EP0634475B1 - Flüssiges Wäscheweichspülerkonzentrat - Google Patents

Flüssiges Wäscheweichspülerkonzentrat Download PDF

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Publication number
EP0634475B1
EP0634475B1 EP94202049A EP94202049A EP0634475B1 EP 0634475 B1 EP0634475 B1 EP 0634475B1 EP 94202049 A EP94202049 A EP 94202049A EP 94202049 A EP94202049 A EP 94202049A EP 0634475 B1 EP0634475 B1 EP 0634475B1
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Prior art keywords
composition
weight
softening
formula
carbon
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EP94202049A
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English (en)
French (fr)
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EP0634475A2 (de
EP0634475A3 (de
Inventor
Amjad Farooq
Regis Cesar
Francoise Deville
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Colgate Palmolive Co
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Colgate Palmolive Co
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Priority claimed from US08/213,308 external-priority patent/US5501806A/en
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Publication of EP0634475A3 publication Critical patent/EP0634475A3/de
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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
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • C11D3/0015—Softening compositions liquid
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/46—Esters of carboxylic acids with amino alcohols; Esters of amino carboxylic acids with alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/528—Carboxylic amides (R1-CO-NR2R3), where at least one of the chains R1, R2 or R3 is interrupted by a functional group, e.g. a -NH-, -NR-, -CO-, or -CON- group
    • 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

Definitions

  • This invention relates to liquid fabric softening compositions. More particularly, the invention relates to super concentrated liquid fabric softening compositions which are effective in softening fabrics in both soft and hard water and which are primarily intended as rinse cycle fabric softening compositions ready-for-use and dilute before use, including both products.
  • compositions containing quaternary ammonium salts or imidazolinium compounds having at least one long chain hydrocarbyl group are commonly used to provide fabric softening benefits when used in a laundry rinse operation. Numerous patents have been issued for these types of compounds and compositions.
  • RNH((CH 2 ) n NR) m R wherein an average of from 20% to 80% of the R groups are C 12 to C 22 acyl, at least 20% of the R groups are -CH 2 CH 2 OH or -CH 2 CHOHCH 3 or mixtures of these groups, and any other R group is hydrogen, n is 2 or 3 and m is an integer of from 2 to 5, are provided as mobile pastes in the presence of lower alkanol solvents.
  • US-A-5,154,838 discloses an aqueous liquid softener composition based on an amidoamine compound which is the condensation reaction product of a di- or tri-amine of formula (I): R 1 NH(C m H 2m NH) n H with a fatty acid of formula (II): wherein R 1 represents a straight or branched chain, saturated or unsaturated hydrocarbon group having 8 to 24 carbon atoms, R 2 represents a straight or branched, saturated or unsaturated hydrocarbon group having 7 to 23 carbon atoms, m represents 2 or 3, and n is 1 or 2.
  • R 1 represents a straight or branched chain, saturated or unsaturated hydrocarbon group having 8 to 24 carbon atoms
  • R 2 represents a straight or branched, saturated or unsaturated hydrocarbon group having 7 to 23 carbon atoms
  • m represents 2 or 3
  • n is 1 or 2.
  • polyamines e.g., diethylentriamine, aminoethyl ethanolamine
  • fabric softening compositions which are aqueous dispersions of a fatty acid ester quat of formula: where one or two R groups represent an aliphatic ester residue of from 12 to 30 carbon atoms of formula CH 2n OCOR 4 , and the remaining R groups represent lower aliphatic, aryl or hydroxyalkyl groups, X - is an anion and "a" represents the ionic valence of the anion, and a fatty acid amidoamine softener of formula: where R 1 is a C 12 to C 30 alkyl or alkenyl group, R 2 represents R 1 ,R 1 CONH(CH 2 ) m or CH 2 CH 2 OH; R 3 represents hydrogen, methyl, or (CH 2 CH 2 O) p H, m is a number of 1 to 5 and p is a number of 1 to 5, at a weight ratio of ester quat to amidoamine of from 10:1
  • the mixture of the soft-rinsing agent (a) and (b) constitutes from 10 to 25% by weight of the composition at ratios of (a):(b) of from 1:9 to 9:1.
  • the alkyl groups in R 7 and R 9 are preferably completely saturated.
  • Viscosity control agents including electrolyte salts, e.g., calcium chloride, may be included.
  • a dispersing aid e.g., HCl
  • quaternary ammonium salt e.g., diamido (alkoxylated) quaternary ammonium salts.
  • electrolyte e.g., CaCl 2
  • EP-A-0295386 discloses a free-flowing softening washing rinse concentrate containing (a) from 18 to 50 weight percent of a mixture of at least two quaternary ammonium salts: (A) 10-90 wt% of triethanol-amine ester quaternary ammonium compound, and (B) 90 to 10 wt% of another quaternary compound including quaterized amidoamine (or equivalent esteramine or thioamine) and (b) water and optional conventional additives.
  • compositions disclosed in the aforesaid USSN 07/995,102 provide highly effective stable and pourable liquid fabric softener compositions; nevertheless, in practice it is found that with concentrations of the amidoamine fabric softening compound (e.g. VarisoftTM 510) in excess of 11 weight percent in the presence of certain emulsifiers, such as hydrogenated tallow, the product viscosity becomes excessively high, even in the presence of electrolytes (e.g. CaCl 2 ) or solvents (e.g. propanol).
