, N-two-dodecyl glycine geranyl ester hydrobromate or hydrogen chlorate; N-butyl-N-(2-spiceleaf oxygen base-2-oxoethyl) glycine geranyl ester hydrobromate or hydrogen chlorate; N-dodecyl-N-(2-spiceleaf oxygen base-2-oxoethyl) glycine geranyl ester hydrobromate or hydrogen chlorate; N, two (2-spiceleaf oxygen base-2-oxoethyl) glycine geranyl ester hydrobromate or the hydrogen chlorates of N-; And/or above-mentioned cats product itself.
Also can use habitual acidic substance.Suitable habitual acidic substance comprise protonic acid (bronstead acid) and lipid acid.The example of suitable acid comprises mineral acid, carboxylic acid, particularly lower molecular weight (C 1-C 5) carboxylic acid and alkylsulphonic acid and composition thereof.
Suitable mineral acid comprises HCl, H 2SO 4, HNO 3And H 3PO 4Appropriate organic comprises formic acid, acetate, methylsulfonic acid and ethyl sulfonic acid.Preferred acid is hydrochloric acid, phosphoric acid, formic acid and methylsulfonic acid.
The amount of acidic substance should make the pH value of composition less than 7, preferred 2.0～5.5.
More preferably wherein use cats product, particularly above-mentioned as biodegradable fabric softener those, when the pH value scope of measuring when composition is 2.0～4.5, the optimum hydrolysis stability of these compositions will be obtained in 20 ℃ of pure compositions.
The amount of general acid is 1～30wt% of cats product, preferred 2～30wt%, more preferably 3～15wt%.
Annexing ingredient
Additional perfume composition can add in the acidic composition.When existing, composition will comprise at the most 5wt%, the more preferably bonus flavor of 0.1～1.5wt%.
Bonus flavor is those odoring substances that are deposited on fabric or the surface in laundry or washing process and felt by the normal sense of smell of people.Many perfume compositions with they the smell correction agent and their physical and chemical performance at " Perfume and Flavor chemicals (flavor chemistry medicine) ", Stephen Arctender, Vols. I and II, Aurthor, Montclair, H.J.and the Merck Index, 8th Edition, Merck ﹠amp; Co., Inc.Rahway provides among the N.J..Perfume composition and composition also can be in the present technique field for example U.S. Pat 4,145,184, US4, find in 152,272, US4,209,417 or US4,515,705.
Known various chemical substance comprises for example aldehyde, ketone, ester etc. as spices.More common is that natural phant and animal oil and the exudate that comprises various chemical composition compounding mixtures are known as spices, and can use these materials herein.Typical spices comprises and for example contains for example wooden/soil property base-material of the rare material of santal oil, civet and patchouli oil.Spices also can be for example rose or violet extract of light flowers spices.And, can prepare spices so that desirable fruit smell for example sour lime, lemon or orange smell to be provided.
The object lesson of perfume composition is a methyl allylphenol arbitrarily, phenyl aldehyde, the acetate benzyl ester, benzylalcohol, the formic acid benzyl ester, isobornyl acetate, amphene, cis citral (neral), geranial, geraniol, geraniol acetate, to cymene, capraldehyde, dihydrolinalool, dihydromyrcenol, dimethylphenylcarbinol, eucalyptol, geranic acid, Geraniol, Geranyl acetate, the geranyl nitrile, acetate is suitable-3-hexenyl ester, laurine, α-Zhu Xi, phantol, the phantol oxide compound, linalyl acetate, propionic acid linalool ester, methyl oaminobenzoate, the Alpha-Methyl ionone, methyl nonyl acetaldehyde, aminomethyl phenyl methyl acetic acid ester, left-handed-acetate  base ester, piperitone, isomenthone, myrcene, myrcenyl acetate, myrcenol, vernol, acetate neryl C10H17-ester, acetate nonyl ester, phenylethyl alcohol, α-Pai Xi, beta-pinene, γ-terpinene, α-terpinol, β-terpinol, tirpinyl acetate, Vertenex acetate is to the tert-butylcyclohexyl ester, amyl cinnamic aldehyde, Whitfield's ointment isopentyl ester, β-caryophyllene, cedrene, styryl carbinol, couramin, dimethylbenzyl ethyl methyl acetic acid ester, vanillal, oxymethoxyallylbenzene, isoeugenol, floracetate, piperonylaldehyde (heliotrophine), Whitfield's ointment 3-is along the hexenyl ester, hexyl salicylate, lilial (to the tertiary butyl-Alpha-Methyl