CN1040835A - The fabric sofetening composition that contains getting imidazoline ester and quaternized ester-ammonium salt mixture - Google Patents
The fabric sofetening composition that contains getting imidazoline ester and quaternized ester-ammonium salt mixture Download PDFInfo
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- CN1040835A CN1040835A CN 89103608 CN89103608A CN1040835A CN 1040835 A CN1040835 A CN 1040835A CN 89103608 CN89103608 CN 89103608 CN 89103608 A CN89103608 A CN 89103608A CN 1040835 A CN1040835 A CN 1040835A
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Abstract
The biodegradable fabric sofetening composition of stable storage is provided, and they are made up of a kind of imidazoline ester of replacement, a kind of quaternised ester-ammonium salt and a kind of liquid-carrier.These Biodegradable compositions have product stability, dispersiveness and the condensability of improvement, and good fabric sofetening conditioning performance.
Description
The application is the further part of the pendent U. S. application 07/342,431 of proposition on April 27th, 1989, and the latter is again that on May 27th, 1988 applied for and further part existing resigned U. S. application 07/199,542.
The present invention relates to a kind fabric treatment compositions, especially the rinse cycle that relates to fabric laundering operation is used, be beneficial to the softness of fabric and the fabric treatment composition of static control, this treatment compositions has good storing stability, condensability and softening performance, and biodegradability.Treatment compositions of the present invention also is used in the hot air dries machine of clothes and handles fabric, and can add in the associating washing type washing agent, and adds in the hair conditioner.
Helping the fabric treatment composition of fabric sofetening and static control in laundering, is called optical imaging in technology, and uses in a large number in industry.Usually, the fabric sofetening composition that adds in the rinsing contains water-insoluble basically, has the cationic substance of two long alkyl chains, as effective softening component.Representative in these materials is chlorination two fat Dimethyl Ammonium and has two substituent imidazolinium compoundss of hard ester acyl.These materials are made into the water slurry form usually.Generally, can not be made into the cation material, and not run into ticklish problems such as the viscosity of product and stability, especially behind high temperature storage about this class water slurry more than 10%.The composition of this high concentration usually can not pour into, and in washings, suspend and solubility property not good.These have limited the level of accessible softening performance under the situation of not using excessive product naturally to the physical property requirement of softer consistency, have also increased the cost that distributes and pack to a certain extent.
Therefore, be starved of and be made into the qualified fabric treatment composition of physical property, it contains the water-insoluble cationic softener material of suitable high concentration and has good softening performance.
There is also a desire for stable and biodegradable fabric sofetening composition in a kind of storage.But biodegradable material often is difficult to prepare stable liquid preparation.
One of purpose of the present invention provides stable and biodegradable fabric sofetening composition in a kind of storage.Further purpose provides this class material of fluid product form, comprises concentrate, in the rinse cycle that is used for fabric laundering operation; With this class material that sheet is provided, to be used for clothing dryer.Above-mentioned and other purpose utilizes the present invention all can reach, and can be found out in open by following.
Manufacturer is usually with slurry form supply cationic softener, promptly contains 70～80% the active principle of having an appointment in a kind of organic solvent, and this solvent can be isopropyl alcohol, contains a spot of water (can reach about 10%) sometimes.The preparation of the fabric softener of retail also will be dispersed in this softener slurry in the warm water under the condition of careful control.But,, be in order to prevent that the domestic consumer from directly using it to the physical form and the dispersed restriction of this industrial concentrate; Really, even for the industrial supplier of retail fabric softener, these restrictions have also brought serious processing problems.
Use the technology of various quaternised ester-ammonium salts as cationic softener, be that everybody is known, for example, about having a series of quaternised ester-ammonium salt of fabric softener function, can be referring to United States Patent (USP) 4,339,391(Hoffmann et al, issued July 13,1982).Various quaternised ester-ammonium salts, commercial can be by ICI company with the commodity of SYNPROLAMFS or REWO supply of commodities with REWOQUAT.Similarly, the compound method of various quaternised ester-ammonium compoundss is that everybody is known.For example, referring to United States Patent (USP) 3,340,840(Sobolev, on September 19th, 1967 delivered); United States Patent (USP) 3,872,138(Ogatu, on March 18th, 1975 delivered) and a day disclosure special permission communique 49-1510(transferred Gosei chem Ind co, on January 9th, 1974 is open).
Unfortunately, though it is biodegradable rapidly it is believed that quaternised ester-ammonium salt, but it is than common cationic softener (for example chlorination two fat Dimethyl Ammonium and analogs) facile hydrolysis more, thereby may run into thing mutually and chemical stability problems when long-term shelf are stored.For the aqueous dispersion that concentrates, it is difficult day by day that this product stability and viscosity problem become.
In the fabric softener that in rinsing, adds sometimes as the another kind of nitrogen substance of active principle, contain the acid amides-amine and the ester-amine of non-quaternary ammonium.The general material that uses is the product of a higher fatty acids and a polyamine species, and this polyamines is selected from hydroxyl Alkylenediamine and two alkylene triamine and composition thereof class.An example of this material, the product that is higher fatty acids and hydroxyethylethylene diamine is (referring to " condensation product of beta-hydroxyethyl ethylenediamine and aliphatic acid or its Arrcostab and in washing agent as the application of fabric softener " H.W.Eckert, Fette-Seifen-Anstrichmittel, in September, 1972, the 527-533 page or leaf).These materials are the active ingredient that plays emollescence in fabric softener with other cationic quaternary ammonium ammonium salt and imidazoline salt.[for example, can be referring to United States Patent (USP) 4,460,485(Rapisarda et al., on July 17th, 1984 delivered); 4,421,792(Rudy et al., deliver December 20 nineteen eighty-three); With 4,327,133(Rudy et al, deliver April 27 nineteen eighty-two)].
The various imidazolidine derivatives of everybody known use are as fabric finishing agent.For example, british patent specification 1,565,808(1980 is open April 23), a kind of fabric softener composition of being made up of a kind of aqueous dispersion of imidazoline ester derivative is disclosed.Similarly, the method for making of various imidazolidine derivatives is known for everybody.For example, referring to United States Patent (USP) 4,233,451(Pracht, on November 11st, 1980 delivered); United States Patent (USP) 4,189,593(Wechsler et al., on February 19th, 1980 delivered) and day disclosure special permission communique 61-291571.
United States Patent (USP) 4,661,269(Trinh et al., on April 28th, 1987 delivered), the fabric sofetening composition of the product that contains a higher fatty acids and a polyamine species is disclosed, this polyamines is selected from following compounds: hydroxyalkyl Alkylenediamine, two alkylene triamine and composition thereof, and the C that only contains the non-cyclic aliphatic of a long-chain
15-C
22The nitrogenous salt of the CATION of alkyl.
The various solutions of the problem that the concentrated fabric softnessization composition of the suitable family expenses of preparation is run on technology existing people propose.For example, referring to United States Patent (USP) 4,426,299(1984 delivered January 17) and 4,401,578(1983 delivered August 30), Verbruggen, this patent is about the paraffin that is used as viscosity modifier in the softener concentrate, aliphatic acid and ester class extender.
European patent 0,018,039(Clint et al., on March 7th, 1984 delivered), relate to the hydro carbons and soluble cation or the non-ionic surface active agent that in the softener concentrate, are used to improve viscosity and stability.
United States Patent (USP) 4,454,049(MacGilp et al., on June 12nd, 1984 delivered) the concentrated liquid fabric treatment composition of isotropic aqueous solution form is disclosed, wherein contain two-C that water miscible any hydroxyl replaces
16-C
24Alkyl, alkaryl or thiazolinyl cationic fabric softener.In this fabric softener at least about having 70% to be by having complete fusion temperature jointly at least at one or two kind of component more than 20 ℃, a kind of water-soluble nonionic extender (C particularly
10-C
40Hydro carbons or by monohydric alcohol or polyalcohol and C
8-C
24The ester class that aliphatic acid generates) but and a kind of water compatibility organic solvent form.This concentrate has the preparation stability and the dispersiveness of improvement, and good fabric sofetening conditioning performance.
United States Patent (USP) 4,439,330(Ooms, on March 27th, 1984 delivered) provided the concentrated fabric softener that contains the ethoxyquin amine.
United States Patent (USP) 4,476,031(Ooms, on October 9th, 1984 delivered) provided the ethoxyquin amine or its protonated derivative that are used with ammonium, imidazoline and similar substance.
