CN1142847A - Viscosity stable concentrated liquid fabric softener compositions - Google Patents

Viscosity stable concentrated liquid fabric softener compositions Download PDF

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CN1142847A
CN1142847A CN 94194984 CN94194984A CN1142847A CN 1142847 A CN1142847 A CN 1142847A CN 94194984 CN94194984 CN 94194984 CN 94194984 A CN94194984 A CN 94194984A CN 1142847 A CN1142847 A CN 1142847A
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textiles
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CN1161450C (en
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J·C·塞弗恩斯
A·M·沃格尔
E·H·瓦尔
R·默梅斯坦
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Procter and Gamble Co
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • C11D3/0015—Softening compositions liquid
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/645—Mixtures of compounds all of which are cationic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds

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  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
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Abstract

Viscosity stable, concentrated, aqueous, liquid fabric softening compositions contain a mixture of biodegradable diester quaternary ammonium softening materials and specific co-active fabric softening materials which include substituted imidazoline compounds and specific quaternary ammonium salts. The compositions have superior stability at both normal and lower temperatures. The best process for preparing such compositions uses a molten premix of the fabric softening materials which is dispersed in an aqueous phase through the use of high shear milling.

Description

The concentrated liquid fabric softener compositions of stable viscosity
Technical field
The present invention relates to spissated water liquid textile treatment composition.Particularly relate to the composition of the rinse cycle that is used for the textile washing operation, so that textiles has soft and anlistatig advantage, the feature of said composition is to have fabulous package stability and fabulous viscosity stability after freeze.Background of invention
Make textiles have the water liquid textile treatment composition of soft and anlistatig advantage when being adapted at washing and starching, be well-known in the art, and obtaining large-scale industrial application.By convention, the aqueous textiles soft compound that adds when rinsing mainly contains the water-fast basically cationic materials that two chain alkyls are arranged as active ingredient.This typical material is chlorination dihydro tallow dimethylammonium and the imidazolinium compounds that replaced by two stearyl-s.This class material is normally to be dispersed in form preparation in the water.In general, adopt about cationic materials more than 10% to prepare this aqueous dispersion, be certain to product viscosity and stable aspect run into reluctant problem, after particularly under lower temperature, storing, cause composition can not toppled over, and in rinse water, do not have suitable dispersion and dissolution characteristics.This physics to tenderizer concentration has limited without the accessible softening performance level of excessive product, and has also improved sale and packing cost actually.Therefore, wish very much the acceptable in fact moisture textile treatment composition of preparation, the amount that wherein contains water-fast substantially cationic softener is much higher.
The cationic softener material is normally by producer supply, and it contains 70%～90% the active substance of having an appointment in organic liquid such as Virahol or ethanol, also contain a spot of water (can reach 10%) sometimes.The textiles soft compound of retail is softening agent to be dispersed in warm water or the hot water to prepare under the condition of meticulously control.Because the physical form of these industrial enriched materials and the restriction of dispersing property can not directly be used them by the family consumer, they in addition may cause serious processing problems to the industrial supplier of retail textiles soft compound.
When the moisture textiles soft compound that is suitable for conc forms preparation that the human consumer uses, in the various solutions to its particular problem, many all is unsafty.Generally all (for example can know, the US 3 that issues on August 10th, 1972,681,241 (Rudy)), the dissociable salt that exists in softener composition helps to reduce viscosity really, but this method itself is invalid to the composition that preparation contains the dispersed softening agent more than 12% of having an appointment, because the concentration that viscosity drop is low to moderate the required dissociable salt of any substantial extent has very adverse influence to the stability of product viscosity.
Summary of the invention
Have found that, the product stability and the viscosity characteristics of fabric softener compositions that contains following (A) and enrichment of mixture (B) is all very good under normal temperature and lesser temps: (A) biodegradable dibasic acid esters base quaternary ammonium flexible material (hereinafter being called " (A) "), (B) specific co-activating textiles flexible material (hereinafter being called " (B) ") (i.e. imidazolinium compounds of Qu Daiing and be different from the specific quaternary ammonium salt of (A)), improve the value of long-term viscosity characteristics of spissated positively charged ion textiles aqueous liquid composition and stability with this textiles flexible material mixture, particularly after freezing/thaw cycle, also do not generally acknowledged in the present technique field up to now.Detailed Description Of The Invention (A), biodegradable quaternized ester-amine softener material
The present invention contains a kind of dibasic acid esters base quaternary material (hereinafter being called " DEQA ") as main ingredient.Below the DEQA of the main type of two classes be preferential the selection.1. first kind DEQA preferably includes the compound with following general formula as main active ingredient:
Figure A9419498400111
Substituent R is C in the formula 1-C 6Short chain, preferred C 1-C 3Alkyl or hydroxyalkyl for example select methyl (most preferred), ethyl, propyl group and hydroxyethyl etc., benzyl or its mixture; M is 2 or 3; N is 1～about 4; Y representative-O-(O) C-, or-C (O)-O-, rather than-OC (O) O-; R 2Be C 12-C 22Long chain hydrocarbon groups, or substituted alkyl, preferred C 15-C 19Alkyl or alkylene, more preferably C 15-C 17Straight chained alkyl or alkylidene group make R 2The iodine number (hereinafter being called IV) of maternal fatty acid be lower than about 10, preferably be lower than about 5, most preferably be lower than about 2; Corresponding ion X (-)Can be the negatively charged ion of any softening agent compatibility, the negatively charged ion of preferred strong acid, for example chlorion, bromide anion, methylsulfuric acid radical ion, formate ion, sulfate ion and nitrate ion etc.Negatively charged ion also can be with double charge (but less preferred), under doubly charged situation, and X (-)Represent group half.In general, constituting stable concentrated liquid composition by these materials that contain dianion is the comparison difficulty.
The carbonates of Y=-O-C in the formula (O) O-is a unstable compounds, is not included in the compound of (A) (1).
Obviously, substituent R and R 2Can be randomly replace with various groups, for example alkoxyl group or hydroxyl, and can be straight chain, also can be side chain, as long as R 2Basically the hydrophobic character that keeps them.Preferred compound can be regarded the dibasic acid esters variant in chlorination two tallow dimethylammoniums (hereinafter being called " DTDMAC ") as, and it is a kind of fabric softener that is widely used.At least 80% DEQA is the dibasic acid esters form, and 0～about 20% can be the DEQA monoesters (for example have only an ester group generation hydrolysis generation-Y-H, or produce-OH).
When specifying as used herein dibasic acid esters, can comprise the monoesters of existence.For the purpose of softening, do not having/hang down under the wash conditions of washing composition, the shared percentage ratio of monoesters should be low as far as possible, preferably is not more than about 2.5%.And under the condition of high anionic detergent tensio-active agent or detergent builder, some monoesters is preferential the selection.Dibasic acid esters is to the overall proportion of monoesters about 100: 1～about 2: 1, and preferred about 50: 1～about 5: 1, more preferably from about 13: 1～about 8: 1.Under high washing composition condition, the ratio of dibasic acid esters/monoesters is preferably about 11: 1.The concentration that monoesters exists can be controlled in making the DEQA process.
