CN1231688A - Concentrated fabric softening composition and highly unsaturated fabric softener compound thereof - Google Patents

Concentrated fabric softening composition and highly unsaturated fabric softener compound thereof Download PDF

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Publication number
CN1231688A
CN1231688A CN97197940A CN97197940A CN1231688A CN 1231688 A CN1231688 A CN 1231688A CN 97197940 A CN97197940 A CN 97197940A CN 97197940 A CN97197940 A CN 97197940A CN 1231688 A CN1231688 A CN 1231688A
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Prior art keywords
glycol
methyl
dimethyl
pentanediol
softening agent
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CN97197940A
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Inventor
T·特林
E·R·卡尔
H·B·托迪尔
R·O·凯斯
L·M·迈耶
E·H·瓦尔
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Procter and Gamble Co
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Procter and Gamble Co
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Priority claimed from US08/735,369 external-priority patent/US5759990A/en
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of CN1231688A publication Critical patent/CN1231688A/en
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2003Alcohols; Phenols
    • C11D3/2041Dihydric alcohols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38Cationic compounds
    • C11D1/62Quaternary ammonium compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/001Softening compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2003Alcohols; Phenols
    • C11D3/2041Dihydric alcohols
    • C11D3/2044Dihydric alcohols linear
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2003Alcohols; Phenols
    • C11D3/2041Dihydric alcohols
    • C11D3/2048Dihydric alcohols branched

Abstract

Biodegradable fabric softener compounds that contain ester linkages a substantial level of polyunsaturation in the hydrophobic chains. The compounds can be used to form fabric softening compositions that are aqueous dispersions of the compounds or clear compositions. These compositions have a desirable low viscosity and recover, after freezing and thawing, to have a stable low viscosity.

Description

Spissated fabric sofetening composition and its highly undersaturated fabric soft compound
Technical field
The present invention relates to be used to prepare undersaturated, the biodegradable fabric soft compound of height of the soft compound that is applicable to soft clothes.The present invention be more particularly directed to prepare the concentrate composition of soft fabric, its rinse that is used for the home washings fabric operation circulates and has good freezing/melt recovery character, so that fabulous soft fabric/control static and rewetting ability to be provided.
Background of invention
The fabric sofetening composition that contains high-load softening agent is that prior art is known.But, need have the highly enriched composition that character is restored in good freezing/melt, particularly the composition that can prepare by processing under normal room temperature.
The invention provides highly enriched water fluid fabric treatment composition, its under long-time condition of storage normally, be that the stability that has improvement under room temperature and the subnormal temperature (that is, do not precipitate, gel, retrogradation or curing) and its will restore after freezing to form stable composition.
Summary of the invention
On the one hand, liquid fabric softening composition of the present invention comprises: A. is by the weight of composition, about 15%-50%, and preferably about 16%-35%, the biodegradable fabric softener active matter of 17%-30% more preferably from about, it is selected from:
1. the softening agent that has following formula: [ ( R ) 4 - m - N ( + ) - [ ( C H 2 ) n - Y - R 1 ] m ] X ( - ) - - - - - - ( 1 ) Wherein each R substituting group is short chain C 1-C 6, preferred C 1-C 3Alkyl or hydroxyalkyl, for example methyl (most preferably), ethyl, propyl group, hydroxyethyl etc., benzyl or their mixture; Each m is 2 or 3; Each n is from 1 to about 4; Each Y is-O-(O) C-or-C (O)-O-; Each R 1In the carbonatoms summation, when Y be-to add 1 during O-(O) C-be C 12-C 22, preferred C 14-C 20, each R 1It is the alkyl of alkyl or replacement, preferred alkyl, monounsaturated alkylidene group and polyunsaturated alkylidene group, the softening agent actives that contains polyunsaturated alkylidene group account for existing total softening agent actives weight at least about 3%, preferably at least about 5%, more preferably at least about 10%, (used hereinly contain given R most preferably at least about 15% 1" percentage ratio of softening agent actives " of group and same R 1Group occupies the total R that forms total softening agent actives 1The percentage ratio of group is identical); (iodine number of " parent " lipid acid used herein or " accordingly " lipid acid is to be used for defining R 1The degree of unsaturation of group, this degree of unsaturation with contain same R 1The degree of unsaturation of the lipid acid of base is identical); Gegenion X wherein -Can be any negatively charged ion compatible with softening agent, preferred chlorine, bromine, methylsulfate or nitrate radical, more preferably chlorine.
2. the softening agent that has following formula:
Figure A9719794000071
Wherein each Y, R, R 1And X (-)Definition the same (this compounds comprises those compounds of following formula: [CH 3] 3N (+)[CH 2CH (CH 2O (O) CR 1) O (O) CR 1] Cl (-)C (O) R wherein particularly 1The R of, some unsaturated fatty acidss saturated such as oleic acid and some polyunsaturated lipid acid derived from some 1The mixture of group and each R be methyl or ethyl preferably, each R 1Preferably at C 15-C 19Scope in, the degree of unsaturation that in this hydrocarbyl chain, exist to change); With
3. their mixture; Said fabric softener active matter is stable dispersion form; B. randomly about 0%-is about 10%, preferably about 0.1%-5%, more preferably from about 0.2%-3% spices; C. randomly 0%-is about 2%, preferably about 0.01%-0.2%, more preferably from about 0.035%-0.1% stablizer; With the D. equipoise be liquid vehicle, comprise water and randomly account for about 5%-30% of composition weight, preferably about 8%-25%, the more preferably from about water miscible organic solvent of 10%-20%; The viscosity of said composition is lower than about 500cps, preferably is lower than about 400cps, more preferably less than about 200cps, freezing and thaw after, the viscosity of composition is restored to being lower than about 1000cps, preferably is lower than about 500cps, more preferably less than about 200cps.
On the other hand, said composition is transparent, and it comprises: A. presses composition weight meter, about 2%-80%, and preferably about 13%-75%, 17%-70% more preferably from about, the biodegradable fabric softener active matter of 19%-65% most preferably from about, it is selected from:
1. the softening agent that has following formula: [ ( R ) 4 - m - N ( + ) - [ ( C H 2 ) n - Y - R 1 ] m ] X ( - ) - - - - - - ( 1 ) Wherein each R substituting group is short chain C 1-C 6, preferred C 1-C 3Alkyl or hydroxyalkyl, for example methyl (most preferably), ethyl, propyl group, hydroxyethyl etc., benzyl or their mixture; Each m is 2 or 3; Each n is from 1 to about 4; Each Y is-O-(O) C-or-C (O)-O-; Each R 1In the carbonatoms summation, when Y be-to add 1 during O-(O) C-be C 12-C 22, preferred C 14-C 20, each R 1It is the alkyl of alkyl or replacement, preferred alkyl, monounsaturated alkylidene group and polyunsaturated alkylidene group, the softening agent actives that contains polyunsaturated alkylidene group account for existing total softening agent actives weight at least about 3%, preferably at least about 5%, more preferably at least about 10%, (used hereinly contain given R most preferably at least about 15% 1" percentage ratio of softening agent actives " of group and same R 1Group occupies the total R that forms total softening agent actives 1The percentage ratio of group is identical); (iodine number of " parent " lipid acid used herein or " accordingly " lipid acid is to be used for defining R 1The degree of unsaturation of group, this degree of unsaturation with contain same R 1The degree of unsaturation of the lipid acid of base is identical); Gegenion X wherein -Can be any negatively charged ion compatible with softening agent, preferred chlorine, bromine, methylsulfate or nitrate radical, more preferably chlorine.
2. the softening agent that has following formula:
Figure A9719794000082
Wherein each Y, R, R 1And X (-)Definition the same; With
3. their mixture; With the weight of B. by composition, be lower than about 40%, preferred about 10%-38%, 12%-25% more preferably from about, even the main solvent of 14%-20% more preferably from about, it is about 0.15-0.64 that this main solvent has ClogP, preferred about 0.25-0.62,0.40-0.60 more preferably from about, this main solvent preferably includes 1,2-hexylene glycol or can be 2 in addition, 2,4-trimethylammonium-1,3-pentanediol and 1, the mixture of 4-cyclohexanedimethanol, in order to obtain good phase stability, low temperature phase stability particularly, TMPD and 1, the proportional range of 4-cyclohexanedimethanol preferably about 80: 20 to about 50: 50, more preferably from about 75: 25.
The pH of said composition should be about 1-5, preferably about 1.5-4.5, more preferably from about 2-3.5.
Detailed Description A. fabric softener active matter
Necessary component of the present invention is the weight by composition, about 15%-50%, and preferably about 16%-35%, the biodegradable fabric softener active matter of 17%-30% more preferably from about, it is selected from compound and its mixture of hereinafter definition.These compounds are new compounds, have non-obvious character when the water base concentrated fabric softener compositions that is mixed with traditional type (it is the dispersion/suspensoid of fabric softener active matter).The softening agent actives that contains many unsaturated groups in these compounds should account at least about 3%, more preferably at least about 5%, even more preferably from about 10%, and most preferably from about 15%.This degree of unsaturation provides good freezing/melt to restore character.Usually, people do not wish to exist many unsaturated groups in actives because they than in addition single unsaturated group tendency more unstable.The existence of these high unsaturated materialss makes it more cater to the need, because the existence of many degrees of unsaturation of necessary high level, The compounds of this invention and/or composition should contain antiseptic-germicide, antioxidant and/or reductive agent does not degrade with the protection actives.
Diester quaternary amines fabric sofetening active compound (DEQA)
(1) first kind DEQA preferably contains the following formula: compound as main actives: [ ( R ) 4 - m - N ( + ) - [ ( C H 2 ) n - Y - R 1 ] m ] X ( - ) - - - - - - ( 1 ) Wherein each R substituting group is short chain C 1-C 6, preferred C 1-C 3Alkyl or hydroxyalkyl, for example methyl (most preferably), ethyl, propyl group, hydroxyethyl etc., benzyl or their mixture; Each m is 2 or 3; Each n is from 1 to about 4; Each Y is-O-(O) C-or-C (O)-O-; Each R 1In the carbonatoms summation, when Y be-to add 1 during O-(O) C-be C 12-C 22, preferred C 14-C 20, each R 1It is the alkyl of alkyl or replacement.Preferred this softening agent actives contains alkyl, monounsaturated alkylidene group and polyunsaturated alkylidene group, the softening agent actives that contains polyunsaturated alkylidene group account for existing total softening agent actives weight at least about 3%, preferably at least about 5%, more preferably at least about 10%, (used hereinly contain given R most preferably at least about 15% 1" percentage ratio of softening agent actives " of group is the percentage ratio that accounts for the gross activity thing, promptly given R 1Group accounts for existing total R 1The percentage ratio of group).
These R 1The iodine number of the maternal fatty acid of group (IV hereinafter referred to as) preferably on average is about 60-140, more preferably from about 70-130; Even 75-115 more preferably from about.It is believed that and comprise unsaturated R 1The actives of group preferably accounts for about 50%-100% of existing gross activity thing weight, 55%-95% more preferably from about, even 60%-90% more preferably from about.Contain how unsaturated R 1The actives of group account for existing gross activity thing weight at least about 3%, preferably at least about 5%, more preferably at least about 10%, most preferably at least about 15%.These many unsaturated groups are necessary, so that best viscosity stability to be provided, particularly freezing and thaw after.How unsaturated R in actives 1The content of group is high more, comprises unsaturated R 1The content of the actives of group can be low more.
Above gegenion X (-)Can be any negatively charged ion compatible with softening agent, the negatively charged ion of preferred strong acid, for example chlorine, bromine, methylsulfate, sulfate radical, nitrate radical etc., more preferably chlorine.
These biodegradable quaternary ammonium fabric softening compound things preferably contain C (O) R 1Group, this group is mainly derived from unsaturated fatty acids oleic acid for example, necessary polyunsaturated fatty acid, and/or saturated fatty acid, and/or from the acid of the partial hydrogenation of natural source fat, for example derived from vegetables oil and/or partially hydrogenated vegetable oil as low leaf mustard seed oil, Thistle oil, peanut oil, Oleum Helianthi, Semen Maydis oil, soybean oil, Yatall MA, rice bran wet goods.In another embodiment preferred, lipid acid has following general distribution, correlated DEQA be similar to described in the prior those: fatty acyl group DEQA 1DEQA 2DEQA 3DEQA 4DEQA 5C12 trace trace 00 0,C14 3300 0,C16 4455 5,C18 0056 6C14: 13300 0C16: 1 11 700 3C18: 1 74 73 71 68 67C18: 2488 11 11C18: 30112 2C20: 10022 2C20 and unknown 00667 to amount to 99 99 100 100 102 IV 86-90 88-95,99 100 95 cis/trans 20-30 20-30 455 (C18: 1) TPU 499 13 13 on 00200
The unrestricted example of DEQA is as follows: fatty acyl group DEQA 10DEQA 11C14 0 1,C16 11 25,C18 4 20C14: 10 0C16: 11 0C18: 1 27 45C18: 2 50 6C18: 03 of 370 the unknowns amount to 100 100 IV 125-138,56 cis/trans (C18: 1) do not obtain 7TPU 57 6DEQA10By soya fatty acid preparation, DEQA 11Prepare by slight hydrogenant tallow fatty acid.
Preferably most of at least fatty acyl group is undersaturated, for example about 50-100%, preferably about 55-95%; 60%-90% more preferably from about; the actives total concn (TPU) that contains the polyunsaturated fat acyl group can be about 3-30%, preferably about 5-25%, more preferably from about 10-18%.The cis/trans ratios of unsaturated fatty acyl group is important, and suitable/reverse proportionality is 1: 1 to about 50: 1, and Schwellenwert is 1: 1, preferably at least 3: 1, and more preferably from about 4: 1 to about 20: 1.
Undersaturated, comprise that necessary polyunsaturated fatty acyl group provides effective softness to turn usefulness into astoundingly, but also provide good rewetting characteristic, good antistatic property and excellent freezing-the back restorability thaws.These unsaturated materialss provide fabulous softness and antistatic property, have reduced forfeiture and " greasy " sense of water absorbability simultaneously.This two specific character makes people can use the softening agent higher than common requirement, and it provides several extra benefits, comprises the low color maintenance that damages and coloured article are had improvement to fabric.Generally the ratio that is enough to softening agent actives (gram) and fabric (kilogram) are provided of the usage quantity in the rinse circulation is at least about 3, preferably about 3.2-10, more preferably from about 3.5-7.The fabric color that needs to provide good in rinsing water keeps the concentration C of softening agent actives of the present invention of performance (by ppm, 1,000,000/) also depend on the relative quantity of fabric and rinsing water, weigh by the weight (by gram) and the ratio R of rinsing water weight (by kilogram) of fabric.Ratio=C/R is at least about 3, preferably at least about 3.3, and more preferably from about 3.5, even more preferably from about 3.7.