Ethoxylated amine is well known (for example, referring to German patent application 2,829 as the application of the element of the first species in the softener composition, 022(Jakobi and Schmadel, on January 10th, 1980 is open) and 1,619,043(Mueller et al., on October 30th, 1969 is open) and United States Patent (USP) 4,076,632(Davis, on February 28th, 1978 delivered) and 4,157,307(Jaeger et al, on June 5th, 1979 delivered).
United States Patent (USP) 4,422,949(Ooms, deliver December 27 nineteen eighty-three) about softener concentrate based on chlorination two fat Dimethyl Ammonium (DTDMAC), glycerin monostearate and polycation.
In the United Kingdom's patent application 2,007,734A(Sherman et al., on May 23rd, 1979 is open) in, a kind of fabric softener concentrate is disclosed, contain by having at least one C
8-C
30The aliphatic quaternary ammonium salt of alkyl substituent and oil-soluble or water-insoluble basically and have a mixture that the compound of oil/fatty character is formed.It is said that this concentrate is dispersed/emulsified in easily in the cold water and forms the fabric sofetening composition.
The preparation of the concentrated dispersion of softener, as european patent application 406 and the United Kingdom's patent specification 1,601,360(Goffinet, on October 28th, 1981 is open) described, by carrying out in wherein adding the soft conditioning of some nonionic additives material.
As can be seen, prepare the various solutions of the specific question that is run in the fabric sofetening composition of the conc forms that is suitable for consumer's use, also be not entirely satisfactory.Usually all know, for example at United States Patent (USP) 3,681,241(Rudy, on August 1st, 1972 delivered) in, the existence of ionizable salt in softener helps to reduce viscosity really.But this method is invalid for the composition that contains the dispersion softener of having an appointment more than 12%, and this is because the content that viscosity is reduced to the required ionizable salt of enough degree has severe bad influence for the stability of product.
Have now found that, contain the two the fabric sofetening composition of mixture of the imidazoline ester of specific replacement and quaternised ester-ammonium salt, compare, have very high fabric sofetening opsonizing capacity with its each independent component.These compositions also have an advantage, promptly except that the height condensability with soft conditioning ingredients, are also keeping the fabric sofetening opsonizing capacity of height.In addition, before this, it seems that nobody expects that the mixture with these compounds is applied to laundering with in the fabric sofetening composition, people's soft compound (comprising concentrate) of also not knowing to contain the mixture of these compounds possesses desirable fabric softener/viscosity/performances such as stability/biological degradability is arranged simultaneously.
According to the present invention, it provides a kind of aqueous dispersion form, stable storage/biodegradable fabric sofetening composition, comprising:
(a) about 1% to about 20%(weight) quaternised ester-ammonium class softness conditioning compound, it is selected from following one group of compound:
And composition thereof, each R substituting group can be independently selected from C in the formula
1-C
6Alkyl, thiazolinyl or hydroxyalkyl; R
1Be C
14-C
22Alkyl; R
2Be C
13-C
21Alkyl; A
-For can with the anion of softening amendment compatibility;
(b) about 1% to about 35%(weight) a kind of imidazoline ester softness conditioning compound of replacement, its structural formula is as follows:
X and X in the formula
1Be respectively C
11-C
21Alkyl; M and n are about 2 to 4 respectively; Condition is that the total concentration of component (a) and the soft conditioning compound of component (b) is no more than about 40%(weight);
(c) about 60% to about 98% liquid-carrier.
As long as without being limited by theory, just can believe, ester moiety is given these soft conditioning compounds (being the imidazoline ester of quaternised ester-ammonium salt and replacement) with biological degradability, and in every kind of compound, has only a kind of fact of ester group, make it have enough hydrolytic stabilities, so that can be mixed with fluid composition under the disclosed below condition of the mixture of these compounds with being stabilized.
The composition that only contains quaternised ester-ammonium compounds is compared with the composition that only contains imidazoline ester compound, and typical earth surface reveals the soft opsonizing capacity of height.On the other hand, only contain the composition of imidazoline ester compound, compare, can under higher softener valid density, prepare with the composition that only contains quaternised ester-ammonium compounds.But, have been found that the composition that contains quaternised ester-ammonium compounds and the two mixture of imidazoline ester compound, compare with the softener of making by this class mixture with common technology, can have the soft opsonizing capacity of improvement.And this based composition can prepare under the condition of the soft conditioning compound of high concentration, keeps extra high soft opsonizing capacity simultaneously.
In addition, composition of the present invention is compared with the softener of two fat imidazolines etc. with containing common fabric softener such as chlorination two fat Dimethyl Ammonium (DTDMAC), has biological degradability more rapidly.
Because the quaternised ester-ammonium compounds that contains in the mixture is a cationic, this composition is not only given fiber and fabric with flexibility, and they also help and prevent static.
Fluid composition of the present invention with at PH about 2.0 to about 5.0 times preparations better, preferably arrives about 3.5 times preparations at PH about 2.0, so that stability for storage to be provided.
Here the contained soft conditioning compound of fluid composition preferably is to exist with the graininess that is dispersed in the liquid-carrier.The granularity of these particles is preferably less than 1 micron, and its average diameter is usually in the scope of about 0.10-0.50 micron.This particle dispersion can utilize the non-alkaline emulsifying agent, particularly nonionic extender of standard to come in addition stabilisation, and prevent precipitation.
Importantly, the fluid composition here is substantially free of (in general, by weight less than about 1%) free (promptly unprotonated) amine, because free amine can decompose by the soft conditioning compound of catalysis ester-ammonium in storage.If amine content is less, then they can be by protonated in the softener preparation.Strong acid such as H
3PO
4And HCl, can be used for this purpose.
The low viscosity that soft conditioning compound particle dispersion as described herein is had allows they are mixed with water-reducible fabric softener " highly enriched thing ", and it contains 15% to about 35% (weight) fabric sofetening accent active ingredient of having an appointment.This highly enriched thing can be packaged in the pouch easily, and the latter can be by user's dilute with water, with the softener (typical example is that the concentration of soft conditioning active ingredient is 3-8%) of producing " single intensity ".
Here said compound also can be mixed with solid, for example is mixed with graininess fabric sofetening and antistatic composition with pelleted substrate.Solid composite can contain 1% to about 40% the soft conditioning compound (a) of having an appointment, with about 1% to about 40% soft conditioning compound (b), the weight ratio of soft conditioning compound (a) and soft conditioning compound (b), better to arrive in about 1.5: 1 scope at about 0.04: 1.When being mixed with solid, pH value and have or not amine is certainly unlike strict for liquid softener, because the hydrolytic stability in storage is not so debatable.
Other solid composites here contain the compound that can be attached on the flaky material, thereby can be made into the fabric sofetening and the antistatic composition of sheet, and it can be used in the hot air dries machine of clothes.
The present invention also comprises and a kind of fiber (comprising hair) or fabric is carried out the softness conditioning, perhaps carries out the method for antistatic treatment again, comprises this fiber or fabric are contacted with disclosed this class softener in front.
Here all percentages, ratio and ratio, unless otherwise indicated, all by weight.
Composition of the present invention is based on a kind of discovery, the fabric composition of the aqueous solution form of soft the two mixture of conditioning compound (b) of imidazoline ester that promptly contains the soft conditioning compound (a) of quaternized ester-ammonium and replace, compare with this class mixture that utilizes a kind of common technology preparation, have the soft opsonizing capacity of improvement.And this composition can be prepared under the softness conditioning material conditions of high concentration, is keeping extra high soft opsonizing capacity simultaneously.This based composition has good storing stability, condensability and viscosity performance, and the biological degradability of height.Said composition is made up of mixture and a kind of liquid-carrier of the soft conditioning compound of two kind fabrics [be above-mentioned (a) and (b) two classes].The weight ratio of the soft conditioning compound of quaternised ester-ammonium (a) and the soft conditioning compound of the imidazoline ester that replaces (b), to about 1.5: 1 scope in, being advisable at about 0.04: 1, in about 0.25: 1 to about 0.7: 1 scope better.
The soft conditioning compound of quaternised ester-ammonium
The soft conditioning compound of the quaternised ester of main component-ammonium that the present invention is contained, fabric sofetening composition for dilution, for about 1% to about 20% being about 1% to about 4% better, for the fabric sofetening composition that concentrates, then be about 1% to about 5% better, this compound is selected from a following compounds:
And composition thereof, each R substituting group is the (C of a short chain in the formula
1-C
6, C preferably
1-C
3) alkyl, thiazolinyl or hydroxyalkyl, for example methyl (the most suitable), ethyl, propyl group, propenyl, ethoxy etc. or its mixture; R
1Be a long-chain C
14-C
22Alkyl, wherein C
16-C
18Alkyl is better, the C of long-chain
18Alkyl is best; R
2Be a long-chain C
13-C
21Alkyl, wherein C
13-C
17Alkyl is better, C
17Straight chained alkyl is best.Counter ion counterionsl gegenions A
-Here not being strict regulations, can be any anion that can match with soft conditioning compound, for example chlorion, bromide ion, methanesulfonate, formate, sulfate radical, nitrate radical etc.Self-evident, substituent R, R
1And R
2Can also can have side chain arbitrarily with various groups such as replacements such as alkoxyl, hydroxyl.In addition, R, R
1And/or R
2Also can select undersaturated (being thiazolinyl) arbitrarily for use.Can think that compound preferably is the monoester derivates (for example DTDMAC, a kind of widely used fabric sofetening conditioning compound) of two fat dimethyl ammoniums.