In practice of the present invention, be used as the chemical reaction preparation of the above-claimed cpd available standards of biodegradable quaternised ester-amine flexible material.In a kind of synthetic method of the dibasic acid esters variant of DTDMAC, general formula is RN (CH 2CH 2OH) 2Amine on two hydroxyls, be R with general formula 2The acyl chlorides of C (O) Cl carries out esterification, with alkylogen RX quaterisation takes place then, generates needed reaction product (R and R herein 2Definition with aforesaid identical).Yet the technician of chemical field will appreciate that this response procedures can make the range of choice broadening of preparation reagent.Below be some non-limiting examples (all chain alkyl substituting groups all are straight chains in the example);
[HO-CH(CH 3)CH 2][CH 3]N (+)[CH 2CH 2OC(O)C 15H 31] 2Br (-)
[C 2H 5] 2N (+)[CH 2CH 2OC(O)C 17H 35] 2Cl (-)
[CH 3][C 2H 5]N (+)[CH 2CH 2OC(O)C 13H 27] 2I (-)
[C 3H 7][C 2H 5]N (+)[CH 2CH 2OC(O)C 15H 31] 2[SO 4CH 3] (-)
Figure A9419498400121
[CH 2CH 2OH][CH 3]N (+)[CH 2CH 2OC(O)R 2] 2Cl (-)
[CH 3] 2N (+)[CH 2CH 2OC (O) R 2] 2Cl (-)In the formula-C (O) R 2Be by hardened tallow fatty acid deutero-.
Because above-mentioned materials (di-esters) is to some instability of hydrolysis, when being used herein to preparation textiles soft compound, handling them should be quite careful.For example, prepare some stable liquid compositions at this, its clean pH is about 2～about 5, preferred about 2～and about 4.5, more preferably from about 2.5～about 4.Can add the proton acid for adjusting pH.US 4,767, and 547 (Straathof, promulgations on August 30th, 1988) disclose the pH scope of softener composition, and said composition contains the weaving preparation and contains the pH scope that the softening bonded of diester quaternary ammonium fabric is stablized softener composition.Be incorporated herein this patent and be made for reference.
The example of suitable protonic acid comprises inorganic mineral acid, carboxylic acid, particularly lower molecular weight (C 1-C 5) carboxylic acid and alkylsulphonic acid.Suitable mineral acid comprises HCl, H 2SO 4, HNO 3And H 3PO 4Suitable organic acid comprises formic acid, acetate, citric acid, methylsulfonic acid and ethyl sulfonic acid.Preferred acids is hydrochloric acid, phosphoric acid and citric acid.
2. in the second class DEQA, the general formula of main active compound is:
Figure A9419498400131
Y, R, R in the formula 2And X (-)Implication with aforesaid identical.These compounds comprise the compound with following general formula: [CH 3] 3N (+)[CH 2CH (CH 2OC[O] R 2) OC (O) R 2] Cl (-)C in the formula (O) R 2Be by sclerosis tallow fatty acid deutero-.
R preferable methyl or ethyl, R 2Preferred C 15-C 19To a certain degree side chain and replacement can be arranged on alkyl chain.Negatively charged ion X in the molecule (-)Identical with among the above-mentioned DEQA (1).When specifying as used herein dibasic acid esters, can comprise the monoesters of existence.Identical among the monoesters amount that can exist and the DEQA (1).
The present invention can also contain the DEQA mixture of two kinds of main types.
The type of this this reagent and the universal method of producing them are disclosed in US 4,137, in 180 (people such as Naik, on January 30th, 1979), are incorporated herein and are made for reference.
(B) co-activating textiles softener material
The composition of the present invention's preparation contains as main ingredient co-activating textiles softener material, and as mentioned below, it is different with biodegradable dibasic acid esters quaternary ammonium softener material.
1. this co-activating textiles flexible material is a kind of substituted tetrahydroglyoxaline textiles softener material, and the general formula of its main active compound is: Y in the formula 2Or-N (R 4) C (O)-,-OC (O)-; Or covalency chain, wherein a R 4Be selected from C 1-C 6Alkyl, alkenyl, hydroxyalkyl or hydrogen; R in the formula 3The alkyl of respectively doing for oneself preferably contains the alkyl of about 11～about 31 carbon atoms, wherein preferably contains about 13～about 17 carbon atoms, more preferably straight chained alkyl, n in the formula 2About number of 2～about 4 of respectively doing for oneself, preferred two n 2Be 2.Should be understood that each R 3Can randomly use various groups, replace as alkoxyl group or hydroxyl, it also can have side chain, but the not preferred such material of this paper.In addition, R 3It also can be the unsaturated alkyl of choosing wantonly (for example alkenyl).
The above-mentioned materials that is used as co-activating textiles softener material in enforcement of the present invention can utilize the chemical reaction preparation of standard.With tetrahydroglyoxaline fabric softener material be disclosed in US4,661,267 (Dekker, Konig, Straathof and Gosselink, on April 28th, 1987); US 4,724,089 (Konig and Buzzaccarini, on February 9th, 1988); US4,806,255 (Konig and Buzzaccarini, on February 21st, 1989); US4,855,072 (Trinh, Wahl, Swartley and Hemingway, on Augusts 8th, 1989); US 4,933,096 (DeMeyere, Hardy and Konig, June 12 nineteen ninety); US4,954,635 (Rosario-Jansen and Lichtenwalter, September 4 nineteen ninety).Be incorporated herein above-mentioned whole patent for your guidance.
Preferred co-activating textiles softener material of the present invention is the reaction product of high-grade lipid acid and polyamines, polyamines is selected from hydroxyl Alkylenediamine and two alkylene triamine and their mixture, its technological process is in public affairs US 5,013,846 (Walley, on May 7th, 1993) in, for reference in this proposition.From the viewpoint of polyamines multifunction structure, reaction product is the mixture (seeing the works " Fette-Seifen-Anstrichmittel " that H.W.Eckert for example delivered in September, 1972, the 527-533 page or leaf) of several compounds.