  • the amidoamine fabric softening compound e.g. VarisoftTM 510
  • electrolytes e.g. CaCl 2
  • solvents e.g. propanol
  • a stable, pourable, water dispersible aqueous liquid fabric softener composition includes:
  • Another object of the invention is to provide such low viscosity, stable and flowable aqueous dispersions with nitrogen compound fabric softeners in amounts of at least 25 percent by weight of the composition and which are suitable for use with or without further dilution to provide softening performance at least equivalent to that obtainable with present commercially available rinse cycle fabric softeners.
  • This composition is a dispersion containing particles of softening components (A) and (B) see below, which combined components comprise from 25% to 50% by weight of the softening composition, with the proviso that from 20% to 80% by weight of the total hydrocarbon groups R 1 and R 2 of (A) and R 4 of (B) in these two softening components contain unsaturated carbon to carbon bonds. Further, the composition also requires a third ingredient (C).
  • the present invention also provides a method of imparting softness to fabrics by contacting the fabrics with a softening effective amount of the invention fabric softener composition; generally and preferably, in the rinse cycle of an automatic laundry washing machine.
  • the compositions may be diluted with water prior to adding the composition to the washing machine (e.g., the rinse cycle dispenser), or may be added, at reduced amount, without dilution, i.e., ready to use.
  • the present invention was developed as part of an extensive research program to evaluate available fabric softening compounds which do not pose the risk of, or at least reduce the risk of, causing environmental damage associated with conventional cationic quat fabric softeners, such as dimethyl distearyl ammonium chloride (DMDSAC) yet which offer equivalent or superior softening performance to DMDSAC and which are amenable for use in concentrated products.
  • DMDSAC dimethyl distearyl ammonium chloride
  • the latter requirement is important in view of the trend in the industry to sell concentrated products which require less packaging and lower shipping costs on a per unit or per usage basis and, therefore, can be characterized as environmentally and user friendly.
  • the good softening performance is due to the excellent inherent dispersibility of the finely divided amidoamine softener when the compound is protonated as its acid complex.
  • Such excellent inherent dispersibility is believed to result from the presence of the diamido amine hydrophilic group, which may be further enhanced by a moderate level of ethoxylation (e.g., when R 3 represents (CH 2 CH 2 O) p H).
  • R 3 represents (CH 2 CH 2 O) p H
  • the presence of the two long chain hydrocarbon groups C 8 -C 20 alkyl or alkenyl
  • the concentratability of the fatty tertiary amido amine fabric softeners of formula (I) was found to be limited to no more than about 11% by weight before gelation occurs or otherwise unacceptably high viscosity results. It is presumed that this phenomenon is the result of the crystallinity of fatty tertiary amine, that is, the formation of a liquid crystalline phase.
  • the viscosity increase in concentrated samples and over time is believed to be associated with the formation of multilayered vesicle structures which trap more and more water and thus, in turn, the composition exhibits an increase in viscosity.
  • the phase volume of the composition increases with increasing softener concentration and time while the continuous (aqueous) phase gradually decreases with time.
  • VarisoftTM 512 soft tallow tertiary amine
  • VarisoftTM 510 hydrogenated (hard) tallow tertiary amine
  • This poorer softening efficacy is probably due to the lack of a hydrogen binding site on the protonated compound (i.e., the election pair or nitrogen is "used up" by protonation) for hydrogen bonding with the fabric cellulose.
  • the softening performance of the tertiary amine compound containing higher aliphatic amide or ester groups containing unsaturation (carbon to carbon double bonds), e.g., soft tallow amide, etc. is generally significantly poorer than the corresponding compounds which are fully saturated, e.g., hydrogenated tallow amide.
  • the present inventors have unexpectedly found that the fatty ester quaternary ammonium compound of formula (II), when added to an aqueous dispersion of the fatty amide (or ester) tertiary amine compound fabric softener of the formula (I) containing a significant level of unsaturation creates a stable, pourable, efficacious softening composition. It had previously been believed that efficacious softening could not be obtained from unsaturated alkyl group containing softening compounds. Analysis of such unsaturated alkyl group containing compounds are shown in Tables A and B, below. Table A shows the pourability of such systems and table B the softening efficacy.
  • Table A shows the viscosity effect (pourability) within a representative aqueous dispersion held at 4°C for 3 weeks to ensure stability -- composed of 10.5% by weight of a 100% saturated diesterquat (per formula II), and respectively varying from 0 to 17.5% by weight of a mixture of a soft tallow, about 45% unsaturated, tertiary amidoamine (AA(S) or AmidoAmine(Soft)) and 17.5% to 0% of 100% saturated tertiary amidoamine (per formula I); in the presence of minor quantities of HCl, CaCl 2 , dye, preservative, and perfume.
  • Table B also using an identical three major component system of tertiary amidoamines and diesterquat diluted 8 times as when used by consumers, shows softening efficacy at varying levels of unsaturation versus a standard (the standard being the softening effect using a 5% level of ditallow dimethylammonium chloride (DTDMAC) containing product).