In enforcement of the present invention, as a kind of above-claimed cpd of effective soft conditioning component, be to use the standard reaction chemical preparation.For example, in the typical case of the soft conditioning compound of a kind of quaternized monoesters that above-mentioned (ⅰ) formula is represented was synthetic, molecular formula was RR
1NCH
2CH
2The amine of OH is R at the hydroxyl place with molecular formula
2C(O) acyl chlorides of Cl carries out esterification, carry out with a kind of alkyl halide RX then quaternized, to generate required product (R, R in the formula
1And R
2Definition such as the application described in).After the synthetic method of the soft conditioning compound of a kind of monoesters preferably will be disclosed in detail.But the people who is familiar with this chemical technology understands, adopts this reaction sequence, can extensively select the compound of desiring to make.As an illustration property and nonrestrictive example can be listed following several quaternized monoesters amine salt (all chain alkyl substituting groups all are straight chains in the formula):
[CH
3]
2[C
18H
37]
+NCH
2CH
2OC（O）C
15H
31Br
-
[CH
3]
2[C
18H
37]
+NCH
2CH
2OC（O）C
17H
35Br
-
[CH
3]
2[C
16H
33]
+NCH
2CH
2OC（O）C
17H
35Cl
-
[C
2H
5]
2[C
17H
35]
+NCH
2CH
2OC（O）C
13H
27Cl
-
[C
2H
5][CH
3][C
18H
37]
+NCH
2CH
2OC（O）C
14H
29CH
3SO
-
4
[C
3H
7][C
2H
5][C
16H
33]
+NCH
2CH
2OC（O）C
15H
31Cl
-
[iso-C
3H
7][CH
3][C
18H
37]
+NCH
2CH
2OC（O）C
15H
31I
-
Similarly, in the typical case of the represented soft conditioning compound of a kind of quaternized monoesters ammonium of above-mentioned (ⅱ) formula is synthetic, be R with a kind of molecular formula
2The aliphatic acid of COOH is R with a kind of molecular formula
1N(R)
2Thing uncle neutralize, and generates a kind of aliphatic acid-tertiary amine salt, and the latter reacts with chloropropylene oxide then, generates required product (R, R in the formula
1And R
2Definition as above).
A kind of synthetic method preferably of soft conditioning compound preferably will be after will being disclosed in detail.But the people who is familiar with chemical technology understands, adopts this reaction sequence, can extensively select the compound of desiring to make.
Quaternised 2-hydroxypropyl monoesters ammonium salt (wherein all chain alkyl substituting groups all the are straight chains) illustrative that some are available and nonrestrictive example is listed below:
[CH
3]
2[C
18H
37]
+NCH
2CH（OH）CH
2OC（O）C
17H
35Br
-
[CH
3]
2[C
16H
33]
+NCH
2CH（OH）CH
2OC（O）C
15H
31Cl
-
[C
2H
5]
2[C
17H
35]
+NCH
2CH（OH）CH
2OC（O）C
15H
31Cl
-
[C
2H
5][CH
3][C
18H
37]
+NCH
2CH（OH）CH
2OC（O）C
17H
35CH
3SO
-
4
[C
3H
7][C
2H
5][C
16H
33]
+NCH
2CH（OH）CH
2OC（O）C
15H
31Cl
-
[iso-C
3H
7][CH
3][C
18H
37]
+NCH
2CH（OH）CH
2OC（O）C
15H
31I
-
Because aforesaid compound is easy to hydrolysis a little, when using its compositions formulated here, care should be used to ground is handled.For example here, stable fluid composition, with preparation in about 2.0 to about 5.0 PH scope better, preparation is best in about 2.0 to about 3.5 PH scope.PH can regulate by adding Bronsted acid.The example of the Bronsted acid that is suitable for comprises inorganic mineral acid, carboxylic acid, particularly low-molecular-weight (C
1-C
5) carboxylic acid, also have alkyl sulfonic acid.The inorganic acids that is suitable for comprises HCL, H
2SO
4, HNO
3And H
3PO
4The organic acid that is suitable for comprises formic acid, acetate, methanesulfonic acid and ethyl sulfonic acid.Acids is hydrochloric acid and phosphoric acid preferably.
(ⅰ) the soft conditioning compound of the quaternised monoesters amine of class is synthetic
(ⅰ) synthetic with the soft conditioning compound of the quaternized monoesters amine of falling property of biology preferably in the class, can be undertaken by two following step processes:
Synthesizing of steps A amine
In the three-neck flask with 3 liters of 0.6 mole of octadecyl methyl (monoethanolamine) addings, this flask equipped is flow condenser, argon (or nitrogen) inlet and two charging hoppers once.In a charging hopper, 0.4 mole of triethylamine is housed, 0.6 mole palmitoyl chloride and 1: 1 solution of carrene are housed in another charging hopper.Carrene (750 milliliters) added contain in the flask of above-mentioned amine, and be heated to 35 ℃ (water-baths) and under agitation dropwise added triethylamine through one and a half hours, temperature is elevated to 40-50 ℃.Dropwise add palmitoyl chloride/dichloromethane solution, and heated overnight (12-16 hour) under 40-45 ℃ and in the inert atmosphere.
With the reactant mixture cool to room temperature, dilute with chloroform (1500 milliliters).The chloroformic solution of product is moved in the separatory funnel (4 liters), and with saturated NaCl solution, rare Ca(OH)
2Solution, 50%K
2CO
3Solution (3 times) * washing is at last with saturated NaCl washing.Organic layer is collected and uses MgSO
4Carry out drying, filter again, solvent is removed by rotary evaporation.Final drying (0.25mmHg) under high vacuum is finished.
* annotate: 50%K
2CO
3Layer should be under chloroform layer.
Analyze
The TLC(thin-layered chromatography) * *: solvent system (75% ether: Rf=0.7 25% hexane).
Infrared spectrum (ccl
4): δ 2910,2850,2810,2760,1722,1450,1370cm
-1
1H-nuclear magnetic resonance (CDClL
3): δ 2.1-2.5(8H), 2.1(3H), 1.20(58H), 0.9(6H) ppm(is a benchmark with tetramethylsilane=0ppm)
10 * 20 centimetres of pre-carved glass plates of *, 250 microns silica gel; Develop the color with phosphomolybdic acid colouring (5% phosphomolybdic acid ethanol solution).
Step B: quaternized
The octadecyl palm acyl-oxygen ethyl dimethylamine for preparing in the steps A is got 0.5 mole add in the autoclave sleeve, add 200-300 milliliter acetonitrile (anhydrous) simultaneously.Then sample is added in the autoclave, and uses the He(16275mmHg/21.4 atmospheric pressure) purge three times, use CH
3Cl purges once.Under the atmospheric pressure of 3604mmHg/4.7, reaction is heated to 80 ℃.With CH
3Cl and solvent are by discharging in the reactant mixture.Sample dissolution in chloroform, and is removed solvent by rotary evaporation, under high vacuum (0.25mmHg), carry out drying subsequently.C in this optimum compound
18H
37And C
17H
35Substituting group all is positive alkyl.
Analyze
TLC(5: 1 chloroform: * methyl alcohol): Rf=0.25
Infrared spectrum (ccl
4): δ 2910,2832,1730,1450cm
-1
1H-nuclear magnetic resonance (CDCl
3): δ 4.0～4.5(2H), 3.5(6H), 2.0～2.7(6H), 1.2～1.5(58H), 0.9(6H) ppm(is benchmark with tetramethylsilane=0ppm).
13C nuclear magnetic resonance (CDCL
3): δ 172.5,65.3,62.1,57.4,51.8,33.9,31.8,29.5,28.7,26.2,22.8,22.5,14.0(are benchmark with tetramethylsilane=0ppm).