hydrogen phenylacrolein), γ-methyl ionone, nerolidol, patchouli alcohol, phenyl hexanol, β-selinene, benzenyl trichloride ethyl methyl acetic acid ester, citric acid triethyl ester, Vanillin, veratryl aldehyde, α-Xue Songxi, β-cedrene, the C15H24 sesquiterpene, benzophenone, the Whitfield's ointment benzyl ester, the brassylic acid glycol ester, galaxolide (1,3,4,6,7,8-six hydrogen-4,6,6,7,8,8-hexamethyl cyclopenta-γ-2-chromene), hexyl cinnamic aldehyde, lyral (4-(4-hydroxy-4-methyl amyl group)-3-tetrahydrobenzene-10-aldehyde), vertofix coeur, methyl dihydrojasmonate, methyl-betanaphthyl ketone, musk ambrette, muskidanone, muskone, musk tibetene, musk xylene, aurantiol and phenyl ethyl phenyl acetic ester and composition thereof.
Composition of the present invention is suitable at acidic products and tensio-active agent, and there is use down in the preferred cationic tensio-active agent.This type of acidic products comprises fabric softener, hard surface cleaner, bathroom detergent, shower nozzle gel, reodorant, bar shaped agent, shampoo, amendment.
Fabric softener composition
When as fabric softener composition, also preferably measuring when composition is dilute form as the cats product of fabric softener is 1～8wt% of composition, or when composition is conc forms, preferred amount is 8～80wt%, more preferably 10～50wt%, most preferably 15～35wt%.
Fabric softener composition also can at random comprise habitual softening component for example nonionic supplement, tensio-active agent concentrated assistant, ionogen concentrated assistant, for example known oxidation inhibitor of stablizer and reductive agent, soil release polymer, emulsifying agent, sterilant, tinting material, spices, sanitas, white dyes, anti-ionization agent, antifoams and enzyme.
Method
Here the present invention also provides the method for preparing above-mentioned composition, comprises following step:
A) mixed surfactant and optional components (if any) under the temperature that is higher than the tensio-active agent fusing point.
B) prepare water base material,
C) mixture for preparing in the step a) is disperseed in water base material,
D) adding betaine ester arrives
D1)-mixture of step a) preparation, or
D2)-the water base material of step b), or
D3)-surfactant dispersion of step c), or
D4)-above-mentioned any mixture in,
E) at random cool off resulting dispersion.
Preferably on the Krafft temperature of tensio-active agent, the molten mixture of step a) is distributed in the water base material of step b).
Water base material can at random contain additive for example polyoxyethylene glycol or biocide.
Acid can add step a) or directly join in the water base material of step b).
Or in case before making the step e) of dispersion or after step e), if add the optional components that exists for example dyestuff, spices.
Preferably in steps d 3) the betaine ester dispersion process in, should notice that the temperature of molten mixture is higher than the Krafft temperature of tensio-active agent.Krafft temperature is meant the temperature the when solubleness of tensio-active agent equals micelle-forming concentration (CMC), CMC is at M.J ROSEN, Surfactants and interfacial phenomena (tensio-active agent and surface phenomenon), 1988, definition is arranged in p.215.
Also preferably suitably be incorporated in micella/vesicle to guarantee betaine ester with enough shearing intensity of forces.Shear intensity of force and should be enough to suitably scatter table surface-active agent.Suitable dispersion can be determined by the particle diameter that for example microscopy or light scattering technique are controlled resulting dispersion.Particle diameter preferably should be lower than 50 μ m.
About cooling step, the preferred best result of storage is to be cooled to resulting mixture to be lower than the Krafft temperature of tensio-active agent before product is stored.
Without being limited by theory, it is believed that such method provides effective protection of the weak ester bond of betaine ester by the influence that avoids being subjected to water; Therefore in storage process, avoid premature hydrolysis.In order to provide best protection by this method, employed tensio-active agent is cats product preferably.