  • DTDMAC ditallow dimethylammonium chloride
  • Viscosity (See Note 2) Weight % of AA(S) in Amidoamine Fraction (See Note 1) Viscosity (Pa.s(cp)) 0 ⁇ 10 ( ⁇ 10,000) 20 3.5 (3,400) 32 2.6 (2,600) 45 0.64 (635) 58 0.3 (300) 83 0.13 (130) Notes on Table A: 1. For example, 30% AA(S) composition within the Amidoamine Fraction is equal to an overall weight percent of about 3.8% unsaturation. 2. In subsequent examples, wherein the esterquat component contains unsaturated moieties, the percentage of unsaturated within the amidoamine fraction can be proportionately reduced from that shown in Table A above. Amount of Unsaturation Vs.
  • Table B The softening level shown is on a scale of from 0 to 10; wherein 0 represents no consumer preceivable softening and 10 being the maximum level of consumer preceivable softening.
  • the 8.1 level corresponds to a 40 EQ emulsion, as defined herein.
  • the mixture of the compounds of formulas (I) and (II) allow the compositions to be formulated as concentrates for subsequent dilution (if desired) at ratios as high as 8:1 or higher, while still remaining pourable in the concentrated form.
  • These same concentrated formulas may, of course, be used without dilution but in smaller quantities to achieve superior softening performance.
  • compositions of this invention are stable, pourable, and rapidly water dispersible aqueous dispersions which contain, (A) a fabric softening effective amount of an inorganic or organic acid salt of fatty amido (or ester) tertiary amine of formula, with a significant level of unsaturated bonds, (I) and (B) a synergistic viscosity reducing and fabric softening improving ester quaternary ammonium compound of formula (II), wherein the total amount of (A) and (B), combined is from about 25 to about 50% by weight, especially from 28% to 38% by weight.
  • the aqueous dispersion within these amounts of fabric softening active ingredients is of low viscosity, namely, remains pourable at ambient temperature, particularly less than 1.5 Pa.s (1500 cps) at 20°C.
  • the fabric softening active compound (A) is an amido (or ester) tertiary amine of formula (I):
  • R 1 and R 2 are each, independently, long chain aliphatic hydrocarbons, e.g., alkyl or alkenyl groups having from 12 to 30 carbon atoms, preferably from 16 to 22 carbon atoms.
  • Linear hydrocarbon groups such as, for example, dodecyl, dodecenyl, octadecyl, octadecenyl, behenyl, eicosyl, etc., are preferred.
  • R 1 and R 2 will be derived from natural oils containing fatty acids or fatty acid mixtures, such as coconut oil, palm oil, tallow, rape oil, and fish oil. Chemically synthesized fatty acids are also usable. Generally and preferably R 1 and R 2 are derived from the same fatty acid or fatty acid mixture.
  • R 1 and R 2 are derived from or contain at least 20%, and up to 80%, but preferably not more than 65% by weight of unsaturated (i.e., alkenyl) groups
  • unsaturated moieties of the compound of formula (I) is overcome by the combination with the ester quat compound (B) of formula (II) and an effective amount of a viscosity reducing electrolyte.
  • R 3 in formula (I) represents (CH 2 CH 2 O) p H, CH 3 , or H, or mixtures thereof.
  • p is a positive number representing the average degree of ethoxylation, and is preferably from 1 to 10, especially 1.4 to 6, and more preferably from about 1.5 to 4, and most preferably, from 1.5 to 3.0.
  • n and m are integers of from 1 to 5, preferably 1 to 3, especially 2.
  • R 3 represents the preferred (CH 2 CH 2 O) p H group
  • R 3 represents the preferred (CH 2 CH 2 O) p H group
  • ethoxylated amidoamines when T-NH
  • hydroxyethyl is also used to describe the (CH 2 CH 2 O) p H group.
  • the compound of formula (I) which is commercially available under the tradenames Varisoft 512 (a 90% concentration with a 10% organic solvent), or Varisoft 511 (approximately a 100% active ingredient concentration), available from Sherex Chemical Company, which is bis(tallow-amidoethyl)-hydroxyethyl amine of formula
  • VarisoftTM 512 or 511 the corresponding hydrogenated tallow amidoamine derivative, available from Sherex under the tradename VarisoftTM 510: may be used.
  • the percentage of alkenyl groups is based on the total of both compounds.
  • VarisoftTM 512 which is derived from a natural (beef) tallow (often referred to as “soft-tallow” or sometimes, simply as “tallow” or AA(S))
  • the average fatty chain composition is typically (variations occur depending on the particular source, time of year, feed supply, etc.):
  • H-tallow contains about 100% of saturated chains.
  • the amount of VarisoftTM 512 or 511 should be at least about 25% of the mixture to provide at least about 11% by weight of unsaturated chains within the overall amidoamine component.
  • the long chains (R 1 and R 2 ) of the formula (I) compounds may, theoretically, be entirely unsaturated, in practice the softening performance of such unsaturated compounds is not sufficient. Therefore, it is preferred to limit the amount of the unsaturated chains to no more than about 80%, preferably no more than about 65%, by weight based on the total of the R 1 and R 2 groups.
  • VarisoftTM 512 and VarisoftTM 511 both contain about 45% of unsaturated long chain alkyl groups, either of these amidoamine fabric softeners may be used by itself. However, to achieve still higher softening performance, while maximizing the total amount of fabric softening active ingredients [(A) and (B) combined] it is preferred to maintain the unsaturated alkyl chains at below about 36% by weight, especially below about 30% by weight, based on the total of the higher alkyl groups (R 1 and R 2 ) in the formula (I) compounds.