For example, in the typical substituted imidazoline ester softener material that meets above-mentioned general formula synthetic, general formula R 3The lipid acid of COOH and general formula NH 2-(CH 2) n 2-NH-(CH 2) n 2The reaction of the hydroxyl Alkylenediamine of OH generates a kind of intermediate product tetrahydroglyoxaline precursor, then it and general formula R 3C (O) OCH 3Fatty acid methyl ester reaction generate needed reaction product (R in the formula 3And n 2State as defined above identical).The those of ordinary skill of chemical field all can understand, can select the material that will prepare more widely by this response procedures.The non-limiting instance of property can list following dialkylimidazolium quinoline compound (all chain alkyl substituents all are straight chains) herein: 1-stearoyl keto ethyl-2-imidazoline-based stearyl as an illustration, 1-stearoyl keto ethyl-2-palmityl tetrahydroglyoxaline, 1-stearoyl keto ethyl-2-myristyl tetrahydroglyoxaline, 1-palm acyl-oxygen ethyl-2-palmityl tetrahydroglyoxaline, 1-palm acyl-oxygen ethyl-2-myristyl tetrahydroglyoxaline, 1-stearoyl keto ethyl-2-tallow tetrahydroglyoxaline, 1-Semen Myristicae acyl-oxygen ethyl-2-tallow tetrahydroglyoxaline, 1-palm acyl-oxygen ethyl-2-tallow tetrahydroglyoxaline, 1-coconut oil base oxygen ethyl-2-Oleum Cocois tetrahydroglyoxaline, 1-tallow base oxygen ethyl-2-tallow tetrahydroglyoxaline, 1-[hydrogenated tallow acid amides] ethyl-2-hydrogenated tallow tetrahydroglyoxaline, the 1-[stearylamide] ethyl-2-imidazoline-based stearyl, the 1-[palmitic amide] ethyl-2-palmityl tetrahydroglyoxaline, the 1-[oleylamide] ethyl-2-oil-based imidazoline and these tetrahydroglyoxaline mixtures of material.
At this substituted imidazoline softener material that also can adopt other type, the example of these materials comprises:
Figure A9419498400151
R in the formula 3And n 2Definition with aforesaid identical.Above-listed example is used for illustrating the substituted imidazoline softener material of other type, and they optionally use in the present invention, but are not preferred.
2. two (2-acid amides ethyl) methyl quaternary ammonium also is suitable as the component (B) in the present composition, particularly has the quaternary ammonium salt of following general formula:
Figure A9419498400162
R in the formula 7Be selected from C 14-C 20Alkyl and alkenyl, R in the formula 8Be selected from methyl, ethyl and-(C mH 2mO) n 3H, n in the formula 3Be 1～about 5, preferred 3, and m and X in the formula (-)Implication with aforesaid identical.This class reagent is at US 4,134, and is open among 840 people such as (, on January 16th, 1979) Minegishi, is incorporated herein for your guidance.
Typical material is sulfuric acid two (2-hydrogenated tallow acid amides ethyl) ethoxylation (2-oxyethyl group) first ammonium methyl esters, bromination two (2-oleylamide ethyl) propoxylation (3-propoxy-) first ammonium, sulfuric acid two (2-plam oil acid amides ethyl) dimethylammonium ethyl ester and sulfuric acid two (2-stearylamide ethyl) propoxylation (2-propoxy-) first ammonium methyl esters.
Here the typical commercial material that is suitable as component (B) is sulfuric acid two (2-tallow acid amides ethyl) ethoxylation first ammonium methyl esters (I.V. of B component is about 31), is sold with Varisoft merchant's name by Witco chemical company.
3. the co-activating textiles softener material that is used as component (B) in composition of the present invention also can have the compound of following general formula:
Figure A9419498400171
R in the formula 9Be C 15-C 17Alkyl, it makes R 9The IV of maternal fatty acid about 20～about 100, preferred about 30～about 70, most preferably from about 35～about 60; The connotation of X (-) is with aforesaid identical.
Preferred textiles softener material is according to US 3,915 among the present invention, and disclosed synthetic method prepares in 867 (Kang etc., on October 28th, 1975), is incorporated herein for your guidance.Textiles softener material of the present invention generally comprises the C of purifying 14-C 18The reaction of lipid acid alkane ester mixture, trolamine and quaternizing agent, quaternizing agent preferably sulfuric acid dimethyl ester.The mixture of oleic acid, palmitinic acid and stearic acid alkane ester that selected lipid acid alkane ester is preferably a large amount of also can comprise other fatty substance on a small quantity.
4. in composition of the present invention, be suitable as the co-activating textiles softener material of component (B), also following general formula can be arranged: R in the formula 10Be C 12-C 22The hydrocarbyl substituent of alkyl or replacement, preferred C 15-C 19Alkyl or alkylene, most preferably C 15-C 17Straight chained alkyl or alkylene make R 10The IV of maternal fatty acid about 20～about 100, preferred about 30～about 70, most preferably from about 35～about 60; R and X (-)Implication with aforesaid identical.
With regard to chain alkyl and alkylene material, tallow be a kind of easily, inexpensive chain alkyl and alkenyl source.
Being fit in the present invention, the specific examples of the dibasic acid esters base quaternary ammonium compound of use comprises:
1,2-two tallow base oxygen base-3-(trimethylammonio) chlorination propane
Being fit to other dibasic acid esters base quaternary ammonium of the present invention obtains by metalepsy, for example with " tallow base " in the replacement above-claimed cpds such as coconut oil base, palmitoyl, lauryl, oil base, stearyl, palmityl, with " methyl " in the hydroxyl substituent replacement above-claimed cpd of ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl or these groups; With " chlorine " in the replacement above-claimed cpds such as bromine, monomethyl sulfate radical, formate, sulfate radical and nitrate radical.
In fact, negatively charged ion only exists with the gegenion at this disclosed positively charged quaternary ammonium compound.Scope of the present invention does not limit any specific negatively charged ion.When DEQA (A) material was (2), this material can not satisfy the requirement to component (B), and DEQA (A) preferably do not exist except that a small amount of, unless the third tenderizer active compound existence is arranged in mixture.
These materials herein can adopt the raw material that obtains easily to pass through the esterification and the quaterisation preparation of standard.Some commonly used preparation methods are at US 4,137, and are open in 180, are incorporated herein for your guidance.
5. in composition of the present invention, the co-activating textiles softener material that is suitable as component (B) also can have following general formula:
Figure A9419498400181
R in the formula 11Be C 12-C 22Long chain hydrocarbon groups, or the hydrocarbon substituent after being substituted, preferred carbochain is C 15-C 19Alkyl or alkylene, C most preferably 15-C 17Straight chained alkyl or alkylene, make R 11The IV of maternal fatty acid be about 20～about 100, preferred about 30～about 70, most preferably from about 35～about 60; M, n, Y, R and X (-)Implication with aforesaid identical.When DEQA (A) material was (1), this material can not satisfy the requirement to component (B), and therefore this material does not preferably exist except that a small amount of, unless there is the third tenderizer active compound to exist in mixture.
The present invention also can contain the mixture of various co-activating textiles softener materials.
Composition of the present invention comprises component (A)+component (B) of about 15%～about 35%, preferred about 20%～about 32%, most preferably from about 22%～about 27%.
Component (A) is about 0.2: 1～about 8: 1 to the ratio of component (B), preferred about 0.25: 1～about 4: 1, and most preferably from about 0.3: 1～about 1.5: 1.(C) acid constituents
The present invention utilizes enough dense acid that pH is maintained on the needed level, and component (B) is fully protonated to making it can not quaternised again degree.Composition of the present invention is (hereinafter being called premixture) of adopting the molten prepolymer mixture preparation of component (A)+(B).This premixture is injected acid/water seat, carry out high shear grinding then, and add ionogen in any order.This ionogen is selected from the salt of IA and IIA family metal in the periodic table of elements, for example calcium chloride, sodium-chlor, Potassium Bromide, lithium chloride and ammonium salt (for example ammonium chloride and lysine hydrochloride.The acid concentration of typical acid/water seat can reach about 2%.