(ⅱ) the soft conditioning compound of the quaternized monoesters amine of class is synthetic
(ⅱ) the soft conditioning compound of biodegradable preferably quaternized monoesters ammonium synthetic in the class, available following " still " method is carried out:
50 gram (0.175 mole) stearic acid and 80 gram isopropyl alcohols are added 500 milliliters be equipped with one and circle round in the three neck round-bottomed flasks of condenser, stir with a magnetic stirring bar then.52.7 gram (0.175 mole) dimethyl stearmides are added in the stearic acid-isopropanol mixture that stirs, add 30 gram water subsequently.With this mixture stir about 1/2 hour (till obtaining clear solution).Then, 18.4 gram (0.190 mole) chloropropylene oxides are added in this mixture.Temperature is elevated to 80 ℃ (oil baths), continues to stir 20 hours.
With the reactant mixture cool to room temperature, so there is a kind of white precipitate to form.Solid matter is collected in (use Buchner funnel) on the Whatman #1 filter paper, in (60 ℃) isopropyl alcohol of heat, is recrystallized then.Solid matter was carried out drying 24 hours under vacuum (0.2mmHg).
Analyze
The TLC(thin-layered chromatography): 10 * 20 centimetres of glass plates, 250 microns silica gel; Solvent system, chloroform: methyl alcohol: water (15: 6: 0.6; Volume/volume/volume); Colour developing; 5% phosphomolybdic acid ethanol solution; Rf=0.61.
Infrared spectrum (ccl
4): δ 3140,2920,2850,1958,1724,1525,1464,1210,1170cm
-1
1H-nuclear magnetic resonance (CDCl
3): δ 6.02(1H), 4.6-4.4(1H), 4.3-4.0(2H), 3.7-3.3(10H), 2.3(2H), 1.8-1.4(4H), 1.2(58H), 0.8(6H) ppm(is benchmark with the tetramethylsilane).
13C-nuclear magnetic resonance (CDCl
3): δ 173.4,66.4,66.0,65.9,63.5,52.5,52.4,34.3,31.9,29.7,29.5,29.3,29.2,26.6,25.0,22.7,22.6,14.1ppm(are as the criterion with tetramethylsilane).
The soft conditioning compound of the quaternized ester of other types-ammonium can selectively use arbitrarily at this as di esters etc.The example of these compounds comprises:
Z is in the formula
R, R
2And A
-Described as defined above.The soft conditioning compound of ester-ammonium that is intended to illustrate other types listed above, they can selectively be used for the present invention arbitrarily, and should not regard as restrictive or all-embracing.
The soft conditioning compound of the imidazoline ester that replaces
The soft conditioning compound of the contained key component substituted imidazoline ester of the present invention, for the fabric sofetening care composition of dilution,, better with about 4% to about 8% for about 1% to about 35%; For the fabric sofetening composition that concentrates, then its content is better with about 15% to 25%, and this compound has following structural formula:
X and X in the formula
1Be respectively C
11-C
21Alkyl is wherein with C
13-C
17Alkyl is better, with straight chain C
17Alkyl is best; M and n are respectively about 2 to about 4, are 2 better with m and n.The total concentration of soft conditioning active ingredient can not surpass about 40%(weight).Self-evident, substituent X and X ' can be at random with various groups such as alkoxyl, hydroxyl etc. replacement, can have side chain, but these materials are not preferred here yet.In addition, X and/or X
1Can be any unsaturated group (being thiazolinyl).The imidazoline ester softness conditioning compound that replaces preferably, the back will refer to the soft conditioning compound of dialkylimidazolium quinoline ester.
In enforcement of the present invention, be used as a kind of above-claimed cpd standard reaction chemical preparation of effective soft conditioning ingredients.For example, in a kind of typical case of the soft conditioning compound of imidazoline ester of the replacement with said structure formula (b) was synthetic, making molecular formula was that aliphatic acid and the molecular formula of XCOOH is NH
2-(CH
2) m-NH-(CH
2) the hydroxyl Alkylenediamine reaction of nOH, generate a kind of precursor of intermediate product imidazoline, then the latter and fatty acid methyl ester reaction with following molecular formula:
X
1COOCH
3
To generate required product (X, X in the formula
1, m and n definition such as the application described in).The synthetic method of the soft conditioning compound of a kind of quinoline of dialkylimidazolium preferably ester will be after will being disclosed in detail.But the people who is familiar with chemical technology understands, adopts this reaction sequence, can extensively select the compound of desire preparation.As an illustration property and nonrestrictive example, can point out following various dialkylimidazolium quinoline ester (all chain alkyl substituting groups all are straight chains in the formula): 1-stearoyl keto ethyl-2-imidazoline-based stearyl, 1-stearoyl keto ethyl-2-palmityl imidazoline, 1-stearoyl keto ethyl-2-myristyl imidazoline, 1-palm acyl-oxygen ethyl-2-nutmeg imidazoline, 1-stearoyl keto ethyl-2-fat imidazoline, 1-nutmeg acyl-oxygen ethyl-2-fat imidazoline, 1-palm acyl-oxygen ethyl-2-fat imidazoline, 1-cocoa butter acyl-oxygen ethyl-2-cocoa butter base imidazoline, 1-acyl oxygen ethyl-2-fat base imidazoline, and the mixture of these imidazolinium compoundss.
Synthesizing of the soft conditioning compound of dialkylimidazolium quinoline ester
Synthesizing of the soft conditioning compound of biodegradable preferably dialkylimidazolium quinoline ester that the present invention is used, available following method is carried out:
In the there-necked flask with 2 liters of 208.3 gram (2.0 moles) beta-hydroxyethyl ethylenediamines (aminoethyl cholamine) addings, add 426.8 gram (1.5 moles) stearic acid simultaneously.This flask purges with argon gas, and is equipped with reflux condenser, steams and to stay device and overhead.Reactant mixture is heated to 165 ℃ then, continues 18 hours.Subsequently, under 165 ℃ of 0.2mmHg and temperature, vacuumized 4 hours, simultaneously water and unnecessary amine are collected.With reactant mixture be cooled to 120 ℃ and add 447.8 the gram (1.5 moles) methyl stearates.Reaction temperature is elevated to 170 ℃, at this moment, reaction flask was vacuumized under 0.2mmHg pressure 22 hours.Above-mentioned reaction generates 1-stearoyl keto ethyl-2-imidazoline-based stearyl.
Analyze
TLC（90∶10∶1.5 CHCl
3/MeOH/NH
4OH）＊：Rf＝0.4。
Infrared spectrum (ccl
4): δ 2920,2850,1740,1615,1460/1455,1160cm
-1
1H-nuclear magnetic resonance (CDCl
3): δ 4.1-4.3(2H), 3.2-3.7(6H), 2.1-2.5(4H), 1.3(60H), 0.9-1.1(6H) ppn(is benchmark with tetramethylsilane=0ppm).
13C-nuclear magnetic resonance (CDCl
3): δ 173.3,61.6,52.2,50.1,45.5,34.0,31.8,29.5,27.6,26.3,24.7,22.5,13.9ppm(are benchmark with the tetramethylsilane).
* 10 * 20 centimetres of pre-carved glass plates, 250 microns.
5% ethanolic solution with the PMA(phosphomolybdic acid) chromogenic reagent.
The soft conditioning compound of the imidazoline of the replacement of other types can be arbitrarily selectively in this employing.The example of these compounds comprises:
X, X in the formula
1, m and n described as defined above.The soft conditioning compound of imidazoline that is intended to illustrate the replacement of other types listed above, they can selectively be used for the present invention arbitrarily, should not regard as restrictive or all-embracing.
Liquid-carrier
Composition of the present invention contains a kind of liquid-carrier, and for example water is (as being water and C
1-C
4Monohydric alcohol for example the mixture of ethanol, propyl alcohol, isopropyl alcohol, butanols and composition thereof is then better), isopropyl alcohol is better.These compositions contain 60% to about 98% the liquid-carrier of having an appointment, and are better with about 70% to about 95%.Preferably, the C in the liquid-carrier
1-C
4Monohydric alcohol content account for soft conditioning compound about 5% to about 50%(weight), the surplus of liquid-carrier is a water.
Therefore the used soft conditioning compound of the present invention is insoluble in this aqueous based carrier, here exists with the dispersion form of fine particle.These particles are below 1 micron, its average diameter with about 0.1 to about 0.5 micron better, stir preparation by high shear usually, this compound can be dispersed into fine particle.The method for making of dispersion will be disclosed in the embodiment I-III of back in detail preferably.In addition, because the existence of alkali should be carefully avoided in the easy hydrolysis of soft conditioning compound, and keep processing temperature and pH value within the scope of this specification regulation.