Spices synthesizes embodiment
1-is by the N of the synthetic no hindered alcohols of transesterification, N-dioctyl glycinate and N, N-two-dodecyl glycinate
N under argon gas in toluene (250ml), N-dioctyl glycine methyl ester (47.02g, 150mmol, add lentamente in mixture leq) some sodium methylates (1.01g, 0.019mol, 0.125eq) and Geraniol (27.3ml, 158mmol, 1.05eq).Mixture shows the methyl alcohol distillation that with toluene transesterification was generated after reaction is finished in vacuum (10mmHg) heating down in 1 hour by 1HNMR.Last toluene vaporising under vacuum.Add ether (200ml), before filtration, stored mixture 1 hour at 4 ℃.Filtrate concentrates under vacuum and obtains desired N, and N-dioctyl glycine geranyl ester is light yellow oil (quantitative yield).
This type synthetic also applicable to N, N-dioctyl glycine phenoxy group ethyl (phenoxanyl) ester; N, N-dioctyl glycine is suitable-3-hexenyl ester and N, N-two-dodecyl glycine phenoxy group ethyl ester, N, N-two-dodecyl glycine is suitable-3-hexenyl ester and N, and N-two-dodecyl glycine geranyl ester is last three and uses N, N-dioctyl glycine methyl ester replaces N, and N-two-octyl group glycine methyl ester is used for synthetic.
2-uses their chloracetate or the N of the synthetic hindered alcohols (tertiary alcohol) of bromacetate, N-dioctyl glycinate and N, N-two-dodecyl glycinate
Will the bromoacetic acid dihydromyrcene base ester in the ethyl acetate (50ml) (27.7g, 100mmol, 1eq) join lentamente dioctylamine in the ethyl acetate (100ml) (33ml, 110mmol, 1.1eq) and yellow soda ash (21.2g, 0.2mol, 2eq) in.Show after reaction is finished by 1HNMR reaction mixture was at room temperature stirred 72 hours.Filter out yellow soda ash, filtrate concentrates under vacuum, adds ether (200ml) back and stores 12 hours at 4 ℃ of following solution.Then, filtering solution is also removed ether under vacuum, obtain desired N, and N-dioctyl glycine dihydromyrcene base ester is yellow oil (38.05g, productive rate 87%).
Will the Mono Chloro Acetic Acid linalyl ester in the toluene (50ml) (5.77g, 25mmol, leq) join lentamente two-lauryl amine in toluene (50ml) (10g, 28.3mmol, 1.13eq) and yellow soda ash (5.3g, 0.05mol, 2eq) in.Show after reaction is finished reaction mixture is descended to stir for 2 weeks at 60 ℃ by 1HNMR.Filter out yellow soda ash, filtrate concentrates under vacuum, adds ether (200ml) back and stores 12 hours at 4 ℃ of following solution.Then, filtering solution is also removed ether under vacuum, obtain desired N, and N-two-dodecyl glycine linalyl ester is yellow oil.
The synthetic N that also is applicable to no hindered alcohols of this type, N-dioctyl glycinate and N, the synthesizing of N-two-dodecyl glycinate.
In all these experiments, can be by for example dissolving N in methyl alcohol, ethanol, Virahol, sherwood oil, ether, the toluene at organic solvent, N-dioctyl glycinate or N, N-two-dodecyl glycinate, and the mineral acid (for example HCl in the Virahol) in stoichiometric at least water of adding or the organic solvent, easily obtain N, N-dioctyl glycinate hydrogen villaumite or hydrobromide and N, the sweet ammonia salt of N-two-dodecyl ester hydrogen villaumite or hydrobromate.
3-is by synthetic N-dodecyl-N-(2-spiceleaf oxygen base-2-oxoethyl) the glycine geranyl ester (no hindered alcohols) of transesterification
N-dodecyl-N-under argon gas in toluene (80ml) (2-methoxyl group-2-oxoethyl) glycine methyl ester (6.59g, 20mmol, add some sodium methylate (0.27g in mixture 1eq) lentamente, 0.005mol, 2*0.125eq) and Geraniol (7.3ml, 42mmol, 2*1.05eq).Mixture shows the methyl alcohol distillation that with toluene transesterification was generated after reaction is finished in vacuum (10mmHg) heating down in 2 hours by 1HNMR.Last toluene vaporising under vacuum.Add ether (200ml), before filtration, stored mixture 1 hour at 4 ℃.Filtrate concentrates under vacuum and obtains desired N-dodecyl-N-(2-spiceleaf oxygen base-2-oxoethyl) glycine geranyl ester, is light brown oil (quantitative yield).