Acid is to the typical mol ratio of (B) about 0: 1～about 1.2: 1, acid about 0: 1～0.2: 1 to the typical mol ratio of (A), and the clean pH of final composition preferably about 2.5～about 4.
Suitable acids comprises protonic acid, acid of particularly inorganic ore deposit and organic acid (such as carboxylic acid).Carboxylic acid is R particularly including general formula 12-COOH (R 12Be C 1-C 15Or H alkyl) lower molecular weight (C 1-C 5) carboxylic acid.It is R that suitable organic acid is selected from general formula 13CH 2SO 3The organic acid of H, R in the formula 13Represent hydrogen or C 1-C 4Alkyl.Suitable concrete organic acid comprises formic acid, methylsulfonic acid, ethyl sulfonic acid, citric acid, gluconic acid and aromatic carboxylic acid such as phenylformic acid.Suitable mineral acid comprises HCl, HBr, H 2SO 4, H 2SO 3, HNO 3And H 3PO 4
Preferred acids is phosphoric acid, formic acid, acetate, hydrochloric acid, citric acid and methylsulfonic acid.The mixture of above-mentioned organic acid and mineral acid also suits.Usually the acid of adopting is citric acid, hydrochloric acid, phosphoric acid and sulfuric acid, has also bought easily because their price is low.(D) liquid vehicle
Composition among the present invention comprises about 60%～about 90% aqueous carrier liquid, and preferred about 65%～85%, preferred aqueous carrier is a water, and it may contain a spot of batching.(E) selectable batching
With the textiles softening compositio that method of the present invention is prepared fully, can contain one or more optional following batchings.
1. polysiloxane component
Textiles softening compositio herein can randomly contain based on linear poly-diakyl-or the water miscible liquid of alkylaryl siloxanes, and alkyl wherein has 1～5 carbon atom, and may fluoridize whole or in part.These siloxanes play a part to improve properties of textile.Suitable polysiloxane is a polydimethylsiloxane, under 25 ℃, and about 100～about 100,000 centistokes of its viscosity, preferred about 1,000～about 12,000 centistokes.In some applications, preferably be low to moderate the material of 1 centistoke.
Textiles softening compositio herein can contain 0.1%～about 10% the polysiloxane component of having an appointment.
2. thickening material
Textiles softening compositio herein can randomly contain 0%～about 3% thickening material, and preferred about 0.01%～about 2%.Some suitable thickening material examples comprise: high-molecular weight polymer of derivatived cellulose, synthetic (for example carboxy vinyl polymer and polyvinyl alcohol) and cationic jar (unit of capacitance) glue.
The derivatived cellulose that plays the thickening material effect herein can have the characteristic of some Mierocrystalline cellulose hydroxy ethers, as the Methocel of Dow chemical company sale; And some cationic cellulose ether derivatives, as polymkeric substance JR-125, JR-400 and the JR-30M of Union Carbide company sale.
Other effective thickening material is cationic jar (unit of capacitance) glue, as the JaguarPlus of Stein Hall sale and the Gendrive 458 of General Mills company sale.
This paper preferred thickening is selected from methylcellulose gum, Vltra tears, hydroxy butyl methyl cellulose or its mixture, and 2% aqueous solution of described cellulose polymer compound is about 15～about 75,000 centistokes of its viscosity under 20 ℃.
3. stain remover
In the present invention, can add a kind of optional stain remover.Stain remover can add premixture after ionogen adds forward and backward or making final composition, add acid/water seat.The softener composition of making by method of the present invention can contain 0%～about 10% stain remover herein, and preferred 0.2%～about 5%.Preferred this stain remover is a kind of polymkeric substance.The polymkeric substance stain remover of Shi Yonging comprises the segmented copolymer of terephthalate and polyoxyethylene or polyoxypropylene etc. in the present invention.
A kind of preferred stain remover is the multipolymer with terephthalate and polyoxyethylene blocks.More particularly, these polymkeric substance are made up of terephthalic acid second diester repeating unit and polyoxyethylene terephthalate, the mol ratio of terephthalic acid second two ester units and polyoxyethylene terephthalate unit is 25: 75～about 35: 65, and the polyoxyethylene terephthalic acid ester copolymer of described polyoxyethylene blocks thing contains the polyoxyethylene blocks of molecular weight about 300～2000.The molecular weight of this polymerization stain remover about 5,000～about 55,000.
Another kind of preferred stain remover is a kind of crystallizable polyester, has terephthalic acid second diester repeating unit, it contains terephthalic acid second two ester units and about polyoxyethylene terephthalate unit of 10%～about 50% of 10%～about 15% weight of having an appointment, be by molecular-weight average about 300～about 6,000 polyoxyethylene glycol deutero-, terephthalic acid second two ester units in crystallizable polymerizable compound are 2: 1～6: 1 to the mol ratio of polyoxyethylene terephthalate unit.The example of this polymkeric substance is included in material Zelcon 4780 (Dupont company) and the Milease T (ICI company) that supplies on the market.
Preferred stain remover is the polymkeric substance with following general formula:
Figure A9419498400211
X can be a kind of suitable end group in the formula, and it is selected from H usually and contains the alkyl or the acyl group of 1～about 4 carbon atoms of having an appointment.P selects for water-soluble, is generally about 6～about 113, preferred about 20～about 50.U for the prescription of fluid composition with high relatively ionic strength cause close important.U should be seldom greater than 10 material.U should at least 20% at about material of 3～about 5, and preferably at least 40%.
R 14Part mainly is 1, the 4-phenylene.When this paper adopts term " R 14Part mainly is 1, the 4-phenylene " be meant R 14Part is fully by 1, and the 4-phenylene is formed or its part is replaced by other arylidene or alkarylene, alkylidene group, alkylene group part or its mixture.Can partly replace 1, the arylidene of 4-phenylene and alkarylene partly comprise 1,3-phenylene, 1,2-phenylene, 1,8-naphthylidene, 1,4-naphthylidene, 2,2-biphenylene, 4,4-biphenylene and their mixture.Can the displaced alkylidene group of part and alkylene group partly comprise propylene, tetramethylene, pentamethylene, hexamethylene, 1, the inferior heptyl of 7-, octamethylene, 1,4-cyclohexylidene and their mixture.
R 14By 1, the displaced degree of group beyond the 4-phenylene should be that detergency ability to compound is without any big adverse influence.The displaced degree of general permissible part often depends on the length of compound main chain, and promptly main chain is long more, and part replaces 1, and the degree of 4-phenylene is also just big more.Usually, R 14Comprise about 50%～about 100% 1, the compound of 4-phenylen moiety (have 0%～about 50% be not phenylene) has enough decontamination activity.For example, according to the present invention, benzene two between employing (1, the 3-phenylene) acid/to the sour mol ratio of benzene two (1, the 4-phenylene) is that the polyester of preparation in 40: 60 has enough decontamination activity.But because used most of polyester comprise terephthalic acid second two ester units in fiber production, usually needing will be non-1, and the part replacement of 4-phenylene drops to minimum degree, to obtain best decontamination activity.Preferred R 14Part fully (promptly 100%) by 1,4-phenylene composition, i.e. each R 12Part all is 1, the 4-phenylene.