  • the ratio of the hard-tallow (510TM) to soft tallow (512) compounds is in the range of from about 20 to 60: 80 to 40, more preferably from about 45 to 55: 65 to 45; such as, for example, 55:45 (corresponding to about 20% by weight of unsaturated chains).
  • the amine function of the amidoamine or ester amine compound is at least partially neutralized by a proton contributed by a dissociable acid, which may be inorganic, e.g., HCl, H 2 SO 4 , HNO 3 , etc. or organic, e.g. acetic acid, propionic acid, lactic acid, citric acid, glycolic acid, toluene sulfonic acid, maleic acid, fumaric acid, and the like.
  • a dissociable acid which may be inorganic, e.g., HCl, H 2 SO 4 , HNO 3 , etc. or organic, e.g. acetic acid, propionic acid, lactic acid, citric acid, glycolic acid, toluene sulfonic acid, maleic acid, fumaric acid, and the like.
  • Mixtures of these acids may also be used, as may any other acid capable of neutralizing the amine function.
  • the acid neutralized compound is believed to form a reversible complex, that is, the bond between the amine function and proton will disappear under alkaline pH conditions. This is in contrast to quaternization, e.g., with a methyl group, wherein the quaternizing group is covalently bonded to the positively charged amine nitrogen and is essentially pH independent.
  • the amount of acid used will depend on the "strength" of the acid; strong acids such as HCl, and H 2 SO 4 completely dissociate in water, and, therefore, provide a high amount of free protons (H + ), while weaker acids, such as citric acid, glycolic acid, lactic acid, and other organic acids, do not dissociate completely and, therefore, require a higher concentration to achieve the same neutralizing effect.
  • weaker acids such as citric acid, glycolic acid, lactic acid, and other organic acids
  • the amount of acid required to achieve complete protonation of the amine will be achieved when the pH of the composition is rendered strongly acidic, namely between about 1.5 and 4.
  • HCl and glycolic acid are preferred, and HCl is especially preferred.
  • the amount of acid used for neutralization should be sufficient to provide at least an 0.5:1 molar ratio, and up to about a 1:1 molar ratio of the acid to the total amount of fabric softener fatty amide or ester tertiary amine.
  • the organic carboxylic acids it is preferred to use a molar excess of the neutralizing acid. Molar ratios of organic carboxylic acid to the compound of formula (I) up to about 6:1, for example from 1.5:1 to 6:1, such as 2:1, 3:1 or 4:1, have been found advantageous in terms of stability and/or softening performance. The use of glycolic in molar excess is especially preferred.
  • the second essential fabric softener compound according to this invention is the biodegradable, with a quaternized ammonium ester compound (B) of the following formula (II)
  • Each R 4 independently represents an aliphatic hydrocarbon group having from 8 to 22 carbon atoms, and preferably 14 to 18 carbon atoms.
  • the fatty ester quaternary compounds are diester compounds, i.e. R 7 represents benzyl, phenyl, phenyl substituted by C 1 -C 4 alkyl, hydroxyl (OH) or hydrogen (H). Most preferably R 7 represent OH or H, especially preferably OH, e.g. R 5 is hydroxyethyl.
  • q, r and s each, independently, represents a number of from 1 to 3.
  • X represents a counter ion of valence a.
  • the diester quat of formula (II) may be a compound of the formula: where each R 4 may be, for example, derived from hard or soft tallow, coco, stearyl, oleyl, and the like.
  • Such compounds are commercially available, for example, TetranylTM AT-75, from Kao Corp. Japan, which is di-tallow ester triethanol amine quaternary ammonium methyl sulfate.
  • TetranylTM AT-75 is based on a mixture of about 25% hard tallow and about 75% soft tallow. Accordingly, this product contains about 34% of unsaturated alkyl chains.
  • a second example would be HipochemTM X-89107, from High Point Chemical Corp.; which is an analogue of the TetranylTM AT-75 with about 100% saturation in the tallow moieties.
  • the quaternized ammonium ester compound of formula (III) may contain from about 5% to about 75% of unsaturated (long-chain) alkyl groups, preferably from about 20% to about 50% of unsaturated long-chain alkyl groups.
  • the compounds (A) of formula (I) and compounds (B ) of formula (II) are used in admixture, preferably at ratios of about 5:1 to about 1:5, more preferably from 2:1 to 1:2, especially 1.7:1 to 1:1.7, whereby both softening performance and stability and pourability are improved. That is, notwithstanding the poor softening performance of the unsaturated long-chain alkyl compounds when used individually, when used with the ester quat compound (which also preferably contains carbon to carbon double bonds) either alone or in combination with the hydrogenated amido amine compound a surprisingly substantial improvement in softening performance is observed in pourable liquid formulations.
  • the total amounts of components (A) and (B) is from 25 to 50 wt. percent, preferably from about 28 to about 38 wt%, and the ratio, by weight of (A):(B) is preferably from about 2:1 to 1:2, and especially, from about 1.7:1 to 1:1.
  • compositions of this invention are provided as aqueous dispersions in which the fabric softener compounds of formula (I) and formula (II) are present in finely divided form stably dispersed in the aqueous phase.