Also easier spissated premixture, this concentrated their the low viscosity of premixture maintenance, so easier processing, for example pumping, mixing etc. of being mixed with of height unsaturated materials.These highly undersaturated materials are if only contain usually a small amount of and its bonded solvent, promptly, account for about 5-about 20% of softening agent/solvent mixture gross weight, preferred about 8-about 25%, more preferably from about 10-is about 20%, even then also be mixed with dense, stable dispersion composite of the present invention at ambient temperature easily.This ability of at low temperatures actives being processed is for many unsaturated groups particularly important, because it has reduced degraded.As described later, when containing good antioxidant and/or reductive agent in compound and the softener composition, can provide other anti-degraded provide protection.
Should be clear, R and R 1Substituting group can randomly be replaced by various groups, and for example alkoxyl group or hydroxyl need only R 1Group keeps its hydrophobic basically characteristic.Admissible preferred compound is a kind of widely used fabric softener: the biodegradable diester variations of chlorination ditallow dimethylammonium (being called " DTDMAC " later on).Preferred long-chain DEQA is the DEQA by the thing source preparation that contains the many degrees of unsaturation of high-content, i.e. N, and N-two (acyl group oxygen ethyl)-N, the N-alkyl dimethyl ammonium chloride, wherein acyl group is by the fatty acid derived that contains enough degrees of unsaturation.
As used in this article, when the regulation diester, it can comprise the monoesters of existence.Be diester form at least about 80% DEQA preferably, 0 to about 20% can be that (for example, in formula (1), m is 2, one YR to the DEQA monoesters 1Group is " H " or " C-(O)-OH ").For softnessization, do not having/wash conditions that seldom washing composition is taken out of under, the percentage composition of monoesters should be low as far as possible, preferably is no more than about 5%.But under the high condition of anionic detergent tensio-active agent or detergent builder drag-out, some monoesters is desirable.The overall proportion of diester and monoesters is from about 100: 1 to about 2: 1, preferably from about 50: 1 to about 5: 1, more preferably from about 13: 1 to about 8: 1.Taking out of under the high detergent amount condition, diester/monoesters ratio is preferably about 11: 1.The content of monoesters can be controlled when making DEQA.
As the above compound of biodegradable quaternized ester-amine softnessization material, can prepare in the embodiment of this invention with the chemical reaction of standard.In a kind of synthetic method of the diester variations of DTDMAC, formula RN (CH 2CH 2OH) 2Amine be R all at two hydroxyl places with chemical formula 1The chloride of acid esterification of C (O) Cl makes it quaternized with alkylogen RX then, forms desired reaction product (wherein R and R 1Definition is the same).But chemical field the professional will appreciate that, this reaction sequence can be prepared the reagent of extensive selection.
The another kind of DEQA softening agent actives that is fit to the spissated liquid fabric softener composition of preparation the present invention has above chemical formula (1), and one of them R base is C 1-4Hydroxyalkyl, preferably one of them R base is a hydroxyethyl.The example of this hydroxyethyl ester actives is methylsulfuric acidization two (acyl group oxygen ethyl) (2-hydroxyethyl) ammonium methyl, and wherein acyl group is by above-mentioned fatty acid derived.Another example of such DEQA is by same and DEQA 1Fatty acid derived, hereinafter be expressed as DEQA 8
(2) second class DEQA activess have following general formula:
Figure A9719794000131
Wherein each Y, R, R 1And X (-)Has identical meanings as above.This compounds comprises the compound that chemical formula is following: [CH 3] 3N (+)[CH 2CH (CH 2O (O) CR 1) O (O) CR 1] Cl (-)Wherein each R is methyl or ethyl, preferably each R 1Be C 15-C 19As using in this article, when specifying diester, it can comprise the monoesters of existence.The monoesters quantity that can exist identical with in DEQA (1).
The reagent of these types and general preparation method thereof are disclosed in the United States Patent (USP) 4,137,180 that was presented to Naik etc. on January 30th, 1979, and this patent is quoted as a reference at this paper.The example of preferred formula (2) DEQA is that chemical formula is chlorination 1, " propyl group " ester quaternary ammonium fabric of 2-two (acyloxy)-3-front three aminopropane soft actives, wherein acyl group and DEQA 5Identical, hereinafter be expressed as DEQA 9
The above-mentioned DEQA actives of this paper can contain the lipid acid of low levels, and this lipid acid can be the degrade by product of for example hydrolysis of any part of softening agent actives in unreacted initiator and/or the final product composition having.The content of free fatty acids is preferably lower, preferably is lower than the about 10% of softening agent actives weight, more preferably less than about 5%.Spissated dispersion composite
Use stable " dispersion " composition of this paper new compound/preparation of compositions to be disclosed in the autre action pendante u.s. patent application serial number 08/461,207 of June 5 nineteen ninety-five by applications such as E.H.Wahl, this application is quoted for referencial use at this paper.B. spices
Premixture of the present invention and/or final product composition having can contain the compatible spices of any softening agent.Preferred spices is disclosed in the United States Patent (USP) 5,500,138 of the Bacon of promulgation on March 19th, 1996 etc., and this patent is quoted for referencial use at this paper.Spices can randomly exist, and its content is about 0%-10% of final product composition having weight, preferably about 0.1%-5%, more preferably from about 0.2%-3%.Use advantage of the present invention to be: spices preferably can add in the premixture with the preparation of simplifying the finished product dispersive composition and improve the deposition of said spices on fabric.This premixture can add and contain requirement acid, and preferred mineral acid is more preferably in the water of HCl, to form final product composition having discussed in this article.C. stablizer
Stablizer is at finished product dispersion of the present invention and/or transparent composition and randomly be what highly to need in starting material of the present invention, and or even necessary.The term " stablizer " that text uses comprises antioxidant and reductive agent.Their content in final composition is that 0%-is about 2%, preferably about 0.01%-0.2%, and for antioxidant 0.035%-0.1% more preferably from about, for reductive agent, 0.01%-0.2% more preferably from about.For premixture, this amount can be regulated according to the concentration of softening agent actives in premixture and final product composition having.This has guaranteed under the condition of storage good odor stable is being arranged for a long time.Antioxidant and reductive agent stablizer are crucial especially for the product (not having or few spices) of British plain spirits or low fragrance.
The example that can add the antioxidant in the dispersion composite of the present invention comprises the mixture of xitix, Quicifal, propyl gallate, and by Eastman Chemical Products, Inc. buys, and commodity are called Tenox RPG and Tenox RS-1; The mixture of BHT (butylated hydroxytoluene), BHA (butylated BHA), propyl gallate and citric acid, by EastmanChemical Products, Inc. buys, and commodity are called Tenox R-6; Butylated hydroxytoluene is buied by UOP Process Division, and commodity are called Sustane RBHT; Tertiary butylated hydroquinone, Eastman Chemical Products, Inc. is Tenox RTBHQ; Natural tocopherol, Eastman Chemical Products, Inc. is Tenox RGT-1/GT-2; With butylated BHA, Eastman Chemical Products, Inc. is BHA; The long-chain ester (C8-C22) of training acid, for example dodecyl ester of training acid; Irganox R1010; Irganox R1035; Irganox RB1171; Irganox R1425; Irganox R3114; Irganox R3125 and their mixture; Preferred Irganox R3125, Irganox R1425, Irganox R3114 and their mixture; More preferably single Irganox R3125 or itself and citric acid and/or other sequestrant mixture of citric acid isopropyl ester for example, Dequest R2010, to buy by Monsanto, chemical name is a 1-hydroxy ethylene-1,1-di 2 ethylhexyl phosphonic acid (hydroxyl second (fork two) phosphoric acid) and Tiron R, to buy by Kodak, chemical name is 4, the 5-dihydroxyl--Phenylsulfonic acid/sodium salt, and DTPA R, to buy by Aldrich, chemical name is a diethylene triaminepentaacetic acid(DTPA).D. water and water-miscible organic solvent system
Dispersion composite of the present invention contains water and randomly, comprises to account for the about 5%-30% of composition weight, preferably about 8%-25%, the more preferably from about water-miscible organic solvent of 10%-20%.This solvent preferably mixes with fabric softener DEQA, helps provide low viscosity to be easy to processing, for example pumping and/or mixing, even at ambient temperature.
The preferably water miscible solvent of organic solvent, for example ethanol; Virahol; 1, the 2-propylene glycol; 1, ammediol; Texacar PC; Hexylene glycol etc.
The undersaturated fabric softener compound of the disclosed height of preamble can be under for example about 10 ℃-40 ℃ of envrionment temperature, under preferred about 20 ℃-35 ℃, forms spissated final product composition having with the water-soluble solvent of low amount only under routine is mixed.When dispersion composite contained high-load polyunsaturated softening agent actives, this processing at ambient temperature was very important.Transparent composition
Said composition can be transparent, and comprise: A. presses composition weight meter, about 2%-80%, and preferably about 13%-75%, 17%-70% more preferably from about, the biodegradable fabric softener active matter of 19%-65% most preferably from about, it is selected from:
1. the softening agent that has following formula: [ ( R ) 4 - m - N ( + ) - [ ( C H 2 ) n - Y - R 1 ] m ] X ( - ) - - - - - - ( 1 ) Wherein each R substituting group is short chain C 1-C 6, preferred C 1-C 3Alkyl or hydroxyalkyl, for example methyl (most preferably), ethyl, propyl group, hydroxyethyl etc., benzyl or their mixture; Each m is 2 or 3; Each n is from 1 to about 4; Each Y is-O-(O) C-or-C (O)-O-; Each R 1In the carbonatoms summation, when Y be-to add 1 during O-(O) C-be C 12-C 22, preferred C 14-C 20, each R 1It is the alkyl of alkyl or replacement, preferred alkyl, monounsaturated alkylidene group and polyunsaturated alkylidene group, the softening agent actives that contains polyunsaturated alkylidene group account for existing total softening agent actives weight at least about 3%, preferably at least about 5%, more preferably at least about 10%, (used hereinly contain given R most preferably at least about 15% 1" percentage ratio of softening agent actives " of group and same R 1Group occupies the total R that forms total softening agent actives 1The percentage ratio of group is identical); (iodine number of " parent " lipid acid used herein or " accordingly " lipid acid is to be used for defining R 1The degree of unsaturation of group, this degree of unsaturation with contain same R 1The degree of unsaturation of the lipid acid of base is identical); Gegenion X wherein -Can be any negatively charged ion compatible with softening agent, preferred chlorine, bromine, methylsulfate or nitrate radical, more preferably chlorine.
2. the softening agent that has following formula:
Figure A9719794000162
Wherein each Y, R, R 1And X (-)Definition the same; With
3. their mixture; With the weight of B. by composition, be lower than about 40%, preferably about 10%-38%, more preferably from about 12%-25%, even the main solvent of 14%-20% more preferably from about, it is about 0.15-0.64 that this main solvent has ClogP, preferably about 0.25-0.62, more preferably from about 0.40-0.60, and preferably has identical degree of asymmetry, this main solvent preferably includes 1,2-hexylene glycol or can be 2,2 in addition, 4-trimethylammonium-1, the mixture of 3-pentanediol (TMPD) and 1,4 cyclohexane dimethanol is in order to obtain good phase stability, low temperature phase stability particularly, the proportional range of TMPD and 1,4 cyclohexane dimethanol preferably about 80: 20 to about 50: 50, more preferably from about 75: 25.C. randomly, but preferably, the low-molecular-weight water-soluble solvent such as the ethanol that are enough to improve transparency of significant quantity; Virahol; Propylene glycol; 1, ammediol; Texacar PC; Hexylene glycol etc., said water-soluble solvent exists with the amount that itself does not form transparent composition; D. randomly, but preferably, the water-soluble calcium that improves transparency and/or the magnesium salts of significant quantity, preferred muriate; With the E. equipoise be water.
Optional water-miscible organic solvent has below been described.Transparent composition of the present invention also can contain above-mentioned spices and stabiliser system, and all compositions can contain following optional component.B. main solvent
For preparation have requirement stability liquid state of the present invention, concentrate, the fabric softener composition of preferably transparent, the suitability of any main solvent all has selectivity astoundingly.Suitable solvent can be selected according to its octanol/water partition ratio (P).The octanol/water partition ratio of main solvent is its equilibrium concentration in octanol and the ratio of equilibrium concentration in water.The partition ratio of main solvent component of the present invention can provide by denary logarithm logP form easily.
The existing report of the logP of a lot of components, for example, can be from Daylight Chemical Information System company (Daylight CIS), Irvine, Califonia, the Pomona92 database that obtains comprises a lot of data and has quoted original.But logP value most convenient ground is to calculate with " CLOG P " program, and this program also can obtain from Daylight CIS.This program has also been listed the logP experimental value that has in the Pomona92 database." logP of calculating " is to determine (referring to A.Leo with the segmentation method of Hansch and Leo (ClogP), at " synthetic medicine chemistry " (ComprehensiveMedicinal Chemistry) the 4th volume (C.Hansch, P.G.Sammens, J.B.Taylor and C.A.Ramsden compile), p295, Pergamon Press, 1990, this paper quotes as a reference).Segmentation method is the chemical structure based on each component, and considers number and type, atom connectivity and the chemical bond of atom.These ClogP values are the most reliable and widely used estimated value for these physicochemical property, preferably use the experimental value of ClogP rather than logP when selecting to can be used for main solvent component of the present invention.
For some reason, lower molecular weight and biodegradable solvent also need.As if more asymmetric solvent very desirable, and the symmetric solvent of the height with symmetry centre is as 1,7-heptanediol or 1, two (methylol) hexanaphthenes of 4-show the composition that can not form substantial transparent when using separately, though its ClogP value is in the preferred value scope.People can select optimal main solvent to lead to into to contain 27% chlorination two of having an appointment (oleoyl oxygen ethyl) Dimethyl Ammonium, about 16-20% main solvent and about 4%-6% alcoholic acid composition about 40 °F (about 4.4 ℃) down storage whether keep transparent and under about 0 °F (about 18 ℃), whether can restore to determine from freezing state.