For R 15Part, the suitable ethylidene or the part of alternative ethylidene comprise ethylidene, propylene, 1,2-butylidene, 1,2-hexylidene, 3-methoxyl group-propylene and their mixture.Preferred R 15Part mainly is ethylidene part, propylene part or their mixture.Contain the decontamination activity that the percentage ratio of ethylidene part is tending towards improving compound when big.Beyond thought is to be tending towards improving the water-soluble of compound when containing higher propylene part percentage ratio.
Therefore, for the major portion of any decontamination component that in liquid fabric softener compositions, adds, be ideal with propylene part or similar branching equivalent, the propylene part of preferably about 7 5%-about 100%.
The p value is at least about 6, preferably is at least about 10.The n value is generally about 12～about 113.Typical n value is about 12～about 43.
More complete stain remover content is asked for an interview following patent, proposes for your guidance at this: US4,661,267 (Decker, Konig, Straathof and Gesselink, on April 28th, 1987); US 4,711,730 (Gosselink and Diehl, on December 8th, 1987); US4,749,596 (Evans, Huntington, Steward, Wolf and Zimmere, on June 7th, 1988); US 4,818,596 (Trinh, Gosselink and Rattinger, on April 4th, 1989); US 4,877,896 (Maldonado, Trinh and Gosselink, on October 31st, 1989); US 4,956,447 (people such as Gosselink, September 11 nineteen ninety); US4,976,879 (Maldonado, Trinh and Gosselink, December 11 nineteen ninety).
Also can the spume effect of dispersion agent of these stain removers.
4. scum dispersion agent
In the present invention, except stain remover, also can in premixture, mix optional scum dispersion agent and be heated to the fusing point of component or more than the fusing point.
Preferred herein scum dispersion agent is made of the hydrophobic material of height ethoxylation.Hydrophobic material can be Fatty Alcohol(C12-C14 and C12-C18), lipid acid, aliphatic amide, fatty acid amide, amine oxide, quaternary ammonium compound or the hydrophobic nature part that is used to form soil release polymer.Preferred scum dispersion agent is the height ethoxylation, for example, on average in each molecule the mole number of ethylene oxide greater than about 17, be preferably greater than about 25, more preferably greater than about 40, its polyoxyethylene partly be total molecule weight about 76%～about 97%, be preferably about 81%～about 94%.
The consumption of scum dispersion agent is enough to make scum to remain under the working conditions acceptable, the imperceptible level preferably of human consumer, but is not enough to ramollescence is produced adverse influence.For some purpose, wish not exist scum.The negatively charged ion of carrying secretly in textiles (washings) is different with the quantity of non-ionic detergent surfactivity and washing assistant (particularly phosphoric acid salt and float stone), and this depends in the amount of used negatively charged ion of the cycles of washing of typical washing process or non-ionic detergent etc. and the efficient and the water hardness of rinse step before adding composition.Usually should use minimum scum dispersion agent softening performance to be produced adverse influence to avoid it.Amount with the softening agent active substance is a basic calculation, and typical scum dispersion liquid requires at least about 2%, preferably at least about 4% (in order to avoid scum to greatest extent, at least about 6%, preferably at least about 10%) dispersion agent.Yet, under about 10% (with respect to softening agent material) of content or higher situation, when particularly textiles contains a high proportion of nonionic surface active agent that has been adsorbed in washing operation, have the danger that loses the softening effect of product.
Preferred scum dispersion agent is Brij 700, Varonic U-250, Genapol T-500, Genapol T-800, Plurafac A-79 and NeodoL 25-50.
5. sterilant
The example of used sterilant in composition of the present invention, comprise glutaraldehyde, formaldehyde, 2-bromo-2-nitro-1 that the Inolex Chemicals company that is positioned at philadelphia, pa sells with Bronopol merchant's name, the 5-chloro-2-methyl-4-isothiazoline-3-ketone that 3-dihydroxypropane and Rohm and Hass company sell with KathenCG/ICP merchant's name and the mixture of 2-methyl-4-isothiazoline-3-ketone.The typical amounts of used sterilant in this composition, by reagent weight about 1～about 1,000ppm.
6. other optional component
The present invention can comprise the optional components that is generally used in the textile treatment composition, for example, the stablizer of the short-chain alcohols of ethanol or dipropylene glycol and so on, tinting material, spices, sanitas, brightening agent, opalizer, tensio-active agent, guar gum and polyoxyethylene glycol and so on, antishrinking agent, teb-x-cel, stain remover, sterilant, mycocide, the antioxidant such as butylated hydroxyl toluene, inhibitor etc.
Composition of the present invention is preferred for the conventional rinse cycle of washing operation automatically.About 15 ℃～about 60 ℃ of the temperature of general rinse water.
Textiles or fiber contact with the composition of the about 20ml of significant quantity～about 300ml (textiles of every processing 3.5kg or fiber) this paper in water-bath.Certainly, used amount is based on the judgement that the user is made according to the type of concentration, fiber or the textiles of flexible material (A)+(B) and needed soft degree etc.Usually in the 25 washing rinsings that add human relations are bathed, make the heavy mixed textile product softness of 3.5kg and have antistatic property, need use the dispersion liquid of the flexible material (A)+(B) of about 20ml～300ml 9%～40%.The textiles softener material (A)+(B) that contains about 20ppm～about 250ppm this paper is bathed in preferred rinsing.For the condition of the U.S., more preferably in bathing, rinsing contains the textiles softener material (A)+(B) of about 50ppm～about 150ppm.And for the condition in Europe, more preferably the textiles softener material (A)+(B) that contains about 250ppm～about 450ppm is bathed in rinsing.For the condition of Japan then more preferably rinsing bathe the textiles softener material (A)+(B) that contains about 30ppm～about 80ppm.These concentration of material can obtain the softening and antistatic property of good textiles.