  • particle sizes of the dispersed particles of less than about 25 microns ( ⁇ m), preferably less than 20 ⁇ m, especially preferably no more than 10 ⁇ m, on average are acceptable for both softening and stability insofar as the particle sizes can be maintained during actual use, typically in the rinse cycle of an automatic laundry washing machine.
  • the lower limit is not particularly critical but from a practical manufacturing standpoint will not generally be below about 0.01 ⁇ m, preferably at least about 0.05 ⁇ m.
  • a preferred particle size range of the dispersed softener ingredients is from about 0.1 to about 8 ⁇ m.
  • compositions of this invention are that it is not necessary to subject the composition to high shear conditions, such as by high pressure homogenization.
  • Simple mixing of the ingredients in water with a low shear mixer provides stable dispersions of finely divided particles.
  • the aqueous phase of the dispersion is primarily water, usually deionized or distilled water. Small amounts (e.g. up to about 5% by weight) of co-solvent may be present for adjustment of viscosity.
  • co-solvent lower mono- and poly-hydroxy alcohols and aqueous will be used, generally in amounts up to about 8% by weight of the composition.
  • the preferred alcohols and aqueous are those having from 2 to 4 carbon atoms, such as, for example, ethanol, propanol, isopropanol, and propylene glycol or ethylene glycol. Isopropyl alcohol (2-propanol) is especially preferred.
  • co-solvents are not required and are generally avoided.
  • compositions of this invention include an electrolyte to reduce dispersion viscosity.
  • any of the alkaline earth metal salts of the mineral acids can be used as electrolyte.
  • CaCl 2 , MgCl 2 and MgSO 4 and similar salts of alkaline earth metals are preferred, and CaCl 2 is especially preferred.
  • the amount of the electrolyte will be selected to assure that the composition does not form a gel.
  • amounts of electrolyte salt of from about 0.05 to 2.0 wt%, preferably 0.1 to 1.5 wt%, especially preferably 0.25 to 1.4 wt%, will effectively prevent gelation from occurring.
  • the role of the electrolyte to inhibit gelation can be explained based on the assumption that the invention dispersions of the cationic softening compounds have a vesicular structure.
  • the spacing of the multilayered vesicles in the liquid crystalline phases varies with the electrolyte concentration since it depends on the repulsion between the head groups in adjacent layers.
  • the amount of the enclosed water tends to be reduced at high salt concentrations, causing a lowering of the disperse phase volume and the viscosity.
  • if one exceeds a critical concentration of the electrolyte this may lead to a destabilization of the emulsions by flocculation or coalescence.
  • the phenomenon of flocculation or coalescence can be explained by considering the electrostatic stabilization of colloidal dispersions. Attractive as well as repulsive forces act on the individual particles of a dispersion. The repulsive forces increase exponentially as the particles approach each other, such as when the concentration of dispersion increases, and they become very strong when the electrical double layers (the counterions in the dispersion medium give rise to the electrical double layers that surround the colloidal particles) that envelope each particle overlap.
  • the thickness of the electrical double layers is very sensitive to the ionic strength of the dispersion medium. Increasing the ionic strength significantly dimishes the thickness of the double layer. The repulsive forces then become of insufficient magnitude and are no longer able to overcome the attractive van der Waals forces which may lead to dispersion flocculation or coagulation.
  • a rheology modifier to help reduce or eliminate variations in the aqueous dispersion viscosity over time. It should be understood, however, that so long as the viscosity does not increase to an unacceptably high level over the expected life of the produce (including transportation from the manufacturing plant to the market place, shelf-life in the market place, and duration of consumption by the end user) a rheology modifier is not necessary.
  • the viscosity after, for instance, 8 to 10 weeks should preferably not exceed about 1.5 Pa.s (1500 cps) (at 25°C), especially preferably the viscosity should not exceed about 1.5 Pa.s (1500 cps) (at 25°C) over the expected lifetime of the produce. In many cases, initial viscosities of up to about 0.2 Pa.s (200 cps) can be achieved and maintained.
  • a rheology modifier can be added to the composition.
  • rheology modifiers are well known in the art and may be chosen from, for example, polymeric rheology modifiers and inorganic rheology modifiers.
  • the former type include polyquaternium compounds, such as Polyquaternium-24 (a hydrophobically modified polymeric quaternary ammonium salt hydroxyethyl-cellulose, available from Amercho, Inc.); cationic polymers such as copolymers of acrylamide and quaternary ammonium acrylate; the CarbopolsTM, and the like.
  • inorganic rheology modifiers include, for example, alumina. Generally, only minor amounts, up to about 1.0%, preferably up to about 0.8%, such as, for example, 0.01 to 0.60 percent, by weight, provide acceptable viscosity levels over time.
  • citric acid Another additive which has been found to be useful as a rheology modifier is citric acid, generally in amounts of from about 0.05 to 1.0 wt%, preferably from about 0.1 to 0.6 weight percent.
  • Fatty alcohols and non-ionic surfactants may also be included in minor amounts (e.g. up to about 5% by weight, preferably up to about 2% by weight) as viscosity modifiers and/or emulsifying agents.
  • Typical components of this type include, but are not limited to colorants, e.g., dyes or pigments, bluing agents, preservatives, germicides, and perfumes.