The solvent that is fit to comprises 2,2,4-trimethylammonium-1,3-pentanediol; 2,2,4-trimethylammonium-1, the derivative of the ethoxylate of 3-pentanediol, diethoxy thing or triethoxy thing; And/or 2-ethyl-1,3-hexylene glycol, and/or its mixture; I. monohydroxy-alcohol comprises:
A. n-propyl alcohol; And/or
Term " (C used herein x) " be meant the carbonatoms in the oxyalkylated base mateiral] comprising:
1.1,2-propylene glycol (C3) 2 (Me-E 3-4); 1,2-propylene glycol (C3) PO 4The 2-methyl isophthalic acid, 2-propylene glycol (C4) (Me-E 4-10); The 2-methyl isophthalic acid, 2-propylene glycol (C4) 2 (Me-E 1); The 2-methyl isophthalic acid, 2-propylene glycol (C4) PO 3The 2-methyl isophthalic acid, 2-propylene glycol (C4) BO 11, ammediol (C3) 2 (Me-E 6-8); 1, ammediol (C3) PO 5-62,2-diethyl-1, ammediol (C7) E 1-72,2-diethyl-1, ammediol (C7) PO 12,2-diethyl-1, ammediol (C7) n-BO 1-22 (C5) 2 (Me E 1-2); 2 (C5) PO 3-42-(1-methyl-propyl)-1, ammediol (C7) E 1-72-(1-methyl-propyl)-1, ammediol (C7) PO 12-(1-methyl-propyl)-1, ammediol (C7) n-BO 1-22-(2-methyl-propyl)-1, ammediol (C7) E 1-72-(2-methyl-propyl)-1, ammediol (C7) PO 12-(2-methyl-propyl)-1, ammediol (C7) n-BO 1-22-ethyl-1, ammediol (C5) (Me E 6-10); 2-ethyl-1, ammediol (C5) 2 (Me E 1); 2-ethyl-1, ammediol (C5) PO 32-ethyl-2-methyl isophthalic acid, ammediol (C6) (Me E 1-6); 2-ethyl-2-methyl isophthalic acid, ammediol (C6) PO 22-ethyl-2-methyl isophthalic acid, ammediol (C6) BO 12-sec.-propyl-1, ammediol (C6) (Me E 1-6); 2-sec.-propyl-1, ammediol (C6) PO 22-sec.-propyl-1, ammediol (C6) BO 1The 2-methyl isophthalic acid, ammediol (C4) 2 (Me E 2-5); The 2-methyl isophthalic acid, ammediol (C4) PO 4-5The 2-methyl isophthalic acid, ammediol (C4) BO 22-methyl-2-sec.-propyl-1, ammediol (C7) E 2-92-methyl-2-sec.-propyl-1, ammediol (C7) PO 12-methyl-2-sec.-propyl-1, ammediol (C7) n-BO 1-32-methyl-2-propyl group-1, ammediol (C7) E 1-72-methyl-2-propyl group-1, ammediol (C7) PO 12-methyl-2-propyl group-1, ammediol (C7) n-BO 1-22-propyl group-1, ammediol (C6) (Me E 1-4); 2-propyl group-1, ammediol (C6) PO 22-propyl group-1, ammediol (C6) BO 1
2.1,2-butyleneglycol (C4) (Me E 2-8); 1,2-butyleneglycol (C4) PO 2-31,2-butyleneglycol (C4) BO 12,3-dimethyl-1,2-butyleneglycol (C6) E 1-62,3-dimethyl-1,2-butyleneglycol (C6) n-BO 1-22-ethyl-1,2-butyleneglycol (C6) E 1-32-ethyl-1,2-butyleneglycol (C6) n-BO 1The 2-methyl isophthalic acid, 2-butyleneglycol (C5) (Me E 1-2); The 2-methyl isophthalic acid, 2-butyleneglycol (C5) PO 13,3-dimethyl-1,2-butyleneglycol (C6) E 1-63,3-dimethyl-1,2-butyleneglycol (C6) n-BO 1-2The 3-methyl isophthalic acid, 2-butyleneglycol (C5) (MeE 1-2); The 3-methyl isophthalic acid, 2-butyleneglycol (C5) PO 11,3 butylene glycol (C4) 2 (Me E 3-6); 1,3 butylene glycol (C4) PO 51,3 butylene glycol (C4) BO 22,2,3-trimethylammonium-1,3 butylene glycol (C7) (Me E 1-3); 2,2,3-trimethylammonium-1,3 butylene glycol (C7) PO 1-22,2-dimethyl-1,3 butylene glycol (C6) (MeE 3-8); 2,2-dimethyl-1,3 butylene glycol (C6) PO 32,3-dimethyl-1,3 butylene glycol (C6) (Me E 3-8); 2,3-dimethyl-1,3 butylene glycol (C6) PO 32-ethyl-1,3 butylene glycol (C6) (Me E 1-6); 2-ethyl-1,3 butylene glycol (C6) PO 2-32-ethyl-1,3 butylene glycol (C6) BO 12-ethyl-2-methyl isophthalic acid, 3-butyleneglycol (C7) (Me E 1); 2-ethyl-2-methyl isophthalic acid, 3-butyleneglycol (C7) PO 12-ethyl-2-methyl isophthalic acid, 3-butyleneglycol (C7) n-BO 2-42-ethyl-3-methyl isophthalic acid, 3-butyleneglycol (C7) (MeE 1); 2-ethyl-3-methyl isophthalic acid, 3-butyleneglycol (C7) PO 12-ethyl-3-methyl isophthalic acid, 3-butyleneglycol (C7) n-BO 2-42-sec.-propyl-1,3 butylene glycol (C7) (Me E 1); 2-sec.-propyl-1,3 butylene glycol (C7) PO 12-sec.-propyl-1,3 butylene glycol (C7) n-BO 2-4The 2-methyl isophthalic acid, 3-butyleneglycol (C5) 2 (Me E 1-3); The 2-methyl isophthalic acid, 3-butyleneglycol (C5) PO 42-propyl group-1,3 butylene glycol (C7) E 2-92-propyl group-1,3 butylene glycol (C7) PO 12-propyl group-1,3 butylene glycol (C7) n-BO 1-3The 3-methyl isophthalic acid, 3-butyleneglycol (C5) 2 (Me E 1-3); The 3-methyl isophthalic acid, 3-butyleneglycol (C5) PO 41,4-butyleneglycol (C4) 2 (Me E 2-4); 1,4-butyleneglycol (C4) PO 4-51,4-butyleneglycol (C4) BO 22,2,3-trimethylammonium-1,4-butyleneglycol (C7) E 2-92,2,3-trimethylammonium-1,4-butyleneglycol (C7) PO 12,2,3-trimethylammonium-1,4-butyleneglycol (C7) n-BO 1-32,2-dimethyl-1,4-butyleneglycol (C6) (Me E 1-6); 2,2-dimethyl-1,4-butyleneglycol (C6) PO 22,2-dimethyl-1,4-butyleneglycol (C6) BO 12,3-dimethyl-1,4-butyleneglycol (C6) (Me E 1-6); 2,3-dimethyl-1,4-butyleneglycol (C6) PO 22,3-dimethyl-1,4-butyleneglycol (C6) BO 12-ethyl-1,4-butyleneglycol (C6) (Me E 1-4); 2-ethyl-1,4-butyleneglycol (C6) PO 22-ethyl-1,4-butyleneglycol (C6) BO 12-ethyl-2-methyl isophthalic acid, 4-butyleneglycol (C7) E 1-72-ethyl-2-methyl isophthalic acid, 4-butyleneglycol (C7) PO 12-ethyl-2-methyl isophthalic acid, 4-butyleneglycol (C7) n-BO 1-22-ethyl-3-methyl isophthalic acid, 4-butyleneglycol (C7) E 1-72-ethyl-3-methyl isophthalic acid, 4-butyleneglycol (C7) PO 12-ethyl-3-methyl isophthalic acid, 4-butyleneglycol (C7) n-BO 1-22-sec.-propyl-1,4-butyleneglycol (C7) E 1-72-sec.-propyl-1,4-butyleneglycol (C7) PO 1Different third methyl isophthalic acid of 2-, 4-butyleneglycol (C7) n-BO 1-2The 2-methyl isophthalic acid, 4-butyleneglycol (C5) (Me E 6-10); The 2-methyl isophthalic acid, 4-butyleneglycol (C5) 2 (Me E 1); The 2-methyl isophthalic acid, 4-butyleneglycol (C5) PO 3The 2-methyl isophthalic acid, 4-butyleneglycol (C5) BO 12-propyl group-1,4-butyleneglycol (C7) E 1-52-propyl group-1,4-butyleneglycol (C7) n-BO 1-23 ethyls-1-methyl isophthalic acid, 4-butyleneglycol (C7) E 2-93-ethyl-1-methyl isophthalic acid, 4-butyleneglycol (C7) PO 13-ethyl-1-methyl isophthalic acid, 4-butyleneglycol (C7) n-BO 1-32,3-butyleneglycol (C4) (Me E 6-10); 2,3-butyleneglycol (C4) 2 (Me E 1); 2,3-butyleneglycol (C4) PO 3-42,3-butyleneglycol (C4) BO 12,3-dimethyl-2,3-butyleneglycol (C6) E 3-92,3-dimethyl-2,3-butyleneglycol (C6) PO 12,3-dimethyl-2,3-butyleneglycol (C6) BO 1-32-methyl-2,3-butyleneglycol (C5) (Me E 1-5); 2-methyl-2,3-butyleneglycol (C5) PO 22-methyl-2,3-butyleneglycol (C5) BO 1
3.1,2-pentanediol (C5) E 3-101,2-pentanediol (C5) PO 11,2-pentanediol (C5) n-BO 2-3The 2-methyl isophthalic acid, 2-pentanediol (C6) E 1-3The 2-methyl isophthalic acid, 2-pentanediol (C6) n-BO 1The 2-methyl isophthalic acid, 2-pentanediol (C6) BO 1The 3-methyl isophthalic acid, 2-pentanediol (C6) E 1-3The 3-methyl isophthalic acid, 2-pentanediol (C6) n-BO 1The 4-methyl isophthalic acid, 2-pentanediol (C6) E 1-3The 4-methyl isophthalic acid, 2-pentanediol (C6) n-BO 11,3-pentanediol (C5) 2 (Me-E 1-2); 1,3-pentanediol (C5) PO 3-42,2-dimethyl-1,3-pentanediol (C7) (Me-E 1); 2,2-dimethyl-1,3-pentanediol (C7) PO 12,2-dimethyl-1,3-pentanediol (C7) n-BO 2-42,3-dimethyl-1,3-pentanediol (C7) (Me-E 1); 2,3-dimethyl-1,3-pentanediol (C7) PO 12,3-dimethyl-1,3-pentanediol (C7) n-BO 2-42,4-dimethyl-1,3-pentanediol (C7) (Me-E 1); 2,4-dimethyl-1,3-pentanediol (C7) PO 12,4-dimethyl-1,3-pentanediol (C7) n-BO 2-42-ethyl-1,3-pentanediol (C7) E 2-92-ethyl-1,3-pentanediol (C7) PO 12-ethyl-1,3-pentanediol (C7) n-BO 1-3The 2-methyl isophthalic acid, 3-pentanediol (C6) 2 (Me-E 1-6); The 2-methyl isophthalic acid, 3-pentanediol (C6) PO 2-3The 2-methyl isophthalic acid, 3-pentanediol (C6) BO 13,4-dimethyl-1,3-pentanediol (C7) (Me-E 1); 3,4-dimethyl-1,3-pentanediol (C7) PO 13,4-dimethyl-1,3-pentanediol (C7) n-BO 2-4The 3-methyl isophthalic acid, 3-pentanediol (C6) 2 (Me-E 1-6); The 3-methyl isophthalic acid, 3-pentanediol (C6) PO 2-3The 3-methyl isophthalic acid, 3-pentanediol (C6) BO 14,4-dimethyl-1,3-pentanediol (C7) (Me-E 1); 4,4-dimethyl-1,3-pentanediol (C7) PO 14,4-dimethyl-1,3-pentanediol (C7) n-BO 2-4The 4-methyl isophthalic acid, 3-pentanediol (C6) 2 (Me-E 1-6); The 4-methyl isophthalic acid, 3-pentanediol (C6) PO 2-3The 4-methyl isophthalic acid, 3-pentanediol (C6) BO 11,4-pentanediol (C5) 2 (Me-E 1-2); 1,4-pentanediol (C5) PO 3-42,2-dimethyl-1,4-pentanediol (C7) (Me-E 1); 2,2-dimethyl-1,4-pentanediol (C7) PO 12,2-dimethyl-1,4-pentanediol (C7) n-BO 2-42,3-dimethyl-1,4-pentanediol (C7) (Me-E 1); 2,3-dimethyl-1,4-pentanediol (C7) PO 12,3-dimethyl-1,4-pentanediol (C7) n-BO 2-42,4-dimethyl-1,4-pentanediol (C7) (Me-E 1); 2,4-dimethyl-1,4-pentanediol (C7) PO 12,4-dimethyl-1,4-pentanediol (C7) n-BO 2-4The 2-methyl isophthalic acid, 4-pentanediol (C6) (Me-E 1-6); The 2-methyl isophthalic acid, 4-pentanediol (C6) PO 2-3The 2-methyl isophthalic acid, 4-pentanediol (C6) BO 13,3-dimethyl-1,4-pentanediol (C7) (Me-E 1); 3,3-dimethyl-1,4-pentanediol (C7) PO 13,3-dimethyl-1,4-pentanediol (C7) n-BO 2-43,4-dimethyl-1,4-pentanediol (C7) (Me-E 1); 3,4-dimethyl-1,4-pentanediol (C7) PO 13,4-dimethyl-1,4-pentanediol (C7) n-BO 2-4The 3-methyl isophthalic acid, 4-pentanediol (C6) 2 (Me-E 1-6); The 3-methyl isophthalic acid, 4-pentanediol (C6) PO 2-3The 3-methyl isophthalic acid, 4-pentanediol (C6) BO 1The 4-methyl isophthalic acid, 4-pentanediol (C6) 2 (Me-E 1-6); The 4-methyl isophthalic acid, 4-pentanediol (C6) PO 2-3The 4-methyl isophthalic acid, 4-pentanediol (C6) BO 11,5-pentanediol (C5) (Me-E 4-10); 1,5-pentanediol (C5) 2 (Me-E 1); 1,5-pentanediol (C5) PO 32,2-dimethyl-1,5-pentanediol (C7) E 1-72,2-dimethyl-1,5-pentanediol (C7) PO 12,2-dimethyl-1,5-pentanediol (C7) n-BO 1-22,3-dimethyl-1,5-pentanediol (C7) E 1-72,3-dimethyl-1,5-pentanediol (C7) PO 12,3-dimethyl-1,5-pentanediol (C7) n-BO 1-22,4-dimethyl-1,5-pentanediol (C7) E 1-72,4-dimethyl-1,5-pentanediol (C7) PO 12,4-dimethyl-1,5-pentanediol (C7) n-BO 1-22-ethyl-1,5-pentanediol (C7) E 1-52-ethyl-1,5-pentanediol (C7) n-BO 1-2The 2-methyl isophthalic acid, 5-pentanediol (C6) (Me-E 1-4); The 2-methyl isophthalic acid, 5-pentanediol (C6) PO 23,3-dimethyl-1,5-pentanediol (C7) E 1-73,3-dimethyl-1,5-pentanediol (C7) PO 13,3-dimethyl-1,5-pentanediol (C7) n-BO 1-2The 3-methyl isophthalic acid, 5-pentanediol (C6) (Me-E 1-4); The 3-methyl isophthalic acid, 5-pentanediol (C6) PO 22,3-pentanediol (C5) (Me-E 1-3); 2,3-pentanediol (C5) PO 22-methyl-2,3-pentanediol (C6) E 1-72-methyl-2,3-pentanediol (C6) PO 12-methyl-2,3-pentanediol (C6) n-BO 1-23-methyl-2,3-pentanediol (C6) E 1-73-methyl-2,3-pentanediol (C6) PO 13-methyl-2,3-pentanediol (C6) n-BO 1-24-methyl-2,3-pentanediol (C6) E 1-74-methyl-2,3-pentanediol (C6) PO 14-methyl-2,3-pentanediol (C6) n-BO 1-22,4-pentanediol (C5) 2 (Me-E 1-4); 2,4-pentanediol (C5) PO 42,3-dimethyl-2,4-pentanediol (C7) (Me-E 1-4); 2,3-dimethyl-2,4-pentanediol (C7) PO 22,4-dimethyl-2,4-pentanediol (C7) (Me-E 1-4); 2,4-dimethyl-2,4-pentanediol (C7) PO 22-methyl-2,4-pentanediol (C7) (Me-E 5-10); 2-methyl-2,4-pentanediol (C7) PO 33,3-dimethyl-2,4-pentanediol (C7) (Me-E 1-4); 3,3-dimethyl-2,4-pentanediol (C7) PO 23-methyl-2,4-pentanediol (C6) (Me-E 5-10); 3-methyl-2,4-pentanediol (C6) PO 3