By following non-limiting examples the present invention is described, wherein all numerical value is consistent with common experience substantially.Embodiment 1 prescription: 12345
(Wt.%) two (2-acid amides ethyl) methyl seasons 0 6.25 12.50 18.75 25.00 ammonium salt DEQA 224.5 18.75 12.50 6.25 0Genapol T-110 1.00 1.00 1.00 1.00 1.00 ethanol 0.95 0.92 0.61 0.30 0.00Isopropanol 0.00 0.68 1.39 2.08 2.78 spices 1.20 1.20 1.20 1.20 1.20 polysiloxanes DC-200*0.19 0.19 0.19 0.19 0.19 polysiloxane foam preventer *0.32 0.32 0.32 0.32 0.32DC-2210 soil release polymer, 0.50 0.50 0.50 0.50 0.50HCl, 0.03 0.03 0.03 0.03 0.03 FE-5,0.75 0.75 0.75 0.75 0.75 deionized water 70.56 69.40 69.01 68.63 68.23*The product 1 of Dow-Corning company, methylsulfuric acid two (2-tallow acid amides ethyl) ethyl base ammonium methyl (selling) 2, chlorination N with merchant's name Varisoft 222, N-two (hydrogenated-tallow group-oxygen-ethyl)-N, the N-Dimethyl Ammonium prepares example I
First three kind component in each prescription is placed in the palace vulval vycol beaker, covers the concave surface ware,, form premixture about 80～85 ℃ of following congruent meltings 3 hours.Respectively water, HCl and polysiloxane foam preventer are weighed in the container of a sealing, are heated to about 83 ℃, form the water seat.In 3～4 minutes, under about 72 ℃, premixture is injected the water seat then, stir simultaneously, the about 1500～3000r.p.m. of rotating speed.In 7 minutes, under about 71 ℃, 15% Methionin/aqueous hydrochloric acid is joined in water seat/premixture dispersion liquid, stir simultaneously, the about 500～about 1000r.p.m. of rotating speed.In 30 seconds, spices and polysiloxane DC-200 are added in the dispersion liquid.Under about 70 ℃, dispersion liquid was ground 2 minutes the about 4000～about 8000r.p.m. of the rotating speed of mill.Under 66 ℃, in 2 minutes, the 40% soil release polymer aqueous solution is added in the dispersion liquid, stir the about 500～about 1000r.p.m. of rotating speed simultaneously.Then dispersion liquid was cooled off 8 minutes in ice bath at 25 ℃, stir the about 200～about 500r.p.m. of rotating speed simultaneously.
Prescription Initial viscosity (cP 3) The # fate ????0℃ ???(cP) ????4° ??(cP) ????10° ????(cP)
????1 ????59 ????145 Gelling (2d 4) Gelling (3d) Gelling (3d)
????2 ????243 ????28 Gelling (2d) Gelling (3d) 275
????3 ????281 ????28 Gelling (3d) ＞500 248
????4 ????143 ????28 Not gelling 133 132
????5 ????155 ????28 Not gelling ＞500 ＞500
3Centipoise is represented in abbreviation " cP ". 4Fate is represented in abbreviation " d ".
Contain two kinds of softening agent active material components (A) and component (B) enrichment of mixture composition (prescription 2-4) when temperature drops to 10 ℃, the viscosity of composition that its viscosity ratio only contains a kind of softening agent active ingredient (A) or component (B) (prescription 1 and 5) is more stable.
Comparing embodiment II fills a prescription 123
(weight %) two tallow imidazoline amides 525-16.67DEQA 6-25 8.33 soil release polymer-0.5 0.17CaCl 20.4 0.35 0.38 spices, 1.35 1.35 1.35DC-200 polysiloxane *0.19 0.19 0.19DC-2210 polysiloxane *0.32 0.32 0.32 kilfoam sanitas (Kathon), 0.0003 0.0003 0.0003HCl, 1.70 0.02 1.14 ethanol-3.5 1.17 deionized waters 71.0 68.8 70.3 *Dow-Cornign company product 51-[hydrogenated tallow amide group] ethyl-2-hydrogenated tallow tetrahydroglyoxaline 6Chlorination N, N-two (hydrogenated-tallow group-oxygen-ethyl)-N, N--Dimethyl Ammonium
Preparation example II preparation prescription 1
The two tallow imidazoline amides of 375g are heated to about 93 ℃ of fusions.One side stirs under rotating speed 400～600r.p.m. with IKA type RW20 DZM agitator then, one side was distributed to the fused softening agent in 5 minutes in 82 ℃ of deionized waters of 376g, and this water contains HCl solution and the 4.8g DC-2210 polysiloxane foam preventer of 90g 28.25%.With the dispersion liquid restir that obtains 4 minutes.In 2.5 minutes, second part of about 82 ℃ 580g deionized water stirred in the into thick dispersion liquid.Mixture with 20.25g spices and 2.85g DC-200 polyorganosiloxane fluid adds in 30 seconds in the dispersion liquid then, then mixes 2.5 minutes under the 8000r.p.m. rotating speed with IKA Ultra-Turrax T50 high shear mill.Make dispersion liquid pass through a small-sized plate and frame interchanger then, arrive room temperature at 3 minutes internal cooling.At room temperature add the 0.3g sanitas after cooling down.Preparation prescription 2
With 431g chlorination N, N-two (hydrogenated-tallow group-oxygen-ethyl)-N, N-Dimethyl Ammonium and 24g ethanol are in about 91 ℃ of following fusions.Under about 82 ℃, in 5.5 minutes, these fused softening agents are distributed in the 954g deionized water, this water contains the soil release polymer solution of 8.25g 0.968 N HCl solution, 4.89g DC-2210 polysiloxane foam preventer and 18.75g 40%, stirs under 800～1100r.p.m. simultaneously.Then in 4.5 minutes with the CaCl of 35g 15% 2The aqueous solution stirs in the dispersion liquid.Subsequently in 30 seconds, the mixture of 20.25g spices and 2.85g DC-200 polyorganosiloxane fluid is joined in the dispersion liquid, then under the 8000r.p.m. rotating speed, mixed 2.5 minutes with high shear mill.Just before finishing, cooling adds the 0.3g sanitas.Make dispersion liquid pass through a small-sized plate and frame interchanger then, arrive room temperature at 2.5 minutes internal cooling.Preparation prescription 3
The product of 105g prescription 2 is at room temperature mixed with the product of 210g prescription 1.
Prescription Initial viscosity (cP) Fate under 4 ℃ 4 ℃ of viscosity (cP) of transferring postpone
????1 ????38 ????5 ??＞5000
????2 ????78 ????3 Own gelling
????3 ????43 ????3 Own gelling
This preparation method's shortcoming that last illness that has not attacked the vital organs of the human body is real, described as example II, in the method, actives is not by congruent melting.When adopting the premixture of fused softening agent active ingredient (A) and component (B), can make product have good viscosity stability.
EXAMPLE III IV V VI
(Wt.%) two tallow imidazoline amides 714.3 14.3 14.3 11.0DEQA 87.7 8.7 9.7 12.0CaCl 20.375 0.375 0.375 0.375 spices, 1.35 1.35 1.35 1.35DC-200 polysiloxane *0.19 0.19 0.19 0.19DC-2210 polysiloxane *0.32 0.32 0.32 0.32 anticorrisive agent (Kathon), 0.0003 0.0003 0.003 0.003 antifoaming agent HCl, 0.97 0.97 0.97 0.75 ethanol, 1.25 1.42 1.58 1.95 deionized waters 73.5 72.3 71.2 72.1*The product of DOW-Corning company. 71-[hydrogenated tallow amide group] ethyl-2-hydrogenated tallow tetrahydroglyoxaline 8Chlorination N, N-two (hydrogenated-tallow group-oxygen-ethyl)-N, N-Dimethyl Ammonium
Preparation EXAMPLE Example III
With 214g two tallow imidazoline amides, 115.5g chlorination N, N-two (tallow base-oxygen-ethyl) N, N-Dimethyl Ammonium and 19g ethanol are in about 91 ℃ of following congruent meltings.In 5.5 minutes this fused softening agent mixture is distributed to 1 under about 82 ℃, in the 102g deionized water, this water contains 14.55gHCl and 4.8g DC-2210 polysiloxane foam preventer, stirs under 800～1100r.p.m. simultaneously.Subsequently in 4.5 minutes with the CaCl of 37.5g 15% 2The aqueous solution stirs in the dispersion liquid.In 30 seconds, 20.25g spices and 2.85g DC-200 polyorganosiloxane fluid are joined in the dispersion liquid then, then under 8000r.p.m., mixed 2.5 minutes with high shear mill.Make dispersion liquid pass through a small-sized plate and frame interchanger then, arrive room temperature at 2.5 minutes internal cooling.