  • the subject liquid fabric softener compositions may be prepared by adding the active ingredients, usually as a melt, to the heated aqueous phase to which the acid component has been pre-mixed, under mixing. Low-shear mixing is generally sufficient to adequately and uniformly disperse the active ingredients in an throughout the aqueous phase. Further particles size reduction can be obtained by subjecting the composition to further treatment such as in a colloid mill or by high pressure homogenization, however, as previously noted, no significant improvement in softening performance has been associated with such particle size reduction.
  • final product viscosity (for a freshly prepared sample) should not exceed about 1.5 Pa.s (1500 centipoise), preferably not more than 1 Pa.s (1000 centipoise), but should not be too low, for example not less than about 50 centipoise.
  • the preferred viscosity for the invention concentrated product is in the range of 0.12 to 1 Pa.s (120 to 1000 centipoise). As used herein, unless otherwise specified, viscosity is measured at 25°C (22-26°C) using a BrookfieldTM RVTD Digital Viscometer with Spindle #4 at 20 rpm.
  • the concentrated compositions may be diluted by a factor of generally 4:1 or more, preferably up to about 8:1 or even 9 to 10:1.
  • Concentrated products with up to about 40 weight percent of softeners may be prepared and will remain pourable and stable against phase separation or suspended particle agglomeration for extended periods of time.
  • the concentrated products of this invention provide equivalent softness at the same use level (e.g., about 110 ml for standard European washing machines) as a (hypothetical) softener product containing up to about 50 weight percent or more of ditallow dimethyl ammonium chloride (DTDMAC).
  • DTDMAC ditallow dimethyl ammonium chloride
  • a composition with about 28% of softeners see Example 2, Composition No.
  • composition 14 hereinafter can be diluted to about 5% actives to provide equivalent or superior softening performance to a product containing about 7% of DTDMAC.
  • the composition will normally contain sufficient softener to be effective when added to the rinse water in an amount of about one-eighth to three-quarters of a cup (28 to 170g (1 to 6 ounces)) providing about 25 ppm to about 90 ppm of softener in the rinse water.
  • This example demonstrates the ability of the partially unsaturated amidoamine compound of formula (I) to control the viscosity of aqueous dispersion of softening active compounds with total amounts of the active softening compounds (A) and (B) in excess of about 25 weight percent.
  • compositions shown in Table 1 were prepared as described below.
  • VarisoftTM 512 A) 12 12 15 16 17 17 Esterquat (B) 12 12 15 16 17 17 Emulsifier - - - - - 2 HCl 0.87 0.87 1.08 1.08 1.22 1.22 Defoamer 0.03 0.03 0.02 0.04 0.04 0.04 CaCl 2 0.78 0.4 1.25 0.8 1.09 0.95 H 2 O balance to 100 balance to 100 balance to 100 balance to 100 balance to 100 balance to 100 balance to 100 balance to 100 balance to 100 balance to 100 balance to 100 balance to 100 balance to 100 balance to 100
  • compositions Nos. 1-6 were prepared by adding a molten mixture of the ester quat and Varisoft 512 at 35° to 45°C to an aqueous (deionized water) solution of HCl (and emulsifier for Run No. 6) at 60°C while stirring with a Premier mixer connected to a variac for control of motor speed.
  • the melt of softening active compounds was added slowly in three equal increments.
  • CaCl 2 solution was added into the hot dispersions which were allowed to cool to room temperature slowly with stirring. During cooling, a few drops of Dow Corning 1430 antifoam was added.
  • a second sample with the same composition had an initial viscosity of 1260 cps and a 10 week viscosity of 910 cps. Note 2.
  • a sample diluted to 5% of (A) and (B) combined exhibited a softening efficacy of 5 EQ. EQ values are the softening performance of an equivalent weight of ditallowdimethyl ammonium chloride as described below.
  • compositions 1-5 were stable (no phase separation) and low viscosity dispersions of Varisoft-512 and ester quat softeners at up to 34% active level in the presence or absence of an emulsifier.
  • Softening efficacy of the dispersions at full strength (undiluted) or diluted (composition No. 5) were compared with ditallow dimethyl ammonium chloride.
  • the softening efficacy of the dispersion No. 5 at 5% solid level was 5 EQ.
  • Product activity of 1EQ is the softening obtained by 1% dispersion of ditallow dimethyl ammonium chloride.
  • the undiluted dispersions 1-6 under similar conditions exhibited a product activity of 20 EQ.
  • composition #6 The softening efficacy of composition #6 was 5 EQ at 5% use level and was 35 EQ for the undiluted 34% actives composition.
  • the softening corresponding to 5% level of ditallow dimethylammonium chloride (DTDMAC) is referred as 5EQ and at double dosage level (corresponding to 10% level of DTDMAC) is referred to as 10 EQ. If one plots a graph of softening versus the dosage amount of ditallow dimethylammonium chloride (a standard used for the softening evaluation), the softening increases linearly with the dosage of DTDMAC up to about 9-10% and then it levels off.
  • DTDMAC ditallow dimethylammonium chloride
  • This example further demonstrates the synergistic interaction between components (A) and (B) using a mixture of VarisoftTM 510 and VarisoftTM 512.
  • compositions Nos. 7-17 were prepared with varying amounts of softening active ingredients (A) and (B) and varying amounts of unsaturated alkyl groups in R 1 and R 2 of formula (I) of component (A) by varying the amounts and proportions of VarisoftTM 510 and VarisoftTM 512 as shown in Table 3. The following procedure was used to prepare these compositions.