4.1,3-hexylene glycol (C6) (Me-E 1-5); 1,3-hexylene glycol (C6) PO 21,3-hexylene glycol (C6) BO 1The 2-methyl isophthalic acid, 3-hexylene glycol (C7) E 2-9The 2-methyl isophthalic acid, 3-hexylene glycol (C7) PO 1The 2-methyl isophthalic acid, 3-hexylene glycol (C7) n-BO 1-3The 2-methyl isophthalic acid, 3-hexylene glycol (C7) BO 1The 3-methyl isophthalic acid, 3-hexylene glycol (C7) E 2-9The 3-methyl isophthalic acid, 3-hexylene glycol (C7) PO 1The 3-methyl isophthalic acid, 3-hexylene glycol (C7) n-BO 1-3The 4-methyl isophthalic acid, 3-hexylene glycol (C7) E 2-9The 4-methyl isophthalic acid, 3-hexylene glycol (C7) PO 1The 4-methyl isophthalic acid, 3-hexylene glycol (C7) n-BO 1-3The 5-methyl isophthalic acid, 3-hexylene glycol (C7) E 2-9The 5-methyl isophthalic acid, 3-hexylene glycol (C7) PO 1The 5-methyl isophthalic acid, 3-hexylene glycol (C7) n-BO 1-31,4-hexylene glycol (C6) (Me-E 1-5); 1,4-hexylene glycol (C6) PO 21,4-hexylene glycol (C6) BO 1The 2-methyl isophthalic acid, 4-hexylene glycol (C7) E 2-9The 2-methyl isophthalic acid, 4-hexylene glycol (C7) PO 1The 2-methyl isophthalic acid, 4-hexylene glycol (C7) n-BO 1-3The 3-methyl isophthalic acid, 4-hexylene glycol (C7) E 2-9The 3-methyl isophthalic acid, 4-hexylene glycol (C7) PO 1The 3-methyl isophthalic acid, 4-hexylene glycol (C7) n-BO 1-3The 4-methyl isophthalic acid, 4-hexylene glycol (C7) E 2-9The 4-methyl isophthalic acid, 4-hexylene glycol (C7) PO 1The 4-methyl isophthalic acid, 4-hexylene glycol (C7) n-BO 1-3The 5-methyl isophthalic acid, 4-hexylene glycol (C7) E 2-9The 5-methyl isophthalic acid, 4-hexylene glycol (C7) PO 1The 5-methyl isophthalic acid, 4-hexylene glycol (C7) n-BO 1-31,5-hexylene glycol (C6) (Me-E 1-5); 1,5-hexylene glycol (C6) PO 21,5-hexylene glycol (C6) BO 1The 2-methyl isophthalic acid, 5-hexylene glycol (C7) E 2-9The 2-methyl isophthalic acid, 5-hexylene glycol (C7) PO 1The 2-methyl isophthalic acid, 5-hexylene glycol (C7) n-BO 1-3The 3-methyl isophthalic acid, 5-hexylene glycol (C7) E 2-9The 3-methyl isophthalic acid, 5-hexylene glycol (C7) PO 1The 3-methyl isophthalic acid, 5-hexylene glycol (C7) n-BO 1-3The 4-methyl isophthalic acid, 5-hexylene glycol (C7) E 2-9The 4-methyl isophthalic acid, 5-hexylene glycol (C7) PO 1The 4-methyl isophthalic acid, 5-hexylene glycol (C7) n-BO 1-3The 5-methyl isophthalic acid, 5-hexylene glycol (C7) E 2-9The 5-methyl isophthalic acid, 5-hexylene glycol (C7) PO 1The 5-methyl isophthalic acid, 5-hexylene glycol (C7) n-BO 1-31,6-hexylene glycol (C6) (Me-E 1-2); 1,6-hexylene glycol (C6) PO 1-21,6-hexylene glycol (C6) n-BO 4The 2-methyl isophthalic acid, 6-hexylene glycol (C7) E 1-5The 2-methyl isophthalic acid, 6-hexylene glycol (C7) n-BO 1-2The 3-methyl isophthalic acid, 6-hexylene glycol (C7) E 1-5The 3-methyl isophthalic acid, 6-hexylene glycol (C7) n-BO 1-22,3-hexylene glycol (C6) E 1-52,3-hexylene glycol (C6) n-BO 12,3-hexylene glycol (C6) BO 12,4-hexylene glycol (C6) (Me-E 3-8); 2,4-hexylene glycol (C6) PO 32-methyl-2,4-hexylene glycol (C7) (Me E 1-2); 2-methyl-2,4-hexylene glycol (C7) PO 1-23-methyl-2,4-hexylene glycol (C7) (Me-E 1-2); 3-methyl-2,4-hexylene glycol (C7) PO 1-24-methyl-2,4-hexylene glycol (C7) (Me-E 1-2); 4-methyl-2,4-hexylene glycol (C7) PO 1-25-methyl-2,4-hexylene glycol (C7) (Me-E 1-2); 5-methyl-2,4-hexylene glycol (C7) PO 1-22,5-hexylene glycol (C6) (Me-E 3-8); 2,5-hexylene glycol (C6) PO 32-methyl-2,5-hexylene glycol (C7) (Me-E 1-2); 2-methyl-2,5-hexylene glycol (C7) PO 1-23-methyl-2,5-hexylene glycol (C7) (Me-E 1-2); 3-methyl-2,5-hexylene glycol (C7) PO 1-23,4-hexylene glycol (C6) E 1-53,4-hexylene glycol (C6) n-BO 13,4-hexylene glycol (C6) BO 1
5.1,3-heptanediol (C7) E 1-71,3-heptanediol (C7) PO 11,3-heptanediol (C7) n-BO 1-21,4-heptanediol (C7) E 1-71,4-heptanediol (C7) PO 11,4-heptanediol (C7) n-BO 1-21,5-heptanediol (C7) E 1-71,5-heptanediol (C7) PO 11,5-heptanediol (C7) n-BO 1-21,6-heptanediol (C7) E 1-71,6-heptanediol (C7) PO 11,6-heptanediol (C7) n-BO 1-21,7-heptanediol (C7) E 1-21,7-heptanediol (C7) n-BO 22,4-heptanediol (C7) E 3-102,4-heptanediol (C7) (Me-E 1); 2,4-heptanediol (C7) PO 12,4-heptanediol (C7) n-BO 32,5-heptanediol (C7) E 3-102,5-heptanediol (C7) (Me-E 1); 2,5-heptanediol (C7) PO 12,5-heptanediol (C7) n-BO 32,6-heptanediol (C7) E 3-102,6-heptanediol (C7) (Me-E 1); 2,6-heptanediol (C7) PO 12,6-heptanediol (C7) n-BO 33,5-heptanediol (C7) E 3-103,5-heptanediol (C7) (Me-E 1); 3,5-heptanediol (C7) PO 13,5-heptanediol (C7) n-BO 3
6.3-methyl-2-sec.-propyl-1,3 butylene glycol (C8) PO 12,3,3-trimethylammonium-2,4-pentanediol (C8) PO 12,2-diethyl-1,3 butylene glycol (C8) E 2-52,3-dimethyl-2,4-hexylene glycol (C8) E 2-52,4-dimethyl-2,4-hexylene glycol (C8) E 2-52,5-dimethyl-2,4-hexylene glycol (C8) E 2-53,3-dimethyl-2,4-hexylene glycol (C8) E 2-53,4-dimethyl-2,4-hexylene glycol (C8) E 2-53,5-dimethyl-2,4-hexylene glycol (C8) E 2-54,5-dimethyl-2,4-hexylene glycol (C8) E 2-55,5-dimethyl-2,4-hexylene glycol (C8) E 2-52,3-dimethyl-2,5-hexylene glycol (C8) E 2-52,4-dimethyl-2,5-hexylene glycol (C8) E 2-52,5-dimethyl-2,5-hexylene glycol (C8) E 2-53,3-dimethyl-2,5-hexylene glycol (C8) E 2-53,4-dimethyl-2,5-hexylene glycol (C8) E 2-53-methyl-3,5-heptanediol (C8) E 2-52,2-diethyl-1,3 butylene glycol (C8) n-BO 1-22,3-dimethyl-2,4-hexylene glycol (C8) n-BO 1-22,4-dimethyl-2,4-hexylene glycol (C8) n-BO 1-22,5-dimethyl-2,4-hexylene glycol (C8) n-BO 1-23,3-dimethyl-2,4-hexylene glycol (C8) n-BO 1-23,4-dimethyl-2,4-hexylene glycol (C8) n-BO 1-23,5-dimethyl-2,4-hexylene glycol (C8) n-BO 1-24,5-dimethyl-2,4-hexylene glycol (C8) n-BO 1-25,5-dimethyl-2,4-hexylene glycol (C8) n-BO 1-22,3-dimethyl-2,5-hexylene glycol (C8) n-BO 1-22,4-dimethyl-2,5-hexylene glycol (C8) n-BO 1-22,5-dimethyl-2,5-hexylene glycol (C8) n-BO 1-23,3-dimethyl-2,5-hexylene glycol (C8) n-BO 1-23,4-dimethyl-2,5-hexylene glycol (C8) n-BO 1-23-methyl-3,5-heptanediol (C8) n-BO 1-22-(1, the 2-dimethyl propyl)-1, ammediol (C8) n-BO 1-22-ethyl-2,3-dimethyl-1,3 butylene glycol (C8) n-BO 12-methyl-2-sec.-propyl-1,3 butylene glycol (C8) n-BO 13-methyl-2-sec.-propyl-1,4-butyleneglycol (C8) n-BO 12,2,3-trimethylammonium-1,3-pentanediol (C8) n-BO 12,2,4-trimethylammonium-1,3-pentanediol (C8) n-BO 12,4,4-trimethylammonium-1,3-pentanediol (C8) n-BO 13,4,4-trimethylammonium-1,3-pentanediol (C8) n-BO 12,2,3-trimethylammonium-1,4-pentanediol (C8) n-BO 12,2,4-trimethylammonium-1,4-pentanediol (C8) n-BO 12,3,3-trimethylammonium-1,4-pentanediol (C8) n-BO 12,3,4-trimethylammonium-1,4-pentanediol (C8) n-BO 13,3,4-trimethylammonium-1,4-pentanediol (C8) n-BO 12,3,4-trimethylammonium-2,4-pentanediol (C8) n-BO 14-ethyl-2,4-hexylene glycol (C8) n-BO 12-methyl-2,4-heptanediol (C8) n-BO 13-methyl-2,4-heptanediol (C8) n-BO 14-methyl-2,4-heptanediol (C8) n-BO 15-methyl-2,4-heptanediol (C8) n-BO 16-methyl-2,4-heptanediol (C8) n-BO 12-methyl-2,5-heptanediol (C8) n-BO 13-methyl-2,5-heptanediol (C8) n-BO 14-methyl-2,5-heptanediol (C8) n-BO 15-methyl-2,5-heptanediol (C8) n-BO 16-methyl-2,5-heptanediol (C8) n-BO 12-methyl-2,6-heptanediol (C8) n-BO 13-methyl-2,6-heptanediol (C8) n-BO 14-methyl-2,6-heptanediol (C8) n-BO 12-methyl-3,5-heptanediol (C8) n-BO 12-(1, the 2-dimethyl propyl)-1, ammediol (C8) E 1-32-ethyl-2,3-dimethyl-1,3 butylene glycol (C8) E 1-32-methyl-2-sec.-propyl-1,3 butylene glycol (C8) E 1-33-methyl-2-sec.-propyl-1,4-butyleneglycol (C8) E 1-32,2,3-trimethylammonium-1,3-pentanediol (C8) E 1-32,2,4-trimethylammonium-1,3-pentanediol (C8) E 1-32,4,4-trimethylammonium-1,3-pentanediol (C8) E 1-33,4,4-trimethylammonium-1,3-pentanediol (C8) E 1-32,2,3-trimethylammonium-1,4-pentanediol (C8) E 1-32,2,4-trimethylammonium-1,4-pentanediol (C8) E 1-32,3,3-trimethylammonium-1,4-pentanediol (C8) E 1-32,3,4-trimethylammonium-1,4-pentanediol (C8) E 1-33,3,4-trimethylammonium-1,4-pentanediol (C8) E 1-32,3,4-trimethylammonium-2,4-pentanediol (C8) E 1-34-ethyl-2,4-hexylene glycol (C8) E 1-32-methyl-2,4-heptanediol (C8) E 1-33-methyl-2,4-heptanediol (C8) E 1-34-methyl-2,4-heptanediol (C8) E 1-35-methyl-2,4-heptanediol (C8) E 1-36-methyl-2,4-heptanediol (C8) E 1-32-methyl-2,5-heptanediol (C8) E 1-33-methyl-2,5-heptanediol (C8) E 1-34-methyl-2,5-heptanediol (C8) E 1-35-methyl-2,5-heptanediol (C8) E 1-36-methyl-2,5-heptanediol (C8) E 1-32-methyl-2,6-heptanediol (C8) E 1-33-methyl-2,6-heptanediol (C8) E 1-34-methyl-2,6-heptanediol (C8) E 1-3And/or 2-methyl-3,5-heptanediol (C8) E 1-3And
7. their mixture.IX. aromatic diol comprises: 1-phenyl-1; 1-phenyl-1, the 2-propylene glycol; 2-phenyl-1, the 2-propylene glycol; 3-phenyl-1, the 2-propylene glycol; 1-(3-aminomethyl phenyl)-1, ammediol; 1-(4-aminomethyl phenyl)-1, ammediol; 2-methyl isophthalic acid-phenyl-1, ammediol; 1-phenyl-1,3 butylene glycol; 3-phenyl-1,3 butylene glycol; 1-phenyl-1, the 4-butyleneglycol; 2-phenyl-1, the 4-butyleneglycol; And/or 1-phenyl-2, the 3-butyleneglycol; X. above structure be the main solvent of homologue or analogue, wherein add-individual or a plurality of CH 2Group, and for added each CH 2Group, all the adjacent carbons from molecule is removed two hydrogen atoms to form carbon-to-carbon double bond, the hydrogen atom sum keeps constant in the molecule thereby make, and comprising: 2,2-two-2-propenyl-1, ammediol; 2-(1-pentenyl)-1, ammediol; 2-(2-methyl-2-propenyl)-2-(2-propenyl)-1, ammediol; 2-(3-methyl-1-butene base)-1, ammediol; 2-(4-pentenyl)-1, ammediol; 2-ethyl-2-(2-methyl-2-propenyl)-1, ammediol; 2-ethyl-2-(2-propenyl)-1, ammediol; 2-methyl-2-(3-methyl-3-butenyl)-1, ammediol; 2,2-diallyl-1,3 butylene glycol; 2-(1-ethyl-1-propenyl)-1,3 butylene glycol; 2-(crotyl)-2-methyl isophthalic acid, the 3-butyleneglycol; 2-(3-methyl-2-butene base)-1,3 butylene glycol; 2-ethyl-2-(2-propenyl)-1,3 butylene glycol; 2-methyl-2-(1-methyl-2-propenyl)-1,3 butylene glycol; 2,3-two (1-methyl ethylidene)-1,4-butyleneglycol; 2-(3-methyl-2-butene base)-3-methylene radical-1, the 4-butyleneglycol; 2-(1,1-dimethyl propyl-2-butylene-1,4-glycol; 2-(1-methyl-propyl)-2-butylene-1, the 4-glycol; 2-butyl-2-butylene-1, the 4-glycol; 2-vinyl-3-ethyl-1, the 3-pentanediol; 2-vinyl-4,4-dimethyl-1,3-pentanediol; 3-methyl-2-(2-propenyl)-1, the 4-pentanediol; 2-(1-propenyl)-1, the 5-pentanediol; 2-(2-propenyl)-1, the 5-pentanediol; 2-ethylidene-3-methyl isophthalic acid, the 5-pentanediol; 2-propylidene-1, the 5-pentanediol; 3-ethylidene-2,4-dimethyl-2,4-pentanediol; 2-(1, the 1-dimethyl ethyl)-4-amylene-1, the 3-glycol; 2-ethyl-2,3-dimethyl-4-amylene-1,3-glycol; 4-ethyl-2-methylene radical-1, the 4-hexylene glycol; 2,3,5-trimethylammonium-1,5-hexadiene-3,4-glycol; 5-ethyl-3-methyl isophthalic acid, 5-hexadiene-3,4-glycol; 2-(1-methyl ethylene)-1, the 5-hexylene glycol; 2-vinyl-1, the 6-hexylene glycol; 5,5-dimethyl-1-hexene-3,4-glycol; 5,5-dimethyl-1-hexene-3,4--glycol; 4-vinyl-2,5-dimethyl-2-hexene-1,5-glycol; 2-vinyl-2,5-dimethyl-3-hexene-1,6-glycol; 2-ethyl-3-hexene-1, the 6-glycol; 3,4-dimethyl-3-hexene-1,6-glycol; 