After cooling finishes, at room temperature add the 0.3g sanitas.EXAMPLE IV, V and VI
Except tetrahydroglyoxaline, chlorination N, beyond N-two (hydrogenated-tallow group-oxygen-ethyl) N, the consumption of N-Dimethyl Ammonium, ethanol and HCl changed by the prescription shown in top, the product of these embodiment all was to prepare with the method identical with example III.
Embodiment Initial viscosity (cP) Fate under 4 ℃ 4 ℃ of viscosity (cP) of transferring postpone
????III ????18 ????42 ????60
????IV ????15 ????23 ????50
????V ????18 ????30 ????95
????VI ????18 ????29 ????33
The foregoing description has proved the advantage of employing molten prepolymer mixture and high-shear dispersion system type (available high shear mill obtains).

Claims (9)

1, a kind of stable aqueous fluid concentrates the textiles soft compound, and said composition comprises: (A) biodegradable dibasic acid esters quaternary ammonium textiles softener material, and this material is selected from:
Figure A9419498400021
R is selected from C in the formula 1-C 6Alkyl or hydroxyalkyl, m are 2 or 3; N is 1～4; R 2Be selected from C 12-C 22Alkyl or substituted hydrocarbon radical, must make R 2The IV of maternal fatty acid of base is lower than 10, Y is-O-(O) C-or-C (O)-O, rather than OC (O) O; X in the formula (-)It is compatible negatively charged ion; Perhaps be selected from:
Figure A9419498400022
Y, R, R in the formula 2And X (1)Connotation with aforesaid identical; Perhaps be selected from the mixture of (1) and (2);
(B) co-activating textiles softener material, this material is selected from:
Figure A9419498400023
Y in the formula 2Or-N (R 4) C (O)-,-OC (O)-; Or single covalent linkage; R wherein 4Be selected from C 1-C 6Alkyl, alkenyl, hydroxyalkyl or hydrogen; R in the formula 3Be the alkyl that contains 11～31 carbon atoms, n in the formula 2Respectively be 2～4; Perhaps be selected from:
Figure A9419498400031
R in the formula 7Be selected from C 14-C 20Alkyl and alkenyl; R in the formula 8Be selected from methyl, ethyl and-(C mH 2mO) n 3H; N in the formula 3Be 1～5; M and X in the formula (-)Connotation with aforesaid identical; Perhaps be selected from:
Figure A9419498400032
R in the formula 9Be C 15-C 17Alkyl must make R 9The IV of the maternal fatty acid of base is 20～100, X (-)Connotation with aforesaid identical; Perhaps be selected from:
Figure A9419498400033
R in the formula 10Be C 12-C 22Alkyl or substituted hydrocarbon radical substituent must make R 10The IV of the maternal fatty acid of base is 20～100, R and X (-)Connotation with aforesaid identical; Perhaps be selected from:
Figure A9419498400034
R in the formula 11Be C 12-C 22Long chain hydrocarbon groups or substituted hydrocarbon radical substituent must make R 11The IV of the maternal fatty acid of base is about 20～100, m, n, Y, R and X (-)Connotation with aforesaid identical; Or comprise (A) and mixture (B), and wherein the total amount of component (A)+(B) is 15%～35%, preferred 20%～about 32%, more preferably 22%～27%; Wherein preferred (A)/(B) than being 0.2: 1～8: 1, more preferably 0.25: 1～4: 1, even preferred again 0.3: 1～1.5: 1; Wherein when (A) was (1), (B) (5) can not satisfy the needs to component (B), and wherein when (A) is (2), (B) (4) can not satisfy the needs to component (B), and wherein the clean pH of final moisture concentrated fabric softener is preferably 2.5～4.
2, a kind of stable aqueous fluid concentrates the textiles soft compound, and said composition comprises:
(A) biodegradable dibasic acid esters base quaternary ammonium textiles softener material, its general formula is:
Figure A9419498400041
R is selected from C in the formula 1-C 6Alkyl or hydroxyalkyl, m are 2 or 3; N is 1～4; R 2Be selected from C 12-C 22Alkyl or substituted hydrocarbon radical must make R 2The IV of the maternal fatty acid of base is lower than 10; Y is-O-(O) C-or-C (O)-O, rather than OC (O) C; X in the formula (-)It is compatible negatively charged ion;
(B) co-activating textiles softener material, its general formula is:
Figure A9419498400042
R in the formula 7Be selected from C 14-C 20Alkyl and alkenyl; R 8Be selected from methyl, ethyl and-(CmH 2mO) n3H, n in the formula 3Be 1～5; M and X in the formula (-)Connotation with aforesaid identical; Wherein the total amount of component (A)+(B) is 15%～35%, is preferably 20%～32%, more preferably 22%～27%; Wherein (A)/(B) than be preferably 0.2: 1～8: 1, more preferably 0.25: 1～4: 1, even be preferably 0.3: 1～1.5: 1 again; Wherein the clean pH of final aqueous concentrated fabric softener is preferably 2.5～4.
3, a kind of stable, aqueous fluid concentrates the textiles soft compound, and said composition comprises:
(A) biodegradable dibasic acid esters quaternary ammonium textiles softener material, its general formula is:
Figure A9419498400051
R is selected from C in the formula 1-C 6Alkyl or hydroxyalkyl; M is 2 or 3; N is 1～4; R 2Be selected from C 12-C 22Alkyl or substituted hydrocarbon radical must make R 2The IV of the maternal fatty acid of base is lower than 10; Y is-O-(O) C-or-C (O)-O, rather than OC (O) O; X in the formula (-)It is compatible negatively charged ion;
(B) co-activating textiles softener material, its general formula is: Y in the formula 2Or-N (R 4) C (O)-,-OC (O)-; Or unit price covalent linkage; R in the formula 4Be selected from C 1-C 6Alkyl, alkenyl, hydroxyalkyl or hydrogen; R in the formula 3Respectively for containing the alkyl of 11～31 carbon atoms; N in the formula 2It respectively is 2～4 number; Wherein the total amount of component (A)+(B) is 15%～35%, and is preferred 20%～32%, more preferably 22%～27%; Wherein (A)/(B) than preferred 0.2: 1～8: 1, and more preferably 0.25: 1～4: 1, even preferred again 0.3: 1～1.5: 1; Wherein the clean pH of final aqueous concentrated fabric softener is preferably 2.5～4.