  • VarisoftTM 510, VarisoftTM 512 and TetranylTM AT-75 were each melted, mixed together with stirring and maintained at 70°C.
  • Perfume (DouscentTM 653, from IFF in the amounts shown in Table 3) was added to the molten mixture just prior to emulsification with the aqueous phase.
  • HCl (in the amounts shown in Table 3) was added to heated (70°C) deionized water.
  • the mixture of molten softening active compounds was added to the acidified water phase with stirring using a 4-pitched-blade impeller. During addition of the molten mixture the stirring speed was increased from 300 to 700 rpm as the emulsion thickened.
  • compositions were measured for initial viscosity, viscosity after storage at 4°C for 24 hours and, softening performance. The results are reported in Table 3, below.
  • composition No. 17 which formed a gel
  • the viscosity can be reduced to acceptable (for pourability) levels.
  • aqueous dispersions containing more than 25% of total active softening compounds and which provide enhanced softening performance yet are easily pourable and remain stable over extended periods of time.

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Claims (15)

  1. Stabile, gießbare und wasserdispergierbare Gewebeweichmacherzusammensetzung, die eine wässrige Dispersion umfasst, die Teilchen aus Komponenten (A) und (B) enthält, die kombiniert, 25 bis 50 Gew.-% der Gesamtzusammensetzung ausmachen, wobei:
    (A) ein anorganisches oder organisches Säuresalz einer gewebeweichmachenden Zusammensetzung der Formel (I):
    Figure 00360001
    ist, in der
    R1 und R2 für aliphatische C12 bis C30-Kohlenwasserstoffgruppen stehen, von denen ein Teil ungesättigte Kohlenstoff-Kohlenstoff-Bindung enthält,
    R3 für (CH2CH2)pH, CH3 oder H steht,
    T für O oder NH steht,
    n = 1 bis 5 ist,
    m = 1 bis 5 ist, und
    p = 1 bis 10 ist,
    (B) eine biologisch abbaubare Fettester-quartäre Ammoniumverbindung mit der Formel (II) ist:
    Figure 00370001
    in der R4 jeweils unabhängig für eine aliphatische Kohlenwasserstoffgruppe mit 8 bis 22 Kohlenstoffatomen steht, von denen ein Teil ungesättigte Kohlenstoff-Kohlenstoff-Bindung enthalten kann,
    R5 für (CH2)sR7 steht, worin R7 eine Alkoxycarbonylgruppe mit 8 bis 22 Kohlenstoffatomen, Benzyl, Phenyl, (C1-bis C4-)-alkylsubstituiertes Phenyl, OH oder H ist,
    R6 für (CH2)tR8 steht, worin R8 Benzyl, Phenyl, (C1- bis C4-)-alkylsubstituiertes Phenyl, OH oder H ist,
    q, r, s und t jeweils unabhängig eine Zahl von 1 bis 3 sind und x an Anion mit einer Wertigkeit a ist,
    mit der Maßgabe, dass 20 bis 80 Gew.-% der gesamten Kohlenwasserstoffgruppen R1 und R2 in Komponente (A) und R4 in Komponente (B) ungesättigte Kohlenstoff-Kohlenstoff-Bindungen enthalten, und
    (C) ein wässriges Lösungsmittel, dass eine gegen Gelbildung wirkende Menge Elektrolyt enthält.
  2. Gewebeweichmacherzusammensetzung nach Anspruch 1, bei der in der Verbindung der Formel (I)
    R1 und R2 = C16- bis C22- Alkyl oder -Alkenyl sind,
    m = 1 bis 3 ist,
    n = 1- bis 3 ist,
    R3 = (CH2CH2O)pH ist, und
    p = 1,5 bis 3,5 ist.
  3. Zusammensetzung nach Anspruch 1, bei der das Gewichtsverhältnis von (A) : (B) im Bereich von etwa 5 : 1 bis etwa 1 : 5 liegt und die gesamte Ungesättigtheit weniger als 70 % des kombinierten Gewichts von (A) und (B) ist.
  4. Zusammensetzung nach Anspruch 3, bei der die Gesamtmenge an (A) und (B) von etwa 28 bis etwa 38 Gew.-%, bezogen auf die Gesamtzusammensetzung, reicht.
  5. Zusammensetzung nach Anspruch 1, bei der die Gesamtmenge an (A) und (B) von etwa 28 bis etwa 38 Gew.-%, bezogen auf die Gesamtzusammensetzung, reicht.
  6. Zusammensetzung nach Anspruch 1, bei der das Gewichtsverhältnis von (A) : (B) im Bereich von etwa 2 : 1 bis 1 : 2 liegt und die gesamte Ungesättigtheit weniger als 70 % des kombinierten Gesamtgewichts von (A) und (B) ist.
  7. Zusammensetzung nach Anspruch 6, bei der die Gesamtmenge von (A) und (B) im Bereich von etwa 28 bis etwa 38 Gew.-% liegt.
  8. Zusammensetzung nach Anspruch 1, bei der die Gewebeweichmacher-Verbindung (A) nicht mehr als etwa 65 % von Kohlenwasserstoffgruppen mit Kohlenstoft-Kohlenstoff-Bindungsungesättigtheit enthält.