The particle dispersion of aforementioned type can utilize standard non-alkaline emulsifying agent, particularly nonionic extender selectively to carry out arbitrarily stabilisation, to prevent precipitation.These non-ionic precursors and consumption thereof, at United States Patent (USP) 4,454,049(MacGilp et al, on June 12nd, 1984 delivered) in open, disclosed content is as with reference to introducing the present invention.
Be applicable to the object lesson of the nonionic extender of composition of the present invention, comprise that (better with Neodol 23-3, it is a kind of C for glyceride (better with glycerol monostearate), fatty alcohol (for example octadecanol), ethoxyquin straight chain alcohol
12-C
13The product of straight chain alcohol and 3 moles of ethylene oxide condensations, Shell chemical Company sells) and composition thereof.The mixture particularly suitable of single stearic glyceride and Neodol 23-3.The typical amounts of non-ionic precursor when using (if) as composition about 0.1% to about 10%(weight).
Optional member
Prepare fabric sofetening composition completely, the soft conditioning compound of imidazoline ester except soft conditioning compound of the represented biodegradable quaternized ester of the chemical formula here-ammonium and replacement, and outside the liquid-carrier, also can selectively contain one or more following ingredients arbitrarily.
The soft conditioning of conventional quaternary ammonium reagent
Composition of the present invention also comprises a kind of soft conditioning of two (senior alkyl) quaternary ammonium reagent of routine.It is 0% to about 25%(better with about 0.1% to about 10% that softener of the present invention can contain) routine two (senior alkyl) quaternary ammonium softness nurse one's health reagent.
The present invention's used " senior alkyl " in the structure of the quaternary ammonium salt of routine refers to and have about 8 alkyl to about 30 carbon atoms, and be wherein better to about 22 carbon atoms with about 11.The example of the quaternary ammonium salt that these are conventional comprises:
(ⅰ) acyclic quaternary ammonium salt, its structural formula is as follows:
B in the formula
1Be non-cycloaliphatic C
15-C
22Alkyl; B
3Be C
1-C
4Saturated alkyl or hydroxyalkyl; B
4Be selected from B
1And B
3, A is an anion;
(ⅱ) diamides based quaternary ammonium salt, its structural formula is as follows:
B in the formula
1Be non-cycloaliphatic C
15-C
22Alkyl; B
2Alkylidene for divalence with 1 to 3 carbon atom; B
5And B
8Be C
1-C
4Saturated alkyl or hydroxyalkyl; A is a kind of anion;
(ⅲ) diamides base alkoxide quaternary ammonium salt, its structural formula is as follows:
N approximates 1 to 5 in the formula; B
1, B
2, B
5Described as defined above with A,
(IV) level Four imidazolinium compounds, its structural formula is as follows:
B in the formula
6Be C
1-C
4Saturated alkyl or H; Z is NH or O; B
1Described as defined above with A.
(ⅰ) dialkyl dimethyl ammonium salt be familiar with for everybody of the example of class component, for example chlorination two fat dimethylamine, methanesulfonic acid two fat dimethylamine, chlorination two (hydrogenated fat) dimethylamine, chlorination two mountain Yu base dimethylamine.
(ⅱ) and (ⅲ) example of class component can be enumerated methyl two (acyl amine ethyl) (2-ethoxy) amine mesylate and methyl two (hydrogenated fat acid amides ethyl) (2-ethoxy) amine mesylate.B in the formula
1Be non-annularity aliphatic C
15-C
17Alkyl; B
2Be ethylidene; B
5Be methyl; B
8Be hydroxyalkyl; A is the methanesulfonate anion; These materials can be by Sherex Chemical Company respectively with commodity Varisoft
222 and Varisoft
110 obtain.
(ⅳ) example of class component can be enumerated 1-methyl isophthalic acid-fat amino-ethyl-2-fat imidazoline mesylate and 1-methyl isophthalic acid-(hydrogenated fat acid amides ethyl)-2-fat imidazoline mesylate.
Unhindered amina
This fluid composition should be substantially free of (being lower than in general, about 1%) free (promptly unprotonated) amine.
A spot of protonated amine (general about 0.05% to about 1.0%), for example contain at least one one-level, secondary and tertiary amine class by the about 12 straight chain organic groups of forming to about 22 carbon atoms, can be used for composition of the present invention, improve dispersion stabilization.In these classes, amine is the ethyoxyl amine preferably, monoester-dimerization amine ethoxylate for example, and its each molecule has about 2 to 30 ethyoxyls.Two amines also are suitable for, fat-N for example, N ', N '-three (2-ethoxy)-1.3-propane diamine or C
16-C
18-alkyl-N-two (2-ethoxy) amine.The example of above-claimed cpd can be enumerated Hoechst AG with trade name GENAMIN C, S, these that O and T sell.
Must be noted that, if these amines are used for improving the dispersion stabilization of composition in a small amount, then in preparation their use acid carry out protonated, otherwise the decomposition that unhindered amina can the biodegradable soft conditioning compound of catalysis in storage.
Silicone components
The fabric sofetening composition here can selectively contain a kind of water-in-oil emulsion that is become to constitute by the polydialkysiloxane of straight chain or poly-alkaryl siloxanes basically arbitrarily, contained alkyl can contain 1 to 5 carbon atom, and can be and fluoridized wholly or in part.These siloxanes can help improving the feel of fabric.The siloxanes that is suitable for is a dimethyl silicone polymer, and its viscosity arrives about 100,000 centistokes for about 100 down at 25 ℃, is preferably about 1,000 to about 12,000 centistokes.
Have been found that the ionic charge characteristic of used siloxanes among the present invention, at the deposition degree and the distributed uniform degree of decision siloxanes, and the aspect of performance of the fabric of handling with its is very important.
Siloxanes with cationic characteristic has very big deposition tendency.Find have and improve the siloxanes that fabric feeling is worth, the straight chain characteristic is arranged basically, wherein better with polydialkysiloxane, contained alkyl is the most common with methyl.These siloxane polymers are usually used emulsion polymerization production industrial, adopt a kind of strong acid or strong alkali catalyst and nonionic or nonionic and anion mixed emulsifier system.Except that the feel of improving fabric, this silicone components has also improved the water imbibition of the fabric of crossing with softnessization compositions-treated of the present invention.
Optional silicone components comprises a kind of siloxanes with cationic characteristic, be defined as following several one of:
(a) two-C of straight chain basically
1-C
5Alkyl or C
1-C
5The alkaryl siloxanes makes with emulsion polymerization, with cationic or nonionic surface active agent as emulsifying agent;
(b) a kind of α-ω-two-quaternary ammoniated two-C
1-C
5Alkyl or C
1-C
5The alkaryl siloxane polymer; Or
(c) a kind of two-C of amino-functionalizing
1-C
5Alkyl or alkaryl siloxane polymer, contained about amino can be substituted, and can be quaternized; The degree of its replacement (d.s) is between about 0.0001 to 0.1, and is better with about 0.01 to about 0.075
Condition is, the viscosity of this siloxanes under 25 ℃ is about 100 to about 100,000 centistokes.
The fabric sofetening composition here can contain the silicone components up to about 15%, and is better with about 0.1% to about 10%.
Thickener
According to any selection, composition of the present invention contains 0% to about 3% the thickener of having an appointment, and is better with about 0.01% to about 2%.The example of the thickener that is suitable for can be enumerated: cellulose derivative, synthetic high polymer weight polymers (for example carboxyl vinyl polymer and polyvinyl alcohol) and cationic guar gum.
, having the cellulose derivative that increases to the agent function here, can be some cellulosic hydroxy ether, for example the Methocel that is sold by Dow Chemicals Inc.
, also have some cationic cellulose ether derivatives, for example the polymer JR-125 that sells by Union Carbide Corporation
, JR-400
And JR-30M
Other effective thickeners have cationic guar gum, for example the Jaguar Plus that is sold by Stein Hall company
; Gendrive458 by General Mills sale
The thickener preferably here can be selected from following one group of compound: methylcellulose, hydroxypropyl methylcellulose, hydroxy butyl methyl cellulose or its mixture.The viscosity of 2% aqueous solution under 20 ℃ of above-mentioned cellulosic polymer is about 15 to about 75,000 centipoises.
Soil release agents
According to selection arbitrarily, composition of the present invention contains 0% to about 10% soil release agents, and is better with about 0.2% to about 5%.This soil release agents is better with polymer.Be applicable to that the polymer soil release agents among the present invention comprises copolymer block of terephthalate and poly(ethylene oxide) or poly(propylene oxide) etc.