This type synthetic also applicable to N-dodecyl-N-(2-phenoxy group ethyoxyl (phenoxanyloxy)-2-oxoethyl) glycine phenoxy group ethyl ester and N-dodecyl-N-(2-suitable-3-hexene oxygen base-2-oxoethyl) glycine suitable-3-hexenyl ester and N-butyl-N-(2-spiceleaf oxygen base-2-oxoethyl) glycine geranyl ester; N-butyl-N-(2-phenoxy group ethyoxyl-2-oxoethyl) glycine phenoxy group ethyl ester and N-butyl-N-(2-suitable-3-hexene oxygen base-2-oxoethyl) glycine is suitable-3-hexenyl ester synthesis, be last three N-butyl-N-(2-methoxyl group-2-oxoethyl) glycine methyl ester replace N-dodecyl-N-(2-methoxyl group-2-oxoethyl) glycine methyl ester for the synthesis of in.
4-uses their chloracetate or the synthetic N-dodecyl-N-of bromacetate (2-virtue camphor tree oxygen base-2-oxoethyl) glycine linalyl ester or N-dodecyl-N-(2-dihydromyrcene oxygen base-2-oxoethyl) glycine dihydromyrcene base ester (sterically hindered alcohol is the tertiary alcohol for example)
Will the bromoacetic acid dihydromyrcene base ester in the acetonitrile (75ml) (55.44g, 200mmol, 2eq) join lentamente lauryl amine in the acetonitrile (250ml) (24.2ml, 100mmol, 1eq) and yellow soda ash (42.4g, 0.4mol, 4eq) in.Show after reaction is finished by 1HNMR reaction mixture was at room temperature stirred 48 hours.Filter out yellow soda ash, filtrate concentrates under vacuum, adds ether (200ml) back and stores 12 hours at 4 ℃ of following solution.Then, filtering solution is also removed ether under vacuum, obtains desired N-dodecyl-N-(2-dihydromyrcene oxygen base-2-oxoethyl) glycine dihydromyrcene base ester, is brown oil (56.2g, productive rate 97.2%).
Will the Mono Chloro Acetic Acid linalyl ester in the acetonitrile (75ml) (55.04g, 200mmol, 2eq) join lentamente lauryl amine in the acetonitrile (50ml) (24.2ml, 100mmol, 1eq) and yellow soda ash (42.4g, 0.4mol, 4eq) in.Show after reaction is finished reaction mixture is descended to stir for 2 weeks at 50 ℃ by 1HNMR.Filter out yellow soda ash, filtrate concentrates under vacuum, adds ether (200ml) back and stores 12 hours at 4 ℃ of following solution.Then, filtering solution is also removed ether under vacuum, obtains desired N-dodecyl-N-(2-virtue camphor tree oxygen base-2-oxoethyl) glycine linalyl ester, is brown oil (48.6g, productive rate 84.7%).
Synthetic as mentioned above N-butyl-N-(2-virtue camphor tree oxygen base-2-oxoethyl) glycine linalyl ester and N-butyl-N-(2-dihydromyrcene oxygen base-2-oxoethyl) glycine dihydromyrcene base ester, just butylamine replaces lauryl amine to be used for synthesizing.
Synthetic no the hindered alcohols for example chloracetate or the bromacetate of Geraniol, phenoxyethyl alcohol (phenoxanol), suitable-3-hexenol of also being applicable to of this type.
In all these experiments, can be by for example dissolving for example N-butyl-N-(2-spiceleaf oxygen base-2-oxoethyl) glycine geranyl ester in methyl alcohol, ethanol, Virahol, sherwood oil, ether, the toluene at organic solvent, and the mineral acid (HCl or HBr) (for example HCl in the Virahol) in stoichiometric at least water of adding or the organic solvent, obtain hydrogen chlorate or hydrobromate.