  9. Zusammensetzung nach Anspruch 8, bei der die Gesamtmenge an Kohlenwasserstoffgruppen mit ungesättigten Kohlenstoff-Kohlenstoff-Doppelbindungen in R1 und R2 gemäß Formel (I) im Bereich von etwa 2,4 bis etwa 50 Gew.-% liegt.
  10. Zusammensetzung nach Anspruch 1, bei der das wässrige Lösungsmittel Wasser und etwa 0,05 bis zu etwa 2,0 Gew.-% an Erdalkalimetallsalzelektrolyt umfasst.
  11. Gewebeweichmachende Zusammensetzung nach Anspruch 10, die eine Viskosität bei 25 °C von weniger als 2 Pa·s (2000 cPs) aufweist.
  12. Gewebeweichmachende Zusammensetzung nach Anspruch 10, die eine Viskosität bei 25 °C von weniger als 1 Pa·s (1000 cPs) aufweist.
  13. Gewebeweichmachende Zusammensetzung nach Anspruch 1, die umfasst:
    (A) etwa 10 bis etwa 25 Gew.-% einer Mischung von Salzen von Bis(talgamidoethyl)-2-hydroxyethylamin) und Bis-(hydriertes talgamidoethyl)-2-hydroxyethylamin, wobei mindestens 30 bis zu etwa 65 Gew.-% des Talgs ungesättigt sind,
    (B) etwa 10 bis etwa 18 Gew.-% N-Methyl-N,N,N-triethanolamin-ditalgester-quartäres ammoniummethosulfat, mit einer Gesamtmenge von (A) und (B) in Kombination von 28 bis 38 Gew-%,
    (C) etwa 0,05 bis etwa 2,0 % anorganischen Salzelektrolyten, wobei die Zusammensetzung eine Viskosität von nicht mehr als etwa 1,5 Pa·s (1500 cPs) bei 25 °C aufweist.
  14. Verfahren zum Vermitteln von Weichheit an Gewebe, bei dem die Gewebe mit einer weichmachend wirkenden Menge der Gewebeweichmacherzusammensetzung gemäß Anspruch 1 in Kontakt gebracht werden.
  15. Verfahren nach Anspruch 14, bei dem die Kontaktierung in dem Spülzyklus einer automatischen Waschmaschine erfolgt.
EP94202049A 1993-07-15 1994-07-14 Flüssiges Wäscheweichspülerkonzentrat Expired - Lifetime EP0634475B1 (de)

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US08/213,308 US5501806A (en) 1993-07-15 1994-03-14 Concentrated liquid fabric softening composition

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DE19515646A1 (de) * 1995-04-28 1996-10-31 Henkel Kgaa Avivagemittel
PT850291E (pt) * 1995-08-31 2002-07-31 Colgate Palmolive Co Composicoes estaveis de amaciadores de tecidos
US5723426A (en) † 1996-02-29 1998-03-03 Zhen; Yueqian Liquid laundry detergent compositions containing surfactants and silicone emulsions
EP1062311A1 (de) * 1996-07-19 2000-12-27 The Procter & Gamble Company Konzentrierte textilweichmachungszusammensetzung und stark ungesättigte textilweichmachungsverbindung dafür
DE19743687C1 (de) * 1997-10-06 1998-11-26 Henkel Kgaa Detergensgemische und deren Verwendung
ES2283117T5 (es) * 1998-06-10 2010-06-28 Kao Corporation Composiciones suavizantes.
GB9816659D0 (en) * 1998-07-30 1998-09-30 Dow Europ Sa Composition useful for softening, cleaning, and personal care applications and processes for the preparation thereof
AU3773100A (en) * 1999-03-26 2000-10-16 Dow Chemical Company, The Softener compositions having high hydrolytic stability concentratibility
US6191101B1 (en) * 2000-05-26 2001-02-20 Colgate-Palmolive Co. Fabric softening compositions providing enhanced performance and containing cationic softeners and fatty amides
MXPA04012377A (es) * 2002-06-13 2005-02-25 Procter & Gamble Composiciones que comprenden un sistema activo suavizante de telas que comprende por lo menos dos activos cationicos suavizantes de telas.
US6610640B1 (en) * 2002-07-31 2003-08-26 Colgate Palmolive Company Unit dose nonaqueous liquid softener disposed in water soluble container

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US4661269A (en) * 1985-03-28 1987-04-28 The Procter & Gamble Company Liquid fabric softener
US4772404A (en) * 1986-12-24 1988-09-20 Lever Brothers Company Concentrated liquid fabric softener with whiteners
DE3926740C2 (de) * 1989-08-12 1997-05-15 Witco Surfactants Gmbh Wässrige Weichspülmittel und deren Verwendung
NZ235490A (en) * 1989-10-16 1993-08-26 Colgate Palmolive Co Fabric-softening compositions
JPH0441776A (ja) * 1990-06-01 1992-02-12 Kao Corp 液体柔軟仕上剤
US5399272A (en) * 1993-12-17 1995-03-21 The Procter & Gamble Company Clear or translucent, concentrated biodgradable quaternary ammonium fabric softener compositions
US5427697A (en) * 1993-12-17 1995-06-27 The Procter & Gamble Company Clear or translucent, concentrated fabric softener compositions

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MX9405352A (es) 1995-01-31
EP0634475A3 (de) 1996-12-11

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