2,5-dimethyl-4-hexene-2,3-glycol; 3,4-dimethyl-4-hexene-2,3-glycol; 3-(2-propenyl)-5-hexene-1, the 3-glycol; 2,3-dimethyl-5-hexene-2,3-glycol; 3,4-dimethyl-5-hexene-2,3-glycol; 3,5-dimethyl-5-hexene-2,3-glycol; 3-vinyl-2,5-dimethyl-5-hexene-2,4-glycol; 6-methyl-5-methylene radical-1, the 4-heptanediol; 2,3-dimethyl-1,5-heptadiene-3,4-glycol; 2,5-dimethyl-1,5-heptadiene-3,4-glycol; 3,5-dimethyl-1,5-heptadiene-3,4-glycol; 2,6-two (methylene radical)-1,7-heptanediol; 4-methylene radical-1, the 7-heptanediol; 2,4-dimethyl-1-teracrylic acid, 5-glycol; 2,6-dimethyl-1-teracrylic acid, 5-glycol; 3-vinyl-5-methyl isophthalic acid-teracrylic acid, the 5-glycol; 6,6-dimethyl-1-teracrylic acid, 5-glycol; 4,6-dimethyl-2,4-heptadiene-2,6-glycol; 4,4-dimethyl-2,5-heptadiene-1,7-glycol; 2,5,5-trimethylammonium-2,6-heptadiene-1,4-glycol; 5,6-dimethyl-2-heptene-1,4-glycol; 5-ethyl-2-heptene-1,5 glycol; 2-methyl-2-heptene-1, the 7-glycol; 4,6-dimethyl-3-heptene-1,5-glycol; 3-methyl-6-methylene radical-3-heptene-1, the 7-glycol; 2,4-dimethyl-3-heptene-2,5-glycol; 2,5-dimethyl-3-heptene-2,5-glycol; 2,6-dimethyl-3-heptene-2,6-glycol; 4,6-dimethyl-3-heptene-2,6-glycol; 2,4-dimethyl-5-heptene-1,3-glycol; 3,6-dimethyl-5-heptene-1,3-glycol; 2,6-dimethyl-5-heptene-1,4-glycol; 3,6-dimethyl-5-heptene-1,4-glycol; 2,3-dimethyl-5-heptene-2,4-glycol; 2,2-dimethyl-6-heptene-1,3-glycol; 4-(2-propenyl)-6-heptene-1, the 4-glycol; 5,6-dimethyl-6-heptene-1,4-glycol; 2,4-dimethyl-6-heptene-1,5-glycol; 2-ethylidene-6-methyl-6-heptene-1, the 5-glycol; 4-(2-propenyl)-6-heptene-2, the 4-glycol; 5,5-dimethyl-6-heptene-2,4-glycol; 4,6-dimethyl-6-heptene-2,5-glycol; 5-vinyl-4-methyl-6-heptene-2, the 5-glycol; 2-methylene radical-1, the 3-ethohexadiol; 2,6-dimethyl-1,6-octadiene-3,5-glycol; 3,7-dimethyl-1,6-octadiene-3,5-glycol; 2,6-dimethyl-1,7-octadiene-3,6-glycol; 2,7-dimethyl-1,7-octadiene-3,6-glycol; 3,6-dimethyl-1,7-octadiene-3,6-glycol; 3-vinyl-1-octene-3, the 6-glycol; 2,7-dimethyl-2,4,6-sarohornene-1,8-glycol; 3,7-dimethyl-2,4-octadiene-1,7-glycol; 2,6-dimethyl-2,5-octadiene-1,7-glycol; 3,7-dimethyl-2,5-octadiene-1,7-glycol; 3,7-dimethyl-2,6-octadiene-1,4-glycol (Rosiridol); 2-methyl-2,6-octadiene-1,8-glycol; 3,7-dimethyl-2,7-octadiene-1,4-glycol; 2,6-dimethyl-2,7-octadiene-1,5-glycol; 2,6-dimethyl-2,7-octadiene-1,6-glycol (8-hydroxyl phantol); 2,7-dimethyl-2,7-octadiene-1,6-glycol; The 2-octene-1, the 4-glycol; The 2-octene-1, the 7-glycol; 2-methyl-6-methylene radical-2-octene-1, the 7-glycol; 3,7-dimethyl-3,5-octadiene-1,7-glycol; 2,7-dimethyl-3,5-octadiene-2,7-glycol; 4-methylene radical-3, the 5-ethohexadiol; 2,6-dimethyl-3,7-octadiene-1,6-glycol; 2,7-dimethyl-3,7-octadiene-2,5-glycol; 2,6-dimethyl-3,7-octadiene-2,6-glycol; 4-methyl-3-octene-1, the 5-glycol; 5-methyl-3-octene-1, the 5-glycol; 2,2-dimethyl-4,6-octadiene-1,3-glycol; 2,6-dimethyl-4,7-octadiene-2,3-glycol; 2,6-dimethyl-4,7-octadiene-2,6-glycol; 7-methyl-4-octene-1, the 6-glycol; 2,7-two (methylene radical); The 2-methylene radical-; 2,7-dimethyl-5,7-octadiene-1,4-glycol; 7-methyl-5,7-octadiene-1,4-glycol; The 5-octene-1, the 3-glycol; 7-methyl-6-octene-1, the 3-glycol; 7-methyl-6-octene-1, the 4-glycol; The 6-octene-1, the 5-glycol; 7-methyl-6-octene-1, the 5-glycol; 2-methyl-6-octene-3, the 5-glycol; 4-methyl-6-octene-3, the 5-glycol; 2-methyl-7-octene-1, the 3-glycol; 4-methyl-7-octene-1, the 3-glycol; 7-methyl-7-octene-1, the 3-glycol; The 7-octene-1, the 5-glycol; The 7-octene-1, the 6-glycol; 5-methyl-7-octene-1, the 6-glycol; 2-methyl-6-methylene radical-7-octene-2, the 4-glycol; 7-methyl-7-octene-2, the 5-glycol; 2-methyl-7-octene-3, the 5-glycol; 1-nonene-3, the 5-glycol; 1-nonene-3, the 7-glycol; 3-nonene-2, the 5-glycol; 8-methyl-4,6-nonadiene-1,3-glycol; 4-nonene-2, the 8-glycol; 6,8-nonadiene-1,5-glycol; 7-nonene-2, the 4-glycol; 8-nonene-2, the 4-glycol; 8-nonene-2, the 5-glycol; 1,9-decadiene-3,8-glycol; And/or 1,9-decadiene-4,6-glycol; And
XI. their mixture.
Preferably main solvent content is remained on to making the present composition reach the translucent or transparent minimum level that can realize.The existence of water is for for reaching the transparent required main solvent of these compositions material impact being arranged.Water-content is high more, and is high more for realizing the transparent required main solvent content of product (with respect to softening agent content).Otherwise water-content is few more, and the main solvent (with respect to softening agent) that needs is few more.For example, under the low water content of about 5-15%, the weight ratio of softening agent actives and main solvent is about 55: 45 to about 85: 15, more preferably from about 60: 40 to about 80: 20.Under the water-content of about 15-70%, the weight ratio of softening agent actives and main solvent is preferably about 55: 45 to about 70: 30, more preferably from about 55: 45 to about 70: 30.But under the high water content of about 70-about 80%, the softening agent actives is preferably about 30: 70 to about 55: 45 with the weight of solvent ratio, more preferably from about 35: 65 to about 45: 55.When the water yield was higher, the ratio of softening agent/main solvent also should be higher.
The mixture of above main solvent is superior especially, because one of problem relevant with a large amount of solvents is security.Mixture has reduced the quantity of any existing material.Smell and combustibility also can reduce by using mixture, and especially when one of main solvent was volatility and/or scent of, this was likely for low molecular weight substance.Primary solvent is one or more solvents in confirmed most preferred ClogP scope before this in the preferred mixture.It also is desirable using solvent mixture, and especially when in the preferred main solvent one or more at room temperature were solid, in this situation, mixture was a fluid, or has lower fusing point, thereby has improved the workability of softener composition.
Also find, to replace a part of main solvent of the present invention or main solvent mixture be possible and be desirable with second solvent that itself can not use as main solvent of the present invention or second solvent mixture, as long as still there is the of the present invention suitable main solvent of effective quantity in the fabric softener composition of spissated liquid clear.Effective quantity of main solvent of the present invention, under the situation that at least also has about 15% softening agent actives, about 5% greater than composition at least, be preferably greater than about 7%, more preferably greater than about 10%.Substituting solvent can use with any content, but preferably is substantially equal to or is less than the quantity of the main solvent that is suitable for of the above-mentioned definition that exists in fabric softener composition.
For example, according to the present invention, though 1,4 cyclohexane dimethanol, 1,2-pentanediol, 1, the following hydroxypivalyl hydroxypivalate (claiming HPHP later on) of 3-ethohexadiol and chemical formula is inapplicable solvent:
HO-CH 2-C (CH 3) 2-CH 2-O-CO-C (CH 3) 2-CH 2-OH (CAS#1115-20-4) but these solvents and main solvent are for example with 2,2, and 4-trimethylammonium-1, the mixture of 3-pentanediol also can obtain liquid spissated transparent fabric softener composition.1,4 cyclohexane dimethanol is an ideal, because it has low smell.The major advantage of main solvent is that it provides maximum benefit for the solvent of given weight.Should be appreciated that said " solvent " is meant effect rather than its physical form under assigned temperature of main solvent, because some main solvent is solid at ambient temperature here.F. Ren Xuan component
(A) whitening agent
Premixture of the present invention, particularly finished product dispersion composite also can randomly contain the wetting ability white dyes of some type of 0.005-5% weight of having an appointment, and they also work to suppress dye transfer.If use, preferably contain this fluorescent bleaches of about 0.001-1% weight in the dispersion composite of the present invention.
Can be used for wetting ability white dyes of the present invention is the following compound of structural formula: R wherein 1Be selected from anilino, N-2-two (hydroxyethyl) and NH-2-hydroxyethyl; R 2Be selected from N-2-two (hydroxyethyl), N-2-hydroxyethyl-N-methylamino-, morpholinyl, chlorine and amino; M is a salt-forming cation, as sodium or potassium.
R in above chemical formula 1Be anilino, R 2Be N-2-two (hydroxyethyl), and M is when being positively charged ion such as sodium, whitening agent be 4,4 '-two [(4-anilino-6-(N-2-dihydroxy ethyl)-S-triazine-2-yl) amino]-2,2 '-stilbene disulfonic acid and disodium salt.This special brightener species is sold with the trade name of Tinopal-UNPA-GX  by Ciba-Geigy Corporation.Tinopal-UNPA-GX is the preferred wetting ability white dyes in the dispersion composite that adds when can be used for rinsing of the present invention.
R in above chemical formula 1Be anilino, R 2Be N-2-hydroxyethyl-N-2-methylamino-, and M is when being positively charged ion such as sodium, then whitening agent be 4,4 '-two ((4-anilino-6-(N-2-hydroxyethyl-N-methylamino-)-S-triazine-2-yl) amino)-2,2 '-the stilbene disulfonic acid disodium salt.This special brightener species by Ciba-GeigyCorporation with Tinopal-5BM-GX Trade name sell.
R in following formula 1Be anilino, R 2Be morpholinyl, and M is when being positively charged ion such as sodium, then whitening agent is 4,4 '-two [(4-anilino-6-morpholino-S-triazine-2-yl) amino]-2,2 '-stilbene disulfonic acid, sodium salt.This special whitening agent by Ciba-GeigyCorporation with Tinopal-AMS-GX Trade name sell.
(B) dispersing auxiliary
Dispersion composite of the present invention can randomly contain dispersing auxiliary, for example is selected from those compounds of the cationic quaternary ammonium compound of single-long-chain alkyl, single-long-chain alkyl amine oxide and their mixture, to help to form final dispersion composite.When having described dispersing auxiliary, generally its total content is about 2-25% of composition weight, preferably about 3-17%, and 4-15% more preferably from about, preferably 5-about 13%.These materials or add as the part of REACTIVE SOFTNER raw material (I), or add as isolating component.The total content of dispersing auxiliary comprises any amount that may exist as the part of component (I).(1) monoalkyl cationic type quaternary ammonium compound
When having monoalkyl cationic type quaternary ammonium compound, it is about 25% that its content is generally about 2-of composition weight, and preferably about 3-is about 17%, and more preferably from about 4-about 15%, preferably about 5-is about 13%, and total monoalkyl cationic type quaternary ammonium compound is in effective content range at least.