5-is by the synthetic N of transesterification, N-pair of (2-spiceleaf oxygen base-2-oxoethyl) glycine geranyl esters (or any no hindered alcohols)
N under argon gas in toluene (80ml), two (2-methoxyl group-2-oxoethyl) glycine methyl ester (7.0g, the 30mmol of N-, add lentamente in mixture 1eq) some sodium methylates (0.49g, 0.009mol, 3*0.10eq) and Geraniol (14.57g, 95mmol, 3*1.05eq).Mixture shows the methyl alcohol distillation that with toluene transesterification was generated after reaction is finished in vacuum (10mmHg) heating down in 2 hours by 1HNMR.Last toluene vaporising under vacuum.Add ether (200ml), before filtration, stored mixture 1 hour at 4 ℃.Filtrate concentrates under vacuum and obtains desired N, and two (2-spiceleaf oxygen base-2-oxoethyl) the glycine geranyl esters of N-are yellow oil (quantitative yield).
This type synthetic also applicable to N, two (2-phenoxy group oxyethyl group-2-oxoethyl) glycine phenoxy group ethyl ester and the N of N-, N-two (2-suitable-3-hexene oxygen base-2-oxoethyl) glycine is suitable-3-hexenyl ester synthetic.
6-uses their chloracetate or the synthetic N of bromacetate, N-two (2-virtue camphor tree oxygen base-2-oxoethyl) glycine linalyl ester or N, two (2-dihydromyrcene oxygen base-2-oxoethyl) the glycine dihydromyrcene base esters (sterically hindered alcohol is the tertiary alcohol for example) of N-
Will the bromoacetic acid dihydromyrcene base ester in the acetonitrile (100ml) (83.16g, 300mmol, 3eq) join lentamente ammonia in the acetonitrile (350ml) (the 2N solution 50ml in the 2-propyl alcohol, 100mmol, leq) and yellow soda ash (63.6g, 0.6mol, 6eq) in.Show after reaction is finished by 1HNMR reaction mixture was at room temperature stirred 48 hours.Filter out yellow soda ash, filtrate concentrates under vacuum, adds ether (200ml) back and stores 12 hours at 4 ℃ of following solution.Then, filtering solution is also removed ether under vacuum, obtain desired N, and two (2-dihydromyrcene oxygen base-2-oxoethyl) the glycine dihydromyrcene base esters of N-are brown oil.
Will the Mono Chloro Acetic Acid linalyl ester in the acetonitrile (100ml) (82.56g, 300mmol, 3eq) join lentamente ammonia in the acetonitrile (350ml) (the 2N solution 50ml in the 2-propyl alcohol, 100mmol, leq) and yellow soda ash (63.6g, 0.6mol, 6eq) in.Show after reaction is finished reaction mixture is descended to stir for 2 weeks at 50 ℃ by 1HNMR.Filter out yellow soda ash, filtrate concentrates under vacuum, adds ether (200ml) back and stores 12 hours at 4 ℃ of following solution.Then, filtering solution is also removed ether under vacuum, obtain desired N, and N-two (2-virtue camphor tree oxygen base-2-oxoethyl) glycine linalyl ester is brown oil.
Synthesizing of this type also is applicable to no the hindered alcohols for example chloracetate of Geraniol, phenoxyethyl alcohol, suitable-3-hexenol or synthesizing of bromacetate.
In all these experiments, can be by for example dissolving for example N in methyl alcohol, ethanol, Virahol, sherwood oil, ether, the toluene at organic solvent, N-two (2-virtue camphor tree oxygen base-2-oxoethyl) glycine linalyl ester, and the mineral acid (HCl or HBr) (for example HCl in the Virahol) in stoichiometric at least water of adding or the organic solvent, obtain hydrogen chlorate or hydrobromate.
The present invention is illustrated with following infinite embodiment, and wherein all except as otherwise noted per-cents all by weight.