Soil release agents is the copolymer that contains terephthalate and poly-ethylene oxide block preferably.More particularly, these polymer are made of the repetitive of Polyethyleneglycol Terephthalate and polyoxyethylene terephthalate, and the Polyethyleneglycol Terephthalate unit wherein and the mol ratio of polyoxyethylene terephthalate unit are about 25: 75 to 35: 65.Above-mentioned poly terephthalic acid oxygen vinyl acetate contains poly-ethylene oxide block, and the molecular weight of these blocks is about 300 to about 2000.The molecular weight of this polymer soil release agents is positioned at about 5.000 in about 55,000 scope.
Another kind of better polymerization thing soil release agents is a kind of crystallizable, polyester with Polyethyleneglycol Terephthalate repetitive, it contains have an appointment (weight) Polyethyleneglycol Terephthalate unit of 10% to about 15% and (weight) polyoxyethylene terephthalic acid units of about 10% to about 50%, by mean molecule quantity is that about 300 to about 6,000 polyoxyethylene glycol constitutes; In crystallizable polymer, the mol ratio of Polyethyleneglycol Terephthalate unit and polyoxyethylene terephthalate unit is between 2: 1 and 6: 1.The example of this polymer can be enumerated the product Zelcon of commercial sale
4780(E.I.Du Pont Company produces) and Milease
T(Imperial Chemical Industries produce).
Good soil release agents is the polymer with following general formula:
X can be any suitable end-capping group in the formula, and the optional free H of each X and about 1 is to the alkyl of about 4 carbon atoms or one group of group of acyl group composition; N chooses according to water-soluble, is generally about 6 to about 113, and is better with about 20 to about 50; U is very important for the preparation of the quite high fluid composition of ionic strength.The u value is rarely found greater than 10 material.In addition, the u value should be at least 20% at the content of about 3 to about 5 material, and is better with at least 40%.
D
1Part is 1 substantially, the 4-phenylen moiety.Just as used herein, " D
1Part mainly is 1,4-phenylen moiety * " the words is meant some compounds, wherein D
1Part is fully by 1, and the 4-phenylen moiety is formed, and perhaps part is replaced by other arlydene or alkyl arylene part, alkylene moiety, alkenylene part or its mixture.Can partly replace 1, the arlydene of 4-phenylene and alkyl arylene partly comprise 1,3-phenylene, 1,2-phenylene, 1,8-naphthylene, 1,4-naphthylene, 2,2-diphenylene, 4,4-diphenylene and composition thereof.Can partly replace 1, the alkylidene of 4-phenylene and alkenylene part comprise ethylidene, 1,2-propylidene, 1,4-butylidene, 1,5-pentylidene, 1,6-hexa-methylene, 1,7-heptamethylene, 1,8-eight methylene, 1,4-cyclohexylidene and composition thereof.
For D
1Part, with 1, the part beyond the 4-phenylene is carried out the degree that part replaces, and should avoid the soil release performance of this compound to be had influence on any huge stage nocuously.In general, the part that can allow replaces degree, the backbone length on this compound is decided, and 1 in the promptly long main chain, the 4-phenylen moiety can partly be replaced morely.Usually, D
1Value for about 50% to about 100% 1, the 4-phenylen moiety (contain 0 to about 50% non-1, the 4-phenylen moiety) compound of composition has suitable soil releasability.For example, by the present invention, the polyester that is made by the M-phthalic acid (1, the 3-phenylene) and the terephthalic acid (TPA) (1, the 4-phenylene) of 40: 60 mol ratios has suitable soil releasability.But, because most of polyester comprise the Polyethyleneglycol Terephthalate unit in the fiber manufacturing, to wish usually to reduce with 1 as far as possible, the part beyond the 4-phenylene is carried out the degree that part replaces, to obtain best soil releasability.D
1Part with fully (promptly 100%) by 1,4-phenylen moiety composition, i.e. each D
1Part all is 1, and the 4-phenylene is better.
For D
2Part, the suitable ethylidene or the ethylidene of replacement partly comprise ethylidene, 1,2-propylidene, 1,2-butylidene, 1,2-hexylidene, 3-methoxyl group-1,2-propylidene and composition thereof etc.D
2Part is to be mainly ethylidene part 1, and 2-propylidene part or its mixture are better.The soil that the ethylidene that contains big percentage partly helps to improve compound discharges active.Surprisingly, contain 1 of big percentage, 2-propylidene part helps to improve the water-soluble of this compound.
Therefore, wish to adopt 1,2-propylidene part or similarly any pith in the soil release component in branched chain type group and the liquid fabric softening composition match.D
2About 75% to about 100% is 1 in the part, and 2-propylidene part is better, and about 90% is better to 100%.
Each n value is at least about 6, wherein to be at least about 10 better.Each n arrives in about 113 the scope about 12 usually.Typical situation is that each n value is positioned at about 12 to about 43 scope.
Opener about these good soil release agents has been included in european patent application 185, and 427(Gosselink, on June 25th, 1986 is open) in, it is as with reference to introducing the present invention.
Viscosity modifier
In composition of the present invention, can use viscosity modifier (better in the composition that concentrates).The example of organic viscosity modifier has aliphatic acid and ester class, fatty alcohol and water miscible solvent such as short chain alcohol etc.The example of inorganic viscosity modifier has water-soluble ionogenic salt etc.There is multiple ionogenic salt to use.The example of the salt that is suitable for comprises the halide of I A and II A family metal in the natrium citricum and the periodic table of elements, for example calcium chloride, magnesium chloride, sodium chloride, potassium bromide and lithium chloride.Better with calcium chloride and natrium citricum.Ionogenic salt is specially adapted in the mixed process of each composition, with the preparation cost inventive compositions, and then the viscosity of acquisition institute's phase.The consumption of ionizable salt is decided on the quantity of used active ingredient in the composition, and can adjust according to prescription designer's requirement.The typical amounts that is used to regulate the salt of softener composition viscosity is about 20 to about 3.000ppm of a composition weight, arrives approximately 2 with 20, and 000ppm is better.
Except playing the viscosity adjustment effect, above-mentioned ionogenic salt also has electrolytical function, can further improve the stability of the present composition.Electrolyte is a calcium chloride preferably, used electrolytical typical amounts be composition weight about 20 to about 3.000ppm, arrive approximately 2 with about 20,000ppm is better.
Bactericide
The example that is used for the bactericide of composition of the present invention comprises glutaraldehyde, formaldehyde, 2-bromo-2-nitro-propane-1,3-glycol etc.(by the Inolex Chemicals company that is positioned at Philadelphia, guest sunset state with commodity Bronopol
Sell), or 5-chloro-2-methyl-4-isothiazoline-3-ketone and 2-methyl-4-isothiazoline-3-ketone are (by Rohm and Haas Company (US) Independenec Mall West, Philadelphia, Pennsy Lvania 1 with commodity Kathon
CG/ICP now sells).The typical amounts that is used for the bactericide of composition of the present invention be about composition weight 1 to about 1,000ppm.
Other select composition for use
The present invention can comprise other available compositions that are generally used in the fabric treatment composition, for example colouring agent, spices, preservative agent, fluorescent whitening agent, opacifier, fabric finishing agent, surfactant, stabilizing agent such as guar gum and polyethylene glycol, anti-piping compound, anti-creasing agent, cockline agent, spot agent, bactericide, mould inhibitor, antioxidant such as Yoshinox BHT, preservative agent etc.
Aspect method of the present invention, with fabric or fiber (comprising hair) and effective quantity, be generally about 20 to about 300 milliliters (per 3.5 kilograms of processed fibers or fabric) compositions of the present invention and in aqueous solution bath, contact.Certainly, its consumption is according to user's judgement, decides on the type of concentration, fiber or the fabric of composition, desired pliability etc.Typical situation is with in the potcher, to add 8% dispersion of this about 120～250 milliliters softness conditioning compound one 25 liters launderings in 3.5 gram mixtures.Better to 250ppm fabric sofetening composition of the present invention in the potcher to contain the 100ppm that has an appointment.
Also available solid carrier material replaces liquid.For example, soft conditioning compound of the present invention can be absorbed in granular solids for example on potassium sulfate, micronizing silica, the agramon etc., and adds laundering with in the potcher.Perhaps, this softness conditioning compound can be layered on the thin slice (for example paper handkerchief, nonwoven fabric etc.), and the fabric with humidity rolls in the hot-air fabric drying machine, known BOUNCE in the similar commerce of its mode
The drying machine product of the trade mark.In general, the composition of this solid form contains 1% to the about 20% biodegradable soft conditioning compound and about 75% of having an appointment to about 99% solid carrier.
Following embodiment can illustrate enforcement of the present invention, but is not for restriction of the present invention.