Can be used for the preferably following quaternary ammonium salt of general formula of this class monoalkyl cationic type quaternary ammonium compound of the present invention:
[R 4N +(R 5) 3] X -Wherein: R 4Be C 8-C 22Alkyl or alkenyl, preferred C 10-C 18Alkyl or alkenyl, more preferably C 10-C 14Or C 16-C 18Alkyl or alkenyl; Each R 5Be C 1-6The alkyl of alkyl or replacement (as hydroxyalkyl), preferred C 1-C 3Alkyl, as methyl (most preferably), ethyl, propyl group etc., benzyl, hydrogen has about 2-20 oxygen ethylene unit, preferably about 2.5-13 oxygen ethylene unit, the preferably polyethoxylated chain of about 3-10 oxygen ethylene unit, and their mixture; X-and front are identical to formula (1) definition.
Particularly preferred dispersing auxiliary is single lauryl trimethyl ammonium chloride and single tallow trimethyl ammonium chloride, and they can be by Witco with Varisoft The trade name of 47l has been bought, and can be by Witco with trade name Varisoft 417 single oil base trimethyl ammonium chlorides of having bought.
R 4Base also can contain groups such as one or more esters, acid amides, ether, amine by one and be connected with azonia, and this connection base is an ideal for the condensability that improves component (1) etc.These linking groups are preferably in about 1-3 carbon atom of nitrogen-atoms.
Monoalkyl cationic type quaternary ammonium compound also comprises C 8-C 22The alkyl cholinesterase.The preferred dispersing auxiliary of this type has following chemical formula:
R 1C (O)-O-CH 2CH 2N +(R) 3X -R wherein 1, R and X -Definition the same.
Highly preferred dispersing auxiliary comprises C 12-C 14Cocoyl cholinesterase and C 16-C 18The tallow cholinesterase.
At United States Patent (USP) 4,840, narrated the single-long-chain alkyl dispersing auxiliary of the suitable biodegradation type that in long-chain, contains ester bond among 738 (Hardy and the Walley, on June 20th, 1989 issued), this patent is quoted as a reference in this article.
When dispersing auxiliary comprises the alkyl cholinesterase, preferably also contain in the dispersion composite a spot of, preferably account for the organic acid of the about 2-5% of composition weight.Narrated organic acid in european patent application 404471 (Machin etc., announce December 27 nineteen ninety, preamble), this article is here quoted as a reference.Organic acid preferably is selected from oxyacetic acid, acetate, citric acid and composition thereof.
The ethoxylation quaternary ammonium compound that can be used as the dispersing auxiliary use comprises ethyl two (polyethoxyethanols) the alkyl ethylsulfuric acid ammonium that has 17 moles of ethylene oxide, and it can be obtained trade name Variquat by Sherex ChemicalCompany 66; Polyoxyethylene glycol (15) dihydroxy ethyl methyl oil base ammonium chloride can be obtained trade name Ethoquad by Akzo 0/25; Polyoxyethylene glycol (15) dihydroxy ethyl methyl cocoyl ammonium chloride can be obtained trade name Ethoquad by Akzo C/25.
Though the major function of dispersing auxiliary is to improve the dispersiveness of ester class softening agent, dispersing auxiliary of the present invention preferably also has some softening character so that promote the softness function of composition.Therefore, dispersion composite of the present invention preferably is substantially free of the ethoxylated non-ionic type dispersing auxiliary of non-nitrogen, and this type of material can reduce the total soft voltinism energy of dispersion composite.
In addition, have only the quaternary ammonium compound of a single long alkyl chain can protect cationic softener not interact with aniorfic surfactant and/or the detergent builder from washing soln, brought in the rinsing liquid.
(2) oxidation amine
Suitable amine oxide comprises and has about 8-22 carbon atom, preferably about 10-18 carbon atom, the more preferably from about alkyl or the hydroxyalkyl part of 8-14 carbon atom, and the amine oxide that is selected from two moieties of the alkyl that contains 1-3 the carbon atom of having an appointment and hydroxyalkyl.
Example comprises dimethyloctylamine oxide, diethyl decyl amine oxide, two (2-hydroxyethyl) decyl amine oxide, the dimethyl dodecyl amine oxide, dipropyl tetradecyl amine oxide, methylethyl hexadecyl amine oxide, dimethyl-2-hydroxyl octadecyl amine oxide and cocounut oil aliphatic alkyl dimethyl oxidation amine.(C) dirt release agent
In the present invention, can add optional dirt release agent, particularly add in the final dispersion composite.The adding of dirt release agent can be to be blended in the pre-composition, is blended in acid/water-bed liquid, and before or after adding ionogen, or after making final composition.Can contain 0% to about 10% with the final softnessization composition of the inventive method preparation, preferably from 0.2% to about 5% dirt release agent.Can regulate the concentration in the premixture, to obtain required ultimate density.This class dirt release agent is polymkeric substance preferably.The polymkeric substance dirt release agent that can be used among the present invention comprises segmented copolymer of terephthalate and polyoxyethylene or polyoxypropylene etc.
Preferred dirt release agent is to have terephthalate and polyoxyethylated segmented copolymer.More particularly, these polymkeric substance are to about 35: 65 ethylene glycol terephthalate and polyoxyethylene terephthalate repeating unit to constitute at 25: 75 by mol ratio, and described polyoxyethylene terephthalate contains the polyoxyethylene blocks of molecular weight for about 300-about 2000.The molecular weight ranges of this polymkeric substance dirt release agent is about 5000 to 55000.
But another kind of preferred polymkeric substance dirt release agent is a kind of polyester with crystallization of ethylene glycol terephthalate repeating unit, the polyoxyethylene glycol that wherein contains the ethylene glycol terephthalate unit of about 15% weight of the 10-that has an appointment and about 50% weight of the about 10-polyoxyethylene terephthalate unit of formation of deriving from the about 300-of molecular weight about 6000, but ethylene glycol terephthalate unit and the unitary mol ratio of polyoxyethylene terephthalate are 2: 1 to 6: 1 in the polymkeric substance of crystallization.The example of this polymkeric substance comprises commercial goods Zelcon 4780 (from Dupont) and Milease T (from ICI).
Highly preferred dirt release agent is the following polymkeric substance of general formula:
Figure A9719794000401
Wherein each X can be suitable capping group, and each X is selected from H usually, contains the alkyl or the acyl group of about 4 carbon atoms of about 1-.The selection of p will be considered water solubility, generally is for about 6-is about 113, is preferably about 20-about 50.U is crucial for preparation in having the liquid composition of relative high ionic strength.Wherein u should be seldom greater than 10 material.In addition, should have 20% at least, preferably have 40% wherein u at least is from about 3 to about 5 material.
R 14Part is 1 basically, the 4-phenylen moiety.Terminology used here " R 14Part is 1 basically, the 4-phenylen moiety " be meant the R in the compound 14Part is fully by 1, and the 4-phenylen moiety constitutes, and is perhaps partly replaced by other arylidene or alkyl arylene part, alkylene moiety, alkenylene part or their mixture.Can partly replace 1, the arylidene and the alkyl arylene of 4-phenylene partly comprise: 1, and 3-phenylene, 1,2-phenylene, 1,8-naphthylidene, 1,4-naphthylidene, 2,2-diphenylene, 4,4-diphenylene and their mixture.The alkylidene group and the alkenylene that can partly replace partly comprise: propylene, tetramethylene, pentamethylene, hexamethylene, 1, the inferior heptyl of 7-, octamethylene, 1,4-cyclohexylidene and their mixture.
For R 14Part, with non-1, the degree that the 4-phenylene group partly replaces should make the dirt character of freeing of compound not be subjected to any disadvantageous effect largely.In general, admissible part substitution value depends on the backbone length of compound, that is, long main chain 1, the 4-phenylen moiety can have bigger substitution value.Usually, R wherein 14It is about 100%1 to contain the 50-that has an appointment, and the compound of 4-phenylen moiety (0% to about 50% non-1,4-phenylen moiety) has enough dirt activity of freeing.For example, the polyester made from m-phthalic acid of 40: 60 mol ratios (1, the 3-phenylene) and terephthalic acid (1, the 4-phenylene) according to the present invention has enough dirt activity of freeing.But because the most of polyester that use in the fiber manufacturing contain the ethylene glycol terephthalate unit, so normal hope reduces with 1, the degree that the group outside the 4-phenylene partly replaces is active to obtain optimum solution decontamination dirt.Preferably, R 14Part complete (that is, containing 100%) is by 1, and the 4-phenylen moiety constitutes, that is, and and each R 14Part is 1, the 4-phenylene.
For R 15Part, the suitable ethylidene or the ethylidene of replacement partly comprise ethylidene, propylene, 1,2-butylidene, 1,2-hexylidene, 3-methoxyl group-propylene and their mixture.Preferably, R 15Part is ethylidene, propylene or its mixture basically.The ethylidene part that comprises big percentage composition can be improved the activity that compound is freed dirt.Surprisingly, comprise the water solubility that can improve compound than the propylene part of big percentage composition.
Therefore, using propylene part or similar branching equivalent is desired for mix any most dirt release agent in the fabric softener composition of liquid state.Preferably, propylene partly is about 75-100%.
It is about 6 that each p value is at least, and preferably is at least about 10.Each n value is generally about 12-about 113.Generally, each p value is about 12-about 43.
Illustrating more completely in following document relevant for dirt release agent: United States Patent (USP) 4,661,267 (Decker, Konig, Straathof and Gosselink, on April 28th, 1987 issued); 4,711,730 (Gosselink and Diehl, on December 8th, 1987 issued); 4,749,596 (Evans, Huntington, Stewart, Wolf and Zimmerer, on June 7th, 1988 issued); 4,818,569 (on April 4th, 1989 issued for Trinh, Gosselink and Rattinger); 4,877,896 (on October 31st, 1989 issued for Maldonado, Trinh and Gosselink); 4,956,447 (Gosselink etc., issue September 11 nineteen ninety) and 4,976,879 (issue December 11 nineteen ninety for Maldonado, Trinh and Gosselink).These patents all are cited as a reference in this article.
These dirt release agents also can play the soap scum dispersion agent.(D) soap scum dispersion agent
In the present invention, pre-composition can with a kind of soap scum dispersant that is different from the optional adding of dirt release agent, and be heated to each component fusing point or higher temperature.The soap scum dispersion agent is the desirable component of final dispersion composition of the present invention.
Preferred soap scum dispersion agent is that the lyophobic dust by the height ethoxylation forms.These lyophobic dusts can be Fatty Alcohol(C12-C14 and C12-C18), lipid acid, aliphatic amide, fatty amide, amine oxide, quaternary ammonium compound, or are used for forming the hydrophobic parts of soil release polymers.Preferred soap scum dispersion agent is the height ethoxylation, and for example each molecule on average has and surpasses approximately 17, and preferably more than about 25, more preferably more than about 40 oxyethane moles, it is about 97% that polyoxyethylene partly accounts for about 76-of total molecular weight, preferably about 81-about 94%.
The content of soap scum dispersion agent is enough to make under working conditions soap scum to remain on acceptable, the unnoticed level preferably of human consumer, but is not enough to that softnessization is had disadvantageous effect.For some purpose, wish not exist soap scum.According to the quantity of anionic that in the washing stage of typical laundry processes, uses or non-ionic detergent etc., add the efficient and the water hardness of the rinse stage before the dispersion composite of the present invention, the quantity of negatively charged ion of carrying secretly in fabric (laundry) or nonionic detergent tensio-active agent and detergent builder (especially phosphoric acid salt and zeolite) can change.Usually, should use the soap scum dispersion agent of minimum quantity to avoid disadvantageous effect to soft voltinism matter.Generally, the requirement of soap scum dispersion agent is at least the about 2% of softening agent active matter content, preferably is at least about 4% (for farthest avoiding soap scum, at least 6%, preferably at least 10%).But under about 10% (with respect to softening agent material) or higher content, the softness effect of product has the danger of reduction, especially contains in fabric under the situation of a high proportion of nonionogenic tenside that absorbs during the washing operation.
Preferred soap scum dispersion agent is: Brij700 , VaronicU-250 , GenapolT-500 , GenapolT-800 , PlurafacA-79 And Neodol25-50
(E) sterilant
The example of the sterilant that uses in premixture of the present invention and/or final dispersion composition comprises glutaraldehyde, formaldehyde, 2-bromo-2-nitropropane-1, and (Inolex Chemical sells the 3-glycol, is positioned at Philadelphia, Binzhou, trade name Bronopol ), and mixture (the Rohm ﹠amp of 5-chloro-2-methyl-4-isothiazoline-3-ketone and 2-methyl-4-isothiazoline-3-ketone; Haas Company, trade name KathonCG/ICP ).The general sterilant content that uses in dispersion composite of the present invention is about 1-1000ppm (weight).
(F) sequestrant
Final dispersion composition of the present invention and method can randomly be used one or more copper and/or nickel sequestrant.This water-soluble chelator can be selected from the aromatic chelating agent of aminocarboxylate, amino phosphonates do, multifunctional replacement and their mixture, and they are all with the definition of back.The whiteness of fabric and/or brightness is because this sequestrant and improve greatly or recover, and disperse and transparent composition in each Stability of Substance be improved, particularly when sequestrant in the course of processing and fabric sofetening actives exist simultaneously.
The aminocarboxylate that can be used as sequestrant of the present invention comprises edetate (EDTA), N-hydroxyethyl-ethylenediamine triacetate, nitrilotriacetic acid(NTA) salt (NTA), ethylenediamine tetrapropionic acid(EDTP) salt, quadrol-N, N '-two glutaminate, 2-hydroxyl propylene diamine-N, N '-two succinate, triethylenetetraaminehexaacetic acid salt, diethylentriamine pentacetate (DETPA) and ethanol Diglycocol ester comprise their water-soluble salt, an alkali metal salt for example, ammonium salt of ammonium salt and replacement and composition thereof.
When allowing low total phosphorous to exist in the washing composition dispersion composite at least, amino phosphonates do also is adapted at using as sequestrant in the dispersion composite of the present invention, this comprises ethylenediamine tetraacetic (methylene phosphonic acid salt), diethylenetriamine-N, N, N ', N "; N "-five (methane phosphonic acid) salt (DETMP) and 1-hydroxyl ethane-1,1-diphosphonate (HEDP).Preferably, these amino phosphonates do do not contain alkyl or the alkenyl more than 6 carbon atoms.
The consumption of sequestrant is generally about 2ppm to about 25ppm in rinse stage, soak time from 1 minute until several hours.