In an embodiment, abbreviation component mark has following implication:
DEQA: two-(butter acyl-oxygen base-ethyl) alkyl dimethyl ammonium chlorides
Lipid acid: the stearic acid of IV=1
Ionogen: calcium chloride
DGGE:N-dodecyl glycine geranyl ester hydrogen chlorate
PEG: Macrogol 4000
The CTAB:C16 trimethylammonium bromide
The Cetrimide:C14 trimethylammonium bromide
The average degree of ethoxylation that Dobanol  23-3:Shell sells is 3 C12-C13's
Ethoxylated alcohol
The average degree of ethoxylation that Lutensol  AO30:BASF sells is 30 C13-C15's
The alcohol of ethoxylation
The average degree of ethoxylation that Dobanol  91-10:Shell sells is 10 C19-C21
Ethoxylated alcohol
The average degree of ethoxylation that Dobanol  23-6.5:Shell sells is 6.5 C12-C13
Ethoxylated alcohol
Alkyl sodium sulfate ester: Enichem sells with Isalchem 123  alcohol, i.e. 94% branched chain
C12-13 alcohol be the basis.
Embodiment 1
Be prepared as follows fabric softening compositions of the present invention:
Component A B C D E
DEQA 2.6 2.9 18.0 19.0 19.0
Lipid acid 0.3 - 1.0 - -
Hydrochloric acid 0.02 0.02 0.02 0.02 0.02
PEG - - 0.6 0.6 0.6
Spices 1.0 1.0 1.0 1.0 1.0
The siloxanes antifoams 0.01 0.01 0.01 0.01 0.01
DGGE 1 0.5 1 0.5 1
Ionogen - - 600ppm 600ppm 1200ppm
Dyestuff 10ppm 10ppm 50ppm 50ppm 50ppm
Water and minor materials reach equal amount 100
Embodiment 2
By mixing the following hard surface cleaner composition of the present invention of listed component preparation:
F G H Ⅰ
CTAB 3.2 ?- ???- ??-
Cetrimide - 4.2 ???- ??-
C8-10 dimethylamine oxide compound - - ???- 4.40
LutensolAO30 - - 0.75 3.0
Dobanol91-10 - - 2.60 ??-
Dobanol23- 6.5 - - 0.90 ??-
Dobanol23-3 - - 1.75 ??-
Toxilic acid 8.0 8.6 ??- ??-
Citric acid - - ??- 5.50
The alkyl sodium sulfate ester - - ??- 4.0
Ammonia (NH 4OH) - - ??- 0.40
Propylene glycol - - ??- 1.30
H 2O 2 - - 7.0 ??-
H 2SO 4Regulate the pH value - - 4.0 ??-
DGGE 1.0 0.5 1.0 0.6
Water and other material reach equal amount
The pH value 1.0 0.9 4.0 3.2

Claims (25)

1, the aqueous acidic composition comprises
A) betaine ester of reactive alcohols, its concentration is 0.01～10wt% in said composition, mainly is the micellar form, and/or can introduce in the micella,
B) tensio-active agent,
Said composition comprises and presents in an amount at least sufficient to make the pH value of composition less than 7 acidic substance.
2, the aqueous acidic composition of claim 1, wherein said betaine ester has general formula:
Figure A9719515900021
R wherein 1, R 2, R 3Be selected from hydrogen, alkyl, aryl independently of one another,
Figure A9719515900022
With
Figure A9719515900023
Condition is R wherein 1, R 2And R 3Only be selected from hydrogen, aryl or alkyl, R independently of one another 1, R 2Or R 3In be alkyl or aryl one of at least with at least 8 carbon atoms,
R wherein 4Be alkyl with 7～19 carbon atoms,
R wherein 1', R 2' be selected from independently of one another hydrogen, alkyl, aryl ,-CH 2-COOH ,-CH 2-COOR ,-CH 2-CH 2-COOH and-CH 2-CH 2-COOR,
Wherein n, n 1Be independently of one another 1～20 integer and
N wherein 2Be 0～20 integer,
Each n wherein 3Be 1～3 integer independently, and
Wherein each R is the organic chain of reactive alcohols independently.
3, the aqueous acidic composition of claim 2, wherein said n 2It is 0～6 integer.
4, arbitrary aqueous acidic composition in the claim 2 or 3, wherein each n 3Be 1 or 2 integer independently, be more preferably 1.
5, arbitrary aqueous acidic composition among the claim 2-4, wherein R 1', R 2' be selected from H independently of one another, have the alkyl chain and the phenyl of 1～3 carbon atom.