4, a kind of stable, aqueous fluid concentrates the textiles soft compound, and said composition comprises:
(A) biodegradable dibasic acid esters quaternary ammonium textiles softener material, its general formula is:
Figure A9419498400053
Y is-O-(O) C in the formula, or-C (O) O-, rather than-OC (O) O; R is selected from C in the formula 1-C 6Alkyl or hydroxyalkyl, R 2Be selected from C 12-C 22Alkyl or substituted alkyl must make R 2The IV of the maternal fatty acid of base is lower than 10, X in the formula (-)It is compatible negatively charged ion;
(B) co-activating textiles softener material, its general formula is: R in the formula 7Be selected from C 14-C 20Alkyl and alkenyl; R 8Be selected from methyl, ethyl and-(CmH 2mO) n 3H, n in the formula 3Be 1～5; M and X in the formula (-)Connotation with aforesaid identical; Wherein the total amount of component (A)+(B) is 15%～35%, and is preferred 20%～32%, more preferably 22%～27%; Wherein (A)/(B) than preferred 0.2: 1～8: 1, and more preferably 0.25: 1～4: 1, even preferred again 0.3: 1～1.5: 1; The clean pH preferred 2.5～4 of wherein final aqueous concentrated fabric softener.
5, a kind of stable aqueous fluid concentrates the textiles soft compound, and said composition comprises:
(A) biodegradable dibasic acid esters quaternary ammonium textiles softener material, its general formula is:
Figure A9419498400062
Y is-O (O) C in the formula, or-C (O) O-, rather than-OC (O) O; R is selected from C in the formula 1-C 6Alkyl or hydroxyalkyl, R 2Be selected from C 12-C 22Alkyl or substituted hydrocarbon radical must make R 2The IV of the maternal fatty acid of base is lower than 10, X in the formula (-)It is compatible negatively charged ion;
(B) co-activating textiles softener material, its general formula is:
Figure A9419498400071
Y in the formula 2Or-N (R 4) C (O)-,-OC (O)-; Or unit price covalent linkage; R wherein 4Be selected from C 1-C 6Alkyl, alkenyl, hydroxyalkyl or hydrogen; R 3Respectively for containing the alkyl of 11～31 carbon atoms; N in the formula 2Respectively be 2～4; Wherein the total amount of component (A)+(B) is 15%～35%, and is preferred 20%～32%, more preferably 22%～27%, and wherein (A)/(B) than preferred 0.2: 1～8: 1, and more preferably 0.25: 1～4: 1, even preferred again 0.3: 1～1.5: 1; The clean pH preferred 2.5～4 of wherein final aqueous concentrated fabric softener.
6, a kind of stable aqueous fluid concentrates the textiles soft compound, and said composition comprises:
(A) biodegradable dibasic acid esters quaternary ammonium textiles softener material, its general formula is:
Figure A9419498400072
Y is-O (O) C in the formula, or-C (O) O-, rather than-OC (O) O; R is selected from C in the formula 1-C 6Alkyl or hydroxyalkyl, R 2Be selected from C 12-C 22Alkyl or substituted hydrocarbon radical must make R 2The IV of the maternal fatty acid of base is lower than 10, X in the formula (-)It is compatible negatively charged ion;
(B) co-activating textiles softener material, its general formula is: R in the formula 9Be C 15-C 17Fatty alkyl must make R 9The IV of maternal fatty acid be 20～100, X (-)Connotation with aforesaid identical, wherein the total amount of component (A)+(B) is 15%～35%, and is preferred 20%～32%, more preferably 22%～27%; Wherein (A)/(B) than preferred 0.2: 1～8: 1, and more preferably 0.25: 1～4: 1, even be preferably 0.3: 1～1.5: 1 again; Wherein the clean pH of final aqueous concentrated fabric softener is 2.5～4.
7, a kind of stable aqueous fluid concentrates the textiles soft compound, and said composition comprises:
(A) biodegradable dibasic acid esters quaternary ammonium textiles softener material, its general formula is: Y is-O (O) C in the formula, or-C (O) O-, rather than-OC (O) O; R is selected from C in the formula 1-C 6Alkyl or hydroxyalkyl, R 2Be selected from C 12-C 22Alkyl or substituted hydrocarbon radical must make R 2The IV of maternal fatty acid less than 10, X in the formula (-)It is compatible negatively charged ion;
(B) co-activating textiles softener material, its general formula is: R in the formula 11Be C 12-C 22Long chain hydrocarbon groups, or substituted hydrocarbon radical substituent must make R 11The IV of the maternal fatty acid of base is 20～100, m, n, Y, R and X (-)Connotation with aforesaid identical; Or comprise (A) and (B) mixture; Wherein the total amount of component (A)+(B) is 15%～35%, and is preferred 20%～32%, more preferably 22%～27%, and wherein (A)/(B) than preferred 0.2: 1～8: 1, and more preferably 0.25: 1～4: 1, even preferred again 0.3: 1～1.5: 1; The clean pH preferred 2.5～4 of wherein final moisture concentrated fabric softener.
8, prepare composition in above-mentioned each claim with the method for molten prepolymer mixture, this method comprises:
A. biodegradable dibasic acid esters quaternary ammonium textile softener (A) and second kind of fabric softener (B) are pre-mixed;
B. this premixture is injected acid/water seat, this acid/water seat preferably is selected from the acid of inorganic ore deposit and has general formula R 12The organic acid of COOH, or R 13CH 2SO 3H, wherein R 12Be C 1-C 5Alkyl or H, wherein R 13Be hydrogen or C 1-C 4Alkyl, and their mixture, wherein preferred acid are phosphoric acid, hydrochloric acid, citric acid or its mixture, and the preferred acid concentration of wherein acid/water seat reaches 2%, preferred 0: 1～1.2: 1 of mol ratio of wherein acid/(B);
C. carry out high shear grinding and add ionogen, ionogen preferably is selected from salt, preferably calcium chloride or the ammonium salt of periodic table of elements IA and IIA family metal.
9, composition according to Claim 8, wherein said premixture are and a scum dispersion agent bonded.
CNB941949842A 1993-12-13 1994-12-12 viscosity stable concentrated liquid fabric softener compositions Expired - Lifetime CN1161450C (en)

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WO1995016766A1 (en) 1995-06-22
JP3746294B2 (en) 2006-02-15
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MA23394A1 (en) 1995-07-01
CA2179007A1 (en) 1995-06-22
EP0734433B1 (en) 2000-03-22
BR9408310A (en) 1997-08-26
CN1161450C (en) 2004-08-11
JPH09506684A (en) 1997-06-30
EP0734433B2 (en) 2004-03-24
DE69423650T2 (en) 2000-11-02
DE69423650D1 (en) 2000-04-27
EP0734433A1 (en) 1996-10-02
CA2179007C (en) 2002-04-02
ES2144603T5 (en) 2004-11-16

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