The preferred EDDS (being also referred to as quadrol-N, N '-two succinate) that the present invention uses is the material of describing in the above-mentioned United States Patent (USP) 4,704,233, has following chemical formula (listing free acid form):
Figure A9719794000431
As described in this patent, EDDS can prepare with maleic anhydride and quadrol.(S, S) isomer of preferred biodegradable EDDS can pass through L-aspartic acid and glycol dibromide prepared in reaction.EDDS is that than the superior part of other sequestrant it is all effective to two kinds of positively charged ions of chelating copper and mickel, can biodegradable form obtain, and not phosphorous.The EDDS that uses as sequestrant among the present invention is generally its salt form, that is, one or more in four acidic hydrogens are replaced by water-soluble cationic M (for example sodium, potassium, ammonium, triethanol ammonium etc.).As previously mentioned, the EDDS sequestrant usually also with the consumption use of about 2ppm to about 25ppm, soaked 1 minute to several hours in rinse cycle.Under certain pH, EDDS preferably is used in combination with zinc cation.
As seen by above-mentioned, a very big class sequestrant can be used for the present invention.Really, simple multi-carboxylate and Citrate trianion, hydroxyl two succinates etc. also can use, though these sequestrants are effective not as aminocarboxylate and phosphonate by weight.Therefore, consider different chelating effectiveness degree, can regulate dosage level.Sequestrant to be advisable at least about 5, preferably is at least about 7 to the stability constant (complete Ionized sequestrant) of cupric ion among the present invention.Generally, it is about 10% that sequestrant constitutes about 0.5-of dispersion composite weight of the present invention, and more preferably from about 0.75-about 5%.Preferred sequestrant comprises DETMP, DETPA, NTA, EDDS and their mixture.Multi-carboxylate's sequestrant such as ethylenediamine tetraacetic acid (EDTA) and diethylene triaminepentaacetic acid(DTPA) are preferred.(G) Ren Xuan viscosity/dispersity conditioning agent
The denseer final dispersion composition that the present invention contains unsaturated diester quat can be prepared into stabilising system and needn't add the concentration auxiliary agent.But dispersion composite of the present invention may need organic and/or inorganic concentration auxiliary agent to reach higher concentration and/or to satisfy higher stability criterion, and this depends on other component.May or preferably need these normally concentration auxiliary agents of viscosity modifier, so that guarantee when using the softening agent actives of certain content stability under extreme conditions.The surfactant concentration auxiliary agent is selected from usually: the alkyl cats product of (1) single long-chain; (2) nonionogenic tenside; (3) oxidation amine; (4) lipid acid; (5) their mixture.These auxiliary agents are at P﹠amp; In the application 08/461,207 of G pending trial (application on June 5 nineteen ninety-five, Wahl etc.) explanation is arranged, particularly walk to the 20th page of 12 row at the 14th page 12, this article is quoted as a reference in this article.(H) other optional component that adds
Final dispersion composition of the present invention can be included in normally used optional components in the textile treatment dispersion composite, for example: tinting material, sanitas, tensio-active agent, sanforzing agent, the fabric stiffener, spotting agent, sterilant, mycocide, antioxidant such as Yoshinox BHT, anticorrosive agent etc.
Particularly preferred component comprises that as above at explanation described water-soluble calcium and/or magnesium compound during transparent composition, they can provide additional stability.Chloride salt is preferred, but acetate, nitrate etc. also can use.The consumption of calcium salt and/or magnesium salts is about 2% for about 0-, and preferably about 0.05-is about 0.5%, and more preferably from about 0.1-about 0.25%.These materials preferably add water and/or the acid (water-bed thing) that is used for preparing the final dispersion composition, to help to regulate final viscosity.
The present invention also comprises the component that other is compatible, is included in disclosed compound in the following patent application: the application 08/372,068 of pending trial (submit to January 12 nineteen ninety-five, people such as Rusche); 08/372,490 (submit to January 12 nineteen ninety-five, people such as Shaw); With 08/277,558 (on July 19th, 1994 submitted to, people such as Hartman).Above-mentioned document is quoted as a reference in this article.
Below unrestricted example exemplify explanation the present invention, wherein all numerical value is according to normal empirical approximation.Prepare composition by the softening agent actives of preheating is added in " the water-bed thing " that comprises water and accessory constituent, but be more preferably at room temperature, particularly after actives and spices pre-mixing.The preparation of biodegradable fabric sofetening actives
A kind of preferred triglyceride level source that can be used for preparing fabric sofetening composition of the present invention is a Canola Oil.Canola Oil is to have the suitably mixture of the triglyceride level of chain length distribution and corresponding acyl group degree of unsaturation.Because of the reason of several respects, Canola Oil is a desirable especially initiator in the inventive method.Particularly, the obviously a high proportion of acyl group that contains 18 carbon atoms is arranged in the chain length of each acyl group natural distributed, avoided thus when using other C 18The extra-expense that the lipid acid commercial source is born during as initiator.
The triglyceride level initiator can be partially hydrogenated, if need, with two undersaturated and triunsaturated acyl groups, those acyl groups that particularly contain 18 carbon atoms change into their monounsaturated counterparts.Usually wish to reduce the hydrogenation of single unsaturated acyl group, even avoid hydrogenation fully.Can obtain saturated acyl group by common saturated thing source, and mix with undersaturated acyl group.In some acyl group mixtures that are suitable for, unsaturated C 18Acyl group is no more than 10% with respect to its saturated counterpart and is hydrogenated.For some product, two undersaturated and triunsaturated C 18The hydrogenation of acyl group is preferably maximum, meets the saturated C of minimum formation 18Group.For example, three unsaturated acyl groups can be hydrogenated fully, and two unsaturated acyl groups are not realized complete hydrogenation.
The hydrogenation of the maximum triglyceride level initiator of single unsaturated acyl group can easily be realized by the proper equilibrium that keeps the hydrogenation condition.The effect of the technique change in the triglyceride level hydrogenation and these variations of adjustment is that those skilled in the art very know usually.Generally, the hydrogenation of triglyceride level initiator can more preferably be carried out in about 185 ℃ of-195 ℃ of slightly narrow scopes about 170 ℃-205 ℃ (in general).Other tangible technique change is the pressure of hydrogen in the hydrogenation reactor.Generally, this pressure should be maintained at about 2-20 pound/inch 2(in general), more preferably at about 5-15 pound/inch 2
In these parameter areas, under the situation of having considered these parameter effects especially, can carry out hydrogenation.Lower hydrogen pressure can allow to control to a greater degree reaction in the reactor, particularly for its selectivity." selectivity " meaning is the hydrogenation of two unsaturated acyl groups and three unsaturated acyl groups, and does not have the hydrogenation of the unsaturated acyl group of over-drastic list.On the other hand, higher hydrogen pressure provides lower selectivity.Selectivity is desirable in some instances.
Higher hydrogenation temperature is relevant with the bigger selectivity of hydrogenation speed and hydrogenation faster.On the contrary, lower hydrogenation temperature is relevant with lower selectivity (that is, having increased the hydrogenation of single unsaturated group), and is particularly relevant with general low hydrogenation speed.
These consider also to want the consideration of balance stereochemistry aspect.More particularly, the existence of degree of unsaturation can cause acyl group to form different steric isomers through hydrogenation in the acyl group.Two kinds of possible stereoisomerism configurations of unsaturated fatty acyl group are known as " cis " and " trans " type.It is preferred having the cis type, because its relevant than low melting point with the finished product, so product has bigger flowability.Canola Oil is that another reason of particularly preferred triglyceride level initiator is, as naturally occurring material, the acyl group performance that exists in this triglyceride level only is the cis form.In hydrogenation, also to become trans structural changes trend by cis relevant with reducing acyl group for higher hydrogen-pressure.In addition, for some reason, though higher hydrogenation temperature is favourable, it also with cis insatiable hunger form and relevant to the higher conversion of trans type.By suitably controlling hydroconversion condition, so that obtain the stereochemical structure of selectivity and control product, the product that can obtain having satisfied character.
Hydrogenation is to carry out in the presence of the hydrogenation catalyst that is fit to.This catalyzer is known, and commercial buying.They generally include generally nickel, palladium, ruthenium or the platinum on suitable support of the catalyst.The catalyzer that is fit to is the nickel-base catalyst of being sold with commodity register name " N-545 " by Engelhard.
In a kind of technique change, hydrogenation proceeds to two unsaturated and being hydrogenated to greatest extent of three degrees of unsaturation in the triglyceride level product and the formation of saturated acyl group reduces to the sink node of minimum degree.Process near the hydrogenation reaction of terminal point can easily be monitored by the iodine number of periodic measurement reactive material.Along with the carrying out of hydrogenation, iodine number reduces.For example, when iodine number reaches about 95 the time, hydrogenation reaction can stop.
Other requirement of hydrogenation reaction is known, for example the type of reactor, keep temperature required cooling apparatus, provide the whipping device of the abundant contact between triglyceride level and hydrogen and the catalyzer etc. effectively.
The general hydrolysis of triglyceride level that contains required acyl group obtains required fatty acyl group, for example corresponding lipid acid.That is, three ester bonds in the triglyceride level disconnect, thus acyl group add hydrogen mixture change into acyl group have identical chain length distribution and have the saturated and degree of unsaturation distribution that obtains by hydrogenation reaction the mixture of lipid acid.And other method comprises the use transesterification method to form for example methyl ester, and it is used for the esterification alkanolamine then, and is described above.
Hydrolysis can be carried out under any suitable condition known in the art, triglyceride hydrolysis is become their fatty acid component.Generally, triglyceride level reacts with high-temperature steam in reactor, and wherein lipid acid is isolated from glycerine, and vapor condensation forms the aqueous solution of glycerine and removes this solution then.
The mixture of the lipid acid that obtains at hydrolysing step is used for for example formula R-N (CH of esterification then 2CH 2OH) 2One or more amine, wherein R definition as above, methyl preferably.In addition, can obtain required esterification by transesterification with corresponding fatty acyl group ester such as methyl ester.
Esterification can be carried out under the enzymatic synthesis condition of routine, as long as tart catalyzer and taking-up byproduct of reaction water of condensation.Preferably, a spot of, the Hypophosporous Acid, 50 (HPPA) of the general about reactant of as many as (being acid and amine) 1.0% weight can add in the esterification reaction mixture.HPPA is considered to can catalyzed reaction and protection or even improve the color of the product that obtains in this reaction.
In one embodiment of the present invention, allow esterification to carry out fully, so that lipid acid two esterifications that all amine quilts that exist produce in hydrolysing step in advance.But, wish sometimes to produce a spot of corresponding monoesters, as discussed above.
The mixture of the mixture of diester or diester and monoesters component according to circumstances can be by quaternized.Quaternizedly under condition that common experienced technical staff in the art knows and reactant, carry out.Quaternizing agent has formula RX, preferably methyl, benzyl or ethyl of R wherein, and X is a negatively charged ion as hereinbefore defined.Preferred RX is methyl chloride, benzyl chloride, methyl-sulfate or ethyl sulfate.This quaternized step has produced the mixture of biodegradable fabric sofetening actives as described above.
It would be desirable that compound used herein is the impurity of wishing invariably relatively.Therefore, need process fatty acid source with known several different methods of removing this class impurity, for example under the normal atmosphere of hypoxemia, process, separate unwanted material by filtration, absorption etc., chemical modification before control hydrogenation and/or oxidation and/or afterwards, still, the purity of material is not a part of content of the present invention, the present invention is equally applicable to the material of low-purity, and the coordination between purity and the expense is to adjust according to human consumer's needs and requirement.
Further specify mixture synthetic of the biodegradable fabric sofetening actives of the present invention with following synthetic embodiment.Provide these synthetic embodiment purposes only to be explanation.Synthetic embodiment A compound
The nickel hydrogenation catalyst (Engelhard, " N-545 ") that the merchant that about 1300 gram Canola Oils and about 6.5 grams are equivalent to about 0.13% weight Ni sells is placed in the hydrogenator that agitator is housed.This reactor is sealed and find time.Content is heated to about 170 ℃, and hydrogen is fed in the reactor.Keep the stirring under the 450rpm in during entire reaction.After about 10 minutes, the temperature in the reactor is about 191 ℃, and hydrogen-pressure is about 11 pounds/inch 2This temperature is maintained at about 190 ℃.After about 127 minutes when beginning to feed hydrogen, hydrogen-pressure is about 10 pounds/inch 2Take out the reactant sample, find that iodine number is about 78.0, cis: trans ratio is about 1.098.Under about 190 ℃ in addition after about 20 minutes, hydrogen-pressure is about 9.8 pounds/inch 2Stop feeding hydrogen, stir the material in the cooling reactor.The iodine number of final reacting product is about 74.5, and cis: trans ratio is about 1.35.
The product that taking-up forms in reactor also filters.Its cloud point is about 22.2 ℃.The sample that takes out when being determined at about 127 minutes and the acyl substituent of the finished product chain length distribution, as shown in table 1, wherein " saturated " meaning is saturated, " list " and " two " looks like is respectively monounsaturated and two undersaturated.