6, arbitrary aqueous acidic composition among the claim 2-5, wherein R 1, R 2, R 3Be selected from H independently of one another, have the alkyl chain of 1～20 carbon atom.
7, arbitrary aqueous acidic composition among the claim 2-6, this R group organic chain that is reactive alcohols wherein, this reactive alcohols is selected from flavouring agent alkoxide component, medicine alcohol actives, biological control alcohol reagent, perfume alcohol component.
8, the aqueous acidic composition of claim 7, wherein this R group organic chain that is perfume alcohol.
9, the aqueous acidic composition of claim 8, this R group organic chain that is perfume alcohol wherein, this alcohol is selected from 2-phenoxyethyl alcohol, phenylethyl alcohol, Geraniol, geraniol, 3-methyl-5-phenyl-1-amylalcohol, 2,4-dimethyl-3-tetrahydrobenzene-1-methyl alcohol, phantol, tetrahydrolinalool, 1,2-dihydromyrcenol, hydroxycitronellol, farnesol, menthol, oxymethoxyallylbenzene, Vanillin, suitable-the 3-hexenol, terpinol and composition thereof are preferably selected from Geraniol, geraniol, phantol, dihydromyrcenol and composition thereof.
10, the aqueous acidic composition of claim 9, wherein this betaine ester is selected from bromination or chlorination spiceleaf oxygen base carbonyl-N, N-dimethyl-N-dodecyl methyl ammonium; Bromination or chlorination lemongrass oxygen base carbonyl-N, N-dimethyl-N-dodecyl methyl ammonium; Bromination or chlorination virtue camphor tree oxygen base carbonyl-N, N-dimethyl-N-dodecyl methyl ammonium; Bromination or chlorination dihydromyrcene oxygen base carbonyl-N, N-dimethyl-N-dodecyl methyl ammonium.
11, the aqueous acidic composition of claim 9, wherein this betaine ester is selected from N-dodecyl glycine geranyl ester hydrobromate or hydrogen chlorate; N-dodecyl glycine citronellyl ester hydrobromate or hydrogen chlorate; N-dodecyl glycine linalyl ester hydrobromate or hydrogen chlorate; N-dodecyl glycine dihydromyrcene base ester hydrobromate or hydrogen chlorate.
12, the aqueous acidic composition of claim 9, wherein this betaine ester is selected from N, N-dioctyl glycine geranyl ester hydrobromate or hydrogen chlorate; N, N-dioctyl glycine citronellyl ester hydrobromate or hydrogen chlorate; N, N-dioctyl glycine linalyl ester hydrobromate or hydrogen chlorate; N, N-dioctyl glycine dihydromyrcene base ester hydrobromate or hydrogen chlorate.
13, the aqueous acidic composition of claim 9, wherein this betaine ester is selected from N, N-two-dodecyl glycine geranyl ester hydrobromate or hydrogen chlorate; N, N-two-dodecyl glycine citronellyl ester hydrobromate or hydrogen chlorate; N, N-two-dodecyl glycine linalyl ester hydrobromate or hydrogen chlorate; N, N-two-dodecyl glycine dihydromyrcene base ester hydrobromate or hydrogen chlorate.
14, the aqueous acidic composition of claim 9, wherein this betaine ester is selected from bromination or chlorination N-(2-spiceleaf oxygen base-2-oxoethyl)-N, N-dimethyl-2-spiceleaf oxygen base-2-oxoethyl ammonium; Bromination or chlorination N-(2-lemongrass oxygen base-2-oxoethyl)-N, N-dimethyl-2-lemongrass oxygen base-2-oxoethyl ammonium; Bromination or chlorination N-(2-virtue camphor tree oxygen base-2-oxoethyl)-N, N-dimethyl-2-virtue camphor tree oxygen base-2-oxoethyl ammonium; Bromination or chlorination N-(2-dihydromyrcene oxygen base-2-oxoethyl)-N, N-dimethyl-2-dihydromyrcene oxygen base-2-oxoethyl ammonium and composition thereof.