Embodiment 1
A kind of stable storage of the present invention, biodegradable fabric sofetening preparation of compositions is as follows:
Component percentage (weight)
Isopropyl alcohol 2.0%
Bronopol
0.01%
Dyestuff 20ppm
HCl 0.30%
Cacl
20.02%
Water surplus
The soft conditioning compound of 20 gram biodegradable quaternised monoesters-ammonium, the soft conditioning compound of the biodegradable dialkylimidazolium quinoline ester of 20 grams and 15 gram isopropyl alcohols are mixed and be heated to 80 ℃, fluidised to generate " melt ".Mixture with fusing in one 460 water seat that restrains of impouring, wherein also contains 1.5 gram HCl under the stirring of high shearing then.With water preheat to 70 ℃, before stirring with 20ppm blue dyes and 100ppm Bronopol
Add in the entry.Before in the mixture impouring water of fusing, by evaporating about 2 gram isopropyl alcohols in this mixture.With speed stirring 15 minute (the Tekmar trade mark high shearing blender) of dispersion with 7000 rev/mins.The temperature of dispersion remains on 70～75 ℃ with cooling bath in stirring.Add 0.5 gram CaCL
2(with the form of 5% solution) stirs simultaneously to reduce viscosity.The viscosity of the dispersion that generates is about 100 centipoises (25 ℃ time), and PH is about 3.7, contains free (promptly unprotonated) amine of having an appointment below 1%.Particle mean size in the dispersion is generally about 0.30 micron.
At another kind preferably in the embodiment, can comprise according to the composition of said procedure preparation: 3.0%(weight) the soft conditioning compound of biodegradable quaternised monoesters ammonium; 5.0%(weight) the soft conditioning compound of biodegradable dialkylimidazolium quinoline ester; 2.0%(weight) isopropyl alcohol; 0.01%(weight) Bronopol
; The 20ppm dyestuff; 0.30%(weight) HCl; 0.20%(weight) CaCl
2; Surplus is a water.
Example example II
A kind of stable storage of the present invention, biodegradable fabric sofetening preparation of compositions is as follows:
Component percentage (weight)
Isopropyl alcohol 1.5%
Dimethyl silicone polymer (PDMS) 1.0%
HCl 0.5%
Cacl
20.03%
Water
Surplus
The soft conditioning compounds of the monoesters-ammonium of 15 gram biodegradable quaternary ammoniumizations, the 30 biodegradable dialkylimidazolium quinoline esters of gram and 9.5 gram isopropyl alcohols are mixed and be heated to 75 ℃, fluidised to generate " melt ".Mixture with fusing adds under the stirring of high shearing in the water seat of one 450 gram then.Earlier with water preheat to 70 ℃, and before stirring, in water, add 2.5 gram HCL and 5 gram PDMS.Before in the mixture impouring water of fusing, from this mixture, evaporate earlier about 2 gram isopropyl alcohols.With speed stirring 15 minute (the Tekmar trade mark high shearing agitator) of dispersion at 7000 rev/mins.In stirring, the temperature of dispersion is remained between 70～75 ℃ with cooling bath.In stirring, add 0.15 gram CaCL
2(with the form of 5% solution) is to reduce viscosity.The viscosity that generates dispersion is about 80 centipoises (25 ℃ time), and PH is about 3.9, contains (promptly unprotonated) amine that dissociates of having an appointment 1% below.Particle mean size in the dispersion generally is about 0.25 micron.
The embodiment III
The biodegradable concentrated fabric softnessization preparation of compositions of a kind of stable storage of the present invention is as follows:
Component percentage (weight)
Isopropyl alcohol 3.0%
HCl 1.0%
CaCl
20.1%
Water surplus
The biodegradable quaternised monoesters of 30 grams-soft conditioning compound of ammonium, the 70 biodegradable dialkylimidazolium quinoline esters of gram and 19 gram isopropyl alcohols are mixed, and be heated to 75 ℃, fluidised to form " melt ".Then under the stirring of high shearing in the water seat with one 400 of this fusion mixture impouring gram.Water is preheating to 70 ℃ earlier, and adds 5 gram HCL in stirring forward direction water.Before the mixture impouring water of fusing, from this mixture, evaporate earlier about 4 gram isopropyl alcohols.With 7000 rev/mins speed dispersion is stirred 15 minutes (the high shearing agitator of the Tekmar trade mark).In stirring, the temperature of dispersion is remained between 70～75 ℃ with cooling bath.Under agitation add 0.5 gram CaCL
2(5% solution) is to reduce viscosity.The viscosity of the dispersion that generates is about 90 centipoises (25 ℃ time), and PH is about 2.8, contains (promptly unprotonated) amine that dissociates 1% below.Particle mean size in this dispersion generally is about 0.3 micron.
Under common pattern, this composition that concentrates is packaged in a kind of simple plastic bag, before using it is opened in the water that closes 4 times of volumes of impouring, to be made into the softness composition of " uniform intensity ", thereby saved packing and shipping charges usefulness, and storage space.
The embodiment IV
The biodegradable fabric sofetening preparation of compositions of a kind of stable storage of the present invention is as follows:
Component percentage (weight)
Dimethyl silicone polymer (PDMS) 0.5%
Polyethylene glycol 1.2%
Dyestuff 60ppm
HCl 1.0%
CaCl
20.2%
0.75%
Water surplus
The biodegradable quaternised monoesters of 25 grams-soft conditioning compound of ammonium, the soft conditioning compound of the biodegradable dialkylimidazolium quinoline ester of 25 grams are stirred and are heated to 80 ℃, fluidised to form " melt ".Under the stirring of high shearing, one of this fusion mixture impouring is contained in the 360 gram water seats of 7.5 gram HCL then.Earlier with water preheat to 70 ℃, and before stirring, 15 gram PDMS and 60ppm blue dyes are added in the entry.Under 7000 rev/mins speed, dispersion is stirred 15 minutes (the high shearing agitator of the Tekmar trade mark).During churning, remain between 70～75 ℃ with the temperature of cooling bath this dispersion.When stirring, add 1 gram CaCL
2(with the form of 5% solution) is to reduce viscosity.After dispersion has been cooled to 38 ℃, add 6 gram polyethylene glycol (with the form of 50% solution) and 3.75 gram spices, simultaneously with 5000 rev/mins speed stirring 1 minute.The viscosity of the dispersion that generates is about 100 centipoises (25 ℃ time), and PH is about 2.8, contains (promptly unprotonated) amine that dissociates 1% below.The particle mean size of dispersion generally is about 0.3 micron.
The embodiment V
The biodegradable fabric sofetening preparation of compositions of a kind of stable storage of the present invention is as follows:
Component percentage (weight)
Isopropyl alcohol 1.5%
Bronopol
100ppm
Dyestuff 120ppm
HCl 3.0%
Natrium citricum 2000 ppm
Spices 0.75%
Water surplus
The biodegradable quaternised monoesters of 10 grams-soft conditioning compound of ammonium, the soft conditioning compound of the biodegradable dialkylimidazolium quinoline ester of 150 grams and 10.5 gram isopropyl alcohols are stirred and are heated to 80 ℃, fluidised to form " melt ".One of the impouring under the stirring of high shearing of mixture after will melting then contains in the 285 gram water seats of 15 gram HCL.With water preheat to 70 ℃, before stirring with 120ppm blue dyes and 100ppm Bronopol
Add in the entry.Before in the mixture impouring water of fusing, from this mixture, evaporate about 3 gram isopropyl alcohols.Under 7000 rev/mins speed, dispersion is stirred 15 minutes (the high shearing agitator of the Tekmar trade mark).During churning, remain between 70～75 ℃ with the temperature of cooling bath dispersion.Under agitation add 1 gram natrium citricum (with the form of 5% solution), to reduce viscosity.After dispersion has been cooled to 38 ℃, add 3.75 gram spices, stirred 1 minute with 5000 rev/mins speed simultaneously.The viscosity of the dispersion that generates is about 30 centipoises (25 ℃ time), and PH is about 2.8, contains (promptly unprotonated) amine that dissociates 1% below.The particle mean size of dispersion generally is about 0.25 micron.
Usually, the liquid fabric softening composition in the various embodiments described above is added in the rinse cycle of washing machine commonly used.When adopting repeatedly rinsing, the fabric sofetening composition is to add better in the rinsing the last time.The quantity that adds in rinse cycle is generally about 20 milliliters to the about 300 milliliters compositions (with the dilution kind in the embodiment III) in (per 3.5 kilograms of processed fabrics) embodiment I～II.