Table 1
About percentage ratio (mole)
127 minutes products of long-chain sample
C14-saturated 0.1 0.1
C18-saturated 4.7 4.6
C16-single 0.4 0.4
C18-saturated 8.9 13.25
C18-single 77.0 73.8
C18-2 4.5 3.1
C20-saturated 0.7 0.75
C20-single 2.1 2.0
Other 1.6 2.0 synthetic Embodiment B compound
About 1300 gram Canola Oils and about 5.2 gram Engelhard " N-545 " nickel hydrogenation catalysts are put into the hydrogenator that agitator is housed.This reactor is sealed and find time.Content is heated to about 175 ℃, and hydrogen is fed in the reactor.Keep the stirring under about 450rpm in during entire reaction.After about 5 minutes, the temperature in the reactor is about 190 ℃, and hydrogen-pressure is about 7 pounds/inch 2This temperature is maintained at about 190 ℃.After about 125 minutes when beginning to feed hydrogen, hydrogen-pressure is about 7 pounds/inch 2Take out the reactant sample, find that iodine number is about 85.4.Under about 190 ℃ in addition after about 20 minutes, hydrogen-pressure is about 6 pounds/inch 2Stop feeding hydrogen, stir the material in the cooling reactor.The iodine number of final reacting product is about 80.0.The product that taking-up forms in reactor also filters, and its cloud point is about 18.6 ℃.Synthetic Embodiment C compound
About 1300 gram Canola Oils and about 2.9 gram Engelhard " N-545 " nickel hydrogenation catalysts are put into the hydrogenator that agitator is housed.This reactor is sealed and find time.Content is heated to about 180 ℃, and hydrogen is fed in the reactor.Keep the stirring under about 450rpm in during entire reaction.After about 5 minutes, the temperature in the reactor is about 192 ℃, and hydrogen-pressure is about 10 pounds/inch 2This temperature is maintained at about 190 ± 3 ℃.After about 105 minutes when beginning to feed hydrogen, hydrogen-pressure is about 10 pounds/inch 2Take out the reactant sample, find that iodine number is about 85.5.Under about 190 ℃ in addition after about 20 minutes, hydrogen-pressure is about 10 pounds/inch 2Stop feeding hydrogen, stir the material in the cooling reactor.The iodine number of final reacting product is about 82.4.The product that taking-up forms in reactor also filters, and its cloud point is about 17.2 ℃.Synthetic embodiment D compound
About 1300 gram Canola Oils and about 1.4 gram Engelhard " N-545 " nickel hydrogenation catalysts are put into the hydrogenator that agitator is housed.This reactor is sealed and find time.Content is heated to about 180 ℃, and hydrogen is fed in the reactor.After about 5 minutes, the temperature in the reactor is about 191 ℃, and hydrogen-pressure is about 10 pounds/inch 2This temperature is maintained at about 190+ ± 3 ℃.After about 100 minutes when beginning to feed hydrogen, hydrogen-pressure is about 10 pounds/inch 2Take out the reactant sample, find that iodine number is about 95.4.Under about 190 ℃ in addition after about 20 minutes, hydrogen-pressure is about 10 pounds/inch 2Stop feeding hydrogen, stir the material in the cooling reactor.The iodine number of final reacting product is about 2.3.The product that taking-up forms in reactor also filters, and its cloud point is about 34 ℃.Synthetic embodiment E compound
About 1300 gram Canola Oils and about 1.3 gram Engelhard " N-545 " nickel hydrogenation catalysts are put into the hydrogenator that agitator is housed.This reactor is sealed and find time.Content is heated to about 190 ℃, with hydrogen feed in the reactor to hydrogen-pressure be about 5 pounds/inch 2After about 3 minutes when beginning to feed hydrogen, take out the reactant sample, find that iodine number is about 98.Cut off hydrogenation, add the identical catalyzer of about in addition 0.7 gram, recover reaction conditions down at about 190 ℃, other carried out about 1 hour.Stop feeding hydrogen then, stir the material in the cooling reactor.The iodine number of final reacting product is about 89.9.The product that taking-up forms in reactor also filters, and its cloud point is about 16.0 ℃.Synthetic embodiment F compound
About 1300 gram Canola Oils and about 2.0 gram Engelhard " N-545 " nickel hydrogenation catalysts are put into the hydrogenator that agitator is housed.This reactor is sealed and find time.Content is heated to about 190 ℃, with hydrogen feed in the reactor to hydrogen-pressure be about 5 pounds/inch 2Keep the stirring under about 420rpm between the reaction period of whole feeding hydrogen.After about 130 minutes when beginning to feed hydrogen, stop feeding hydrogen, stir the material in the cooling reactor.The iodine number of final reacting product is about 96.4.The product that taking-up forms in reactor also filters, and its cloud point is about 11.2 ℃.Synthetic embodiment G compound
The mixture of the about 1200 gram winterized stearin that obtained by synthetic embodiment F and about 200 gram winterized stearin of being obtained by synthetic embodiment A is at about 600 pounds/inch 2Down with 250 ℃ of steam by steam: oilyly be hydrolyzed three times about 2.5 hours for about 1.2 (by weight).Remove the isolated aqueous solution that contains glycerine.
The mixture of resulting lipid acid is by about altogether 150 minutes of vacuum distilling, and wherein the temperature of still rises to about 238 ℃ gradually from about 200 ℃, and head temperature rises to about 197 ℃ gradually from about 175 ℃.Keep the vacuum tightness under about 0.3-0.6mm.
The iodine number of the resulting fatty acid product of vacuum distilling is about 99.1, and amine value (AV) is about 197.6, and saponification value (SAP) is about 198.6.Synthetic embodiment H compound
The aqueous solution of HPPA of about 50% weight of mixtures, about 194.4 gram MDEA (methyldiethanolamine), about 2 gram BHT (butylated hydroxytoluene) and about 1 gram of the about 800 gram lipid acid that obtained by Canola Oil by above-mentioned steps are placed in the still bottom the distillation column.Make nitrogen gas stream pass through pillar.Still preheater is to begin distillation under about 150 ℃ in the still temperature, and head temperature is about 102 ℃.In first hour, mixture temperature rises to about 193 ℃, and in ensuing about 4 hours, temperature rises to about 202 ℃ gradually then.In first hour, head temperature rises to about 107 ℃, in ensuing about 4 hours, drops to about 62 ℃ gradually then.Product in the still is cooled then, reclaims and analyzes.Contain the 3% weight MDEA that has an appointment in the distillment, about 51 gram water, presenting total amine value (TAV) is about 0.5.Total amine value (TAV) of the product that keeps in still is about 93.3.Synthetic embodiment I compound
The about 900 gram products that obtain by synthetic embodiment H, about 158 gram ethanol, about 0.3 gram ADPA (sequestrant is used for stable color for 1-hydroxyl ethane-1,1-di 2 ethylhexyl phosphonic acid), about 0.15 gram kilfoam and be about 43 pounds/inch to produce first pressing 2The methyl chloride of q.s be blended in the sealed vessel.After about 7 minutes, temperature is about 106 ℃, and pressure is about 84 pounds/inch 2Inner material was maintained at about 105 ± 1 ℃ times about 3-5 hour then, made pressure be maintained at about 57 ± 2 pounds/inch by adding methyl chloride simultaneously 2Reactor is communicated with atmosphere, and inner material is cooled to about 95 ℃.Use about altogether 110 gram methyl chlorides.Take out product then, on rotatory evaporator at about 65 ℃ of following strippings.The content of diester is about 75.9% in this product, and the content of monoesters is about 11.4%.Embodiment 1-4 component embodiment 1 embodiment 2 embodiment 3 embodiment 4
Weight % weight % weight % weight %DEQA 1(17.7 23.5 30.6 30.685% activess in ethanol) spices 0.8 1 1.35-Tenox6 0.02 0.03 0.04 0.04CaCl 2The method of (25% solution) 1.2 1.5 2 2HCl 1N 0.17 0.23 0.30 0.30 distillation water balance balance balance balance embodiment 1-3
The composition that at room temperature prepares embodiment 1-3 by the following method: 1. preparation contains the water-bed thing of HCl.2. separately with spices and Tenox6 RAntioxidant is sneaked in the diester softening agent actives.3. the mixture with the diester actives mixes with water-bed thing.4. in an about semiosis that adds diester, add about 10-20%CaCl 2Solution.5. after adding diester, add remaining CaCl 2Solution mixes.Embodiment 5-8 component embodiment 1 embodiment 2 embodiment 3 embodiment 4
Weight % weight % weight % weight %DEQA 5(17.7 23.5 30.6 30.685% activess in ethanol) spices 0.8 1 1.35-Tenox6 0.02 0.03 0.04 0.04CaCl 2The method of (25% solution) 1.2 1.5 2 2HCl 1N 0.17 0.23 0.30 0.30 distillation water balance balance balance balance embodiment 4-6
The preparation of compositions of embodiment 5-8 is similar to embodiment 1-4, just uses DEQA 5Replace DEQA 1
The composition of embodiment 1-8 has good viscosity.When being placed on indoor about 3 days of about 0 (approximately-18 ℃) weighing apparatus fixed temperature, they are frozen.After at room temperature thawing, these compositions revert to fluid and have good viscosity.Comparative example 9-12
The preparation of compositions of comparative example 9-12 is similar to embodiment 1-4, and just (a) uses DEQA 11(by hydrogenant tallow fatty acid slightly preparation) replacement DEQA 1, (b) the softening agent actives need be heated fusion under about 75 ℃ before adding water-bed thing, also was preheated to about 75 ℃, (c) need be more than about 50% CaCl 2, at last spices is added in the refrigerative final composition, to avoid the degraded of spices with excellent adhering that product is provided with (d).The composition of embodiment 9-12 has good viscosity when being cooled to room temperature after the preparation.But, after when being placed on indoor about 3 days of about 0 (approximately-18 ℃) weighing apparatus fixed temperature, being frozen, at room temperature thawing then, these compositions do not recover, and still keep denseness or have agglomerating consistence.Embodiment 13-14 component embodiment 13 embodiment 14
Weight % weight %DEQA 8(85% 30.6-actives in ethanol) DEQA 9(85%-30.6 actives in ethanol) spices 1.35 1.35Tenox6 0.04 0.04CaCl 2(25% solution) 2 2HCl 1N 0.30 0.30 distillation water balance balance embodiment 13-14
Embodiment 13 and 14 preparation of compositions are similar to embodiment 3, just use DEQA 8And DEQA 9Replace DEQA 1Embodiment 15-19 component embodiment 15 embodiment 16
Weight % weight %DEQA 10(20.8-85% activess in ethanol) DEQA 11(-20.885% actives in ethanol) spices 1.35 1.35Tenox6 0.04 0.04CaCl 2(25% solution) 2 2HCl 1N 0.30 0.30 distillation water balance balance embodiment 20-22 component embodiment 20 embodiment 21 embodiment 22
Weight % weight % weight % Canola Oil 26.0 42.5 52.0DEQA (100%) ethanol 2.3 3.8 4.6 hexylene glycols 2.3 3.8 4.6TMPD *15.0 22.0 22.01,4-cyclohexanedimethanols, 5.0 8.0 8.0HCl (1N), 0.25 0.40 0.50 spices, 1.25 1.25 2.50DEPA *0.01 (1.5%) 0.02 0.02 0.02 pair of ionized water 47.82 18.17 5.77 of 0.01 0.01 card pine *2,2,4-trimethylammonium-1,3-pentanediol *Diethylene triaminepentaacetic acid(DTPA)
In order to obtain good phase stability, low temperature phase stability particularly, the part by weight scope of TMPD and 1,4 cyclohexane dimethanol is preferably about 80: about 50: 50 of 20-, more preferably from about 75: 25.

Claims (9)

1. be selected from following biodegradable softening agent actives: the compound of (1) following formula: [ ( R ) 4 - m - N ( + ) - [ ( C H 2 ) n - Y - R 1 ] m ] X ( - ) - - - - ( 1 ) Wherein each R substituting group is short chain C 1-C 6Alkyl or hydroxyalkyl, benzyl or their mixture; Each m is 2 or 3; Each n is from 1 to about 4; Each Y is-O-(O) C-or-C (O)-O-; Each R 1Be the alkyl of alkyl or replacement, each R 1In the carbonatoms summation, when Y be-to add 1 during O-(O) C-be C 12-C 22R 1The average iodine number of the maternal fatty acid of group is about 60-about 140; Gegenion X wherein -Be any negatively charged ion compatible with softening agent; The content that contains the softening agent actives of unsaturated alkylene group be existing total softening agent actives weight at least about 3%.(2) have the softening agent of following formula:
Figure A9719794000022
Wherein each Y, R, R 1And X (-)Definition the same; (3) their mixture.
2. the softening agent actives of claim 1, it is selected from following: the compound of (1) following formula: [ ( R ) 4 - m - N ( + ) - [ ( C H 2 ) n - Y - R 1 ] m ] X ( - ) - - - - - - ( 1 ) Wherein each R substituting group is C 1-C 3Alkyl or hydroxyalkyl, or their mixture; Each m is 2 or 3; Each n is from 1 to about 4; Each Y is-O-(O) C-; R 1It is C that middle carbonatoms summation adds 1 14-C 20This R 1The average iodine number of the maternal fatty acid of group is about 70-about 130; Gegenion X wherein -Be chlorine; The total content of many unsaturated activess is at least about 5%.(2) have the softening agent of following formula: Wherein each Y, R, R 1And X (-)Definition the same; (3) their mixture.
3. the softening agent actives of claim 2, it has following formula: [ ( R ) 4 - m - N ( + ) - [ ( C H 2 ) n - Y - R 1 ] m ] X ( - ) - - - - - - ( 1 ) Wherein each R substituting group is C 1-C 3Alkyl or hydroxyalkyl, or their mixture; Each m is 2; N is 2; This R 1The average iodine number of the maternal fatty acid of group is about 80-about 115; Cis/trans ratios is about 1: about 50: 1 of 1-; With the total content of how unsaturated actives be at least about 10%.
4. the softening agent actives of claim 1, wherein the softening agent actives comprises the monoester compound of as many as about 20%, and wherein m is 2, one YR 1Be H or-C (O) OH.
5. transparent water base fabric softener composition, it comprises: A. presses composition weight meter, the biodegradable fabric softener active matter of about 2%-80%, it is selected from:
1. the softening agent that has following formula: [ ( R ) 4 - m - N ( + ) - [ ( C H 2 ) n - Y - R 1 ] m ] X ( - ) - - - - - - ( 1 ) Wherein each R substituting group is short chain C 1-C 6Alkyl or hydroxyalkyl; Each m is 2 or 3; Each n is from 1 to about 4; Each Y is-O-(O) C-or-C (O)-O-; Each R 1In the carbonatoms summation, when Y be-to add 1 during O-(O) C-be C 12-C 22Each R 1Be the alkyl of alkyl or replacement, the content that contains the softening agent actives of unsaturated alkylene group be existing total softening agent actives weight at least about 3%; Gegenion X-wherein can be any negatively charged ion compatible with softening agent;
2. the softening agent that has following formula: Wherein each Y, R, R 1And X (-)Definition the same; With
3. their mixture.B. by the weight of composition, be less than the main solvent of the ClogP value of about 40% weight for about 0.15-0.64.
6. wherein there is the said fabric softener active matter (I) of about 13%-75% weight in the composition of claim 5; Each R is C 1-C 3Alkyl or hydroxyalkyl; Each Y is-O-(O) C-each YR 1Contain C 14-C 20, each R 1Be alkyl, single unsaturated alkylene or many unsaturated alkylenes, the content of many degrees of unsaturation is at least about 5%; X -Be chlorine, bromine, methylsulfate or nitrate radical; The content of main solvent B is about 10%-38%, 12%-25% more preferably from about, even 14%-20% more preferably from about, and the ClogP value of said main solvent B is about 0.25-0.62.
7. wherein there is the said fabric softener active matter (I) of about 17%-70% weight in the composition of claim 6; Each R is methyl, hydroxyethyl or their mixture; The content of degree of unsaturation is at least about 10%; The content of main solvent B is about 10%-38%, and the ClogP value of said main solvent B is about 0.25-0.62.
8. wherein there is the said fabric softener active matter (I) of about 19%-65% weight in the composition of claim 7; Each R is a methyl; The content of degree of unsaturation is at least about 15%; The content of main solvent B is about 12%-25%, and the ClogP value of said main solvent B is about 0.40-0.60.
9. the composition of claim 6, wherein said main solvent B is 2,2,4-trimethylammonium-1,3-pentanediol and 1,4 cyclohexane dimethanol are by weight being about 80: the mixture that 20-is about 50: 50.10. the composition of claim 6, wherein said main solvent B is 2,2,4-trimethylammonium-1,3-pentanediol and 1,4 cyclohexane dimethanol are by weight being about 75: 25 mixture.
CN97197940A 1996-07-19 1997-03-25 Concentrated fabric softening composition and highly unsaturated fabric softener compound thereof Pending CN1231688A (en)

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