15, the aqueous acidic composition of claim 9, wherein this betaine ester is selected from N-butyl-N-(2-spiceleaf oxygen base-2-oxoethyl) glycine geranyl ester hydrobromate or hydrogen chlorate; N-butyl-N-(2-lemongrass oxygen base-2-oxoethyl) glycine citronellyl ester hydrobromate or hydrogen chlorate; N-butyl-N-(2-virtue camphor tree oxygen base-2-oxoethyl) glycine linalyl ester hydrobromate or hydrogen chlorate; N-butyl-N-(2-dihydromyrcene oxygen base-2-oxoethyl) glycine dihydromyrcene base ester hydrobromate or hydrogen chlorate.
16, the aqueous acidic composition of claim 9, wherein this betaine ester is selected from N-dodecyl-N-(2-spiceleaf oxygen base-2-oxoethyl) glycine geranyl ester hydrobromate or hydrogen chlorate; N-dodecyl-N-(2-lemongrass oxygen base-2-oxoethyl) glycine citronellyl ester hydrobromate or hydrogen chlorate; N-dodecyl-N-(2-virtue camphor tree oxygen base-2-oxoethyl) glycine linalyl ester hydrobromate or hydrogen chlorate; N-dodecyl-N-(2-dihydromyrcene oxygen base-2-oxoethyl) glycine dihydromyrcene base ester hydrobromate or hydrogen chlorate.
17, the aqueous acidic composition of claim 9, wherein this betaine ester is selected from N, two (2-spiceleaf oxygen base-2-oxoethyl) glycine geranyl ester hydrobromate or the hydrogen chlorates of N-; N, two (2-lemongrass oxygen base-2-oxoethyl) glycine citronellyl ester hydrobromate or the hydrogen chlorates of N-; N, N-two (2-virtue camphor tree oxygen base-2-oxoethyl) glycine linalyl ester hydrobromate or hydrogen chlorate; N, two (2-dihydromyrcene oxygen base-2-oxoethyl) glycine dihydromyrcene base ester hydrobromate or the hydrogen chlorates of N-.
18, arbitrary aqueous acidic composition among the claim 1-17, wherein this tensio-active agent is selected from negatively charged ion, nonionic and cats product, the preferred cationic tensio-active agent.
19, the aqueous acidic composition of claim 18, wherein this cats product is the cationic fabric softener compound.
20, the aqueous acidic composition of claim 19, wherein this cats product is a positively charged ion Biodegradable fabric softener compound, is selected from the quaternary ammonium compound and the amine precursor that lead to formula I or (II) below having: Or
Figure A9719515900052
Wherein Q be selected from-O-C (O)-,-C (O)-O-,-O-C (O)-O-,-NR 4-C (O)-,-C (O)-NR 4-;
R 1Be (CH 2) n-Q-T 2Or T 3
R 2Be (CH 2) m-Q-T 4Or T 5Or R 3
R 3Be C 1-C 4Alkyl or C 1-C 4Hydroxyalkyl or H;
R 4Be H or C 1-C 4Alkyl or C 1-C 4Hydroxyalkyl;
T 1, T 2, T 3, T 4, T 5Be C independently 11-C 22Alkyl or alkenyl;
N and m are 1～4 integers; With
X -It is the compatible negatively charged ion of softening agent.
21, arbitrary aqueous acidic composition among the claim 1-20, wherein these acidic substance are selected from mineral acid, carboxylic acid, alkylsulphonic acid and composition thereof.
22, arbitrary aqueous acidic composition among the claim 1-21, wherein said composition is a fabric softening compositions.
23, arbitrary preparation method of composition among the claim 1-22 comprises following step:
A) mixed surfactant and optional components (if containing) under the temperature that is higher than the tensio-active agent fusing point,
B) prepare water base material,
C) mixture for preparing in the step a) is dispersed in the water base material,
D) adding betaine ester arrives
D1) mixture of step a) preparation, or
D2) the water base material of step b), or
D3) surfactant dispersion of step c), or
D4) above-mentioned any mixture,
E) at random cool off resulting dispersion.
24, the method for claim 23, wherein steps d 3) the temperature of mixture be higher than Krafft (Krafft) temperature of tensio-active agent.
25, arbitrary method in the claim 23 or 24 wherein with resulting dispersion cooling, makes it to be lower than Krafft (Krafft) temperature of tensio-active agent.
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