Importantly, above-mentioned various biodegradable fluid composition (embodiment I～V) all has good soft opsonizing capacity, the low viscosity under normal temperature and higher temperature, good product stability and concentrated property, dispersiveness for natural and synthetic textiles.
The embodiment VI
The fabric sofetening that is used for the hot-air cloth drying machine is nursed one's health being prepared as follows of sheet:
Fabric finishing agent component percentage (weight)
Single-stearic acid dehydration sorb ester 46.0%
Clay 7.0%
Spices 1.0%
Drying machine flake substrate softener
Rayon fibers 70.0%
Polyvinyl acetate 30.0%
[10 " * 14 " (35.6 centimetres of 25.4 cm x) sheet, 1.4 grams]
With the soft conditioning compound of biodegradable quaternised monoesters-ammonium, the soft conditioning compound of biodegradable dialkylimidazolium quinoline ester, single-stearic acid dehydration sorb ester, clay (Bentolite L, a kind of montmorillonite clay, from Southern Clay Products company) and spices stir and be heated to 80 ℃, to form fluidization " melt ".Then matrix (being made by spiral entangle fiber and polyvinyl alcohol) is coated with active ingredient and dried overnight with about 4 gram fusings.So just make fabric finishing agent: the weight ratio of dry matrices is about 3.
After fabric finishing agent solidifies, matrix is cut with a knife out, above-mentioned otch is parallel to each other basically, one side and by in being stretched over of above-mentioned at least matrix about 1 inch (2.5 centimetres).The width of each otch is about 0.2 inch (0.5 centimetre).The fabric that this drying machine is handled with the desire of humidity with the softener sheet joins (typical situation is per 3.5 kilograms of fabric a slices, dry weight base) in the cloth drying machine.The heating and the rolling action of the dryer rotary drum that rotates are distributed to softener on whole fabrics equably, and with fabric drying.The softness conditioning and the Electrostatic Control of fabric have so also just been finished.
Claims (24)
1, conditioning of a kind of fabric sofetening of liquid and antistatic composition, comprising:
(a) about 1% to the soft conditioning compound of the quaternised ester of about 20% (weight)-ammonium, and this compound is selected from following one group of compound:
And composition thereof, each R substituting group is selected from C respectively in the formula
1-C
6Alkyl, thiazolinyl or hydroxyalkyl; R
1Be a C
14-C
22Alkyl; R
2Be a C
13-C
21Alkyl; A
-The anion that matches for a kind of and soft conditioning compound;
(b) about 1% to the soft conditioning compound of the imidazoline ester of about 35% (weight) replacement, and its structural formula is as follows:
X and X ' are respectively C in the formula
11-C
21Alkyl; M and n are respectively about 2 to about 4; Condition is that the total concentration of component (a) and the soft conditioning compound of component (b) is no more than about 40% (weight); And
(c) about 60% to about 98% liquid-carrier.
2, according to the composition of claim 1, wherein, each R substituting group is C
1-C
3Alkyl; R
1Be C
16-C
18Alkyl; R
2Be C
13-C
17Alkyl; X and X
1Be respectively C
13-C
17Alkyl; M and n are 2.
3, according to the composition of claim 2, wherein, liquid-carrier contains the mixture of being made up of following compounds:
(a) C
1-C
4-unit alcohol or its mixture
(b) water;
The quantity of monohydric alcohol is about 5% to about 50% of soft conditioning compound weight.
4, according to the composition of claim 3, wherein, monohydric alcohol is an isopropyl alcohol.
5, according to the composition of claim 2, wherein, soft conditioning compound is the particle form that is dispersed in the liquid-carrier.
6, according to the composition of claim 5, wherein, the average diameter of particle is about 0.1 to about 0.5 micron.
7, according to the composition of claim 6, it is substantially free of not protonated amines.
8, according to the composition of claim 7, it is preparation in about 2.0 to about 5.0 o'clock at PH.
9, composition according to Claim 8, wherein, the soft conditioning compound of quaternised ester-ammonium (a) arrives in about 1.5: 1 scope at about 0.04: 1 with the ratio of the soft conditioning compound of the imidazoline ester that replaces (b).
10, according to the composition of claim 9, it is preparation between about 2.0 to about 3.5 at PH.
11, according to the composition of claim 9, it also contains 0.1% to the about 10% soft conditioning of two-(senior alkyl) the quaternary ammoniums reagent commonly used of having an appointment.
12, according to the composition of claim 9, it contains soft conditioning compound (a) of 1% to the about 4% quaternised ester of having an appointment-ammonium and the soft conditioning compound (b) of about 4% to about 8% imidazoline ester that replaces.
13, according to the composition of claim 12, wherein, the soft conditioning compound of quaternised ester-ammonium (a) (ⅰ) is
And the soft conditioning compound of the imidazoline ester that replaces (b) is
14, according to the composition of claim 9, it contains has an appointment 1% to about 5%(weight) the soft conditioning compound (a) of quaternised ester-ammonium and about 15% is to about 25%(weight) the imidazoline ester softness conditioning compound (b) of replacement.
15, according to the composition of claim 14, wherein, the soft conditioning compound of quaternised ester-ammonium (a) (ⅰ) is
And the soft conditioning compound of the imidazoline ester that replaces (b) is
16, according to the composition of claim 9, it also contains has an appointment 0.1% to about 10%(weight) the nonionic extender.
17, according to the composition of claim 16, wherein, the nonionic extender is selected from glyceride, fatty alcohol, ethoxyquin straight chain alcohol and composition thereof.
18, according to the composition of claim 9, it also contains a kind of about 20 to about 3000ppm salt, and this salt is selected from calcium chloride, magnesium chloride, sodium chloride, potassium chloride, lithium chloride and composition thereof.
19, according to the composition of claim 18, salt wherein is calcium chloride.
20, composition according to Claim 8, the ratio of the soft conditioning compound of imidazoline ester (b) of soft conditioning compound of wherein quaternised ester-ammonium (a) and replacement about 0.25: 1 to about 0.7: 1.
21, conditioning of a kind of fabric sofetening of solid form and antistatic composition, comprising:
(a) about 1% to about 40%(weight) the soft conditioning compound of quaternised ester-ammonium, this compound is selected from and contains following one group of compound:
And composition thereof, the R substituting group is selected from C respectively in the formula
1-C
6Alkyl, thiazolinyl or hydroxyalkyl; R
1Be C
14-C
22Alkyl; R
2Be C
13-C
21Alkyl; A
-Be the anion that cooperates with soft conditioning compound;
(b) about 1% to about 40%(weight) the imidazoline ester softness conditioning compound that replaces, its structural formula is as follows:
X and X in the formula
1Be respectively C
11-C
22Alkyl; M and n are respectively about 2 to about 4;
(c) a kind of solid carrier;
Above-mentioned soft conditioning compound can break away from or discharge the ground subsides and be bonded on the above-mentioned solid carrier.
22, according to the composition of claim 21, wherein, the soft conditioning compound of quaternised ester-ammonium (a) is about 0.04: 1 to about 1.5: 1 with the ratio of the soft conditioning compound of the imidazate that replaces (b).
23, according to the composition of claim 21, wherein, solid carrier is a flake substrate.
24, a kind of fabric is carried out softness conditioning and antistatic finish method, it is with above-mentioned fabrics and effective quantity, and the composition in the claim 1 contacts to be finished.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US19954288A | 1988-05-27 | 1988-05-27 | |
| US199,542 | 1988-05-27 | ||
| US34429289A | 1989-05-01 | 1989-05-01 | |
| US07/344292 | 1989-05-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1040835A true CN1040835A (en) | 1990-03-28 |
Family
ID=26894878
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89103608 Pending CN1040835A (en) | 1988-05-27 | 1989-05-27 | The fabric sofetening composition that contains getting imidazoline ester and quaternized ester-ammonium salt mixture |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1040835A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101463561B (en) * | 2007-12-21 | 2011-12-28 | 上海和黄白猫有限公司 | Whitening and brightening softening agent |
| CN105829600A (en) * | 2013-12-27 | 2016-08-03 | 陶氏环球技术有限责任公司 | Textile treatment compositions including quternary bis-imidazoline compounds derived from linear tetramines useful to improve moisture management and provide antimicrobial protection |
-
1989
- 1989-05-27 CN CN 89103608 patent/CN1040835A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101463561B (en) * | 2007-12-21 | 2011-12-28 | 上海和黄白猫有限公司 | Whitening and brightening softening agent |
| CN105829600A (en) * | 2013-12-27 | 2016-08-03 | 陶氏环球技术有限责任公司 | Textile treatment compositions including quternary bis-imidazoline compounds derived from linear tetramines useful to improve moisture management and provide antimicrobial protection |
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