EP0891408A1 - Use of a fabric softener composition - Google Patents

Use of a fabric softener composition

Info

Publication number
EP0891408A1
EP0891408A1 EP96910640A EP96910640A EP0891408A1 EP 0891408 A1 EP0891408 A1 EP 0891408A1 EP 96910640 A EP96910640 A EP 96910640A EP 96910640 A EP96910640 A EP 96910640A EP 0891408 A1 EP0891408 A1 EP 0891408A1
Authority
EP
European Patent Office
Prior art keywords
fabric
fabric softener
composition
alkyl
use according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP96910640A
Other languages
German (de)
French (fr)
Inventor
Ellen Schmidt Baker
Frederick Anthony Hartmann
Janet Sue Littig
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority claimed from CA002250225A external-priority patent/CA2250225A1/en
Priority claimed from CN 96180310 external-priority patent/CN1219952A/en
Publication of EP0891408A1 publication Critical patent/EP0891408A1/en
Withdrawn legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/001Softening compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38Cationic compounds
    • C11D1/62Quaternary ammonium compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/001Softening compositions
    • C11D3/0015Softening compositions liquid
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246Silicates, e.g. diatomaceous earth
    • C11D3/1253Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite

Definitions

  • the present invention relates to fabric softener compositions. More particularly, it relates to the use of said fabric softening compositions for imparting fabric appearance benefits upon rinsing and/or drying of the fabrics.
  • the problem has been found exacerbated at the location of the stress points such as seams and zippers but also influenced by the overall characteristics of the fabric, e.g., dye type, weave, thread count, fiber type, etc., and the composition of the laundry load, e.g., size, weight, and number of items. This problem has also been found further exacerbated after multiple washing cycles.
  • An advantage of the invention is therefore to provide fabrics with effective color fidelity and definition. Such advantage is also seen to be greatly enhanced upon multiple washing cycle.
  • the present invention relates to the use of a fabric softening composition, comprising at least one fabric softener component, for inhibiting or reducing loss of fabric appearance.
  • the present invention relates to the use of a fabric softener composition comprising at least one fabric softener component, for inhibiting or reducing loss of fabric appearance.
  • the essential component of the invention is a fabric softener component.
  • Typical levels of said fabric softener components within the softener compositions are from 1 % to 99% by weight of the compositions.
  • a preferred level of fabric softening components from 1 % to 5%, or concentrated, with a preferred level of fabric softening components from 5% to 80%, more preferably 10% to 50%, most preferably 15% to 35% by weight.
  • the level of nonionic softener in the compositions will typically be from 0.1 % to 10%, preferably from 1 % to 5%.
  • the preferred level of fabric softener components will preferably be from 20% to 99%, more preferably from 30% to 90% by weight, and even more preferably from 35% to 80% by weight.
  • Said fabric softening component may be selected from cationic, nonionic, amphoteric or anionic fabric softening component.
  • the preferred, typical cationic fabric softening components include the water-insoluble quaternary-ammonium fabric softening actives, the most commonly used having been di-long alkyl chain ammonium chloride or methyl sulfate.
  • Preferred cationic softeners among these include the following:
  • DTDMAC ditallow dimethylammonium chloride
  • Ci2 _ 1 a'kyl hydroxyethyl dimethylammonium chloride
  • DSOEDMAC di(stearoyloxyethyl) dimethylammonium chloride
  • the quaternary ammonium compounds and amine precursors herein have the formula (I) or (II), below :
  • Q is selected from -O-C(O)-, -C(O)-O-, -O-C(O)-O-, -NR 4 -C(O)-, -
  • R 2 is (CH 2 ) m -Q-T 4 or T ⁇ or R3;
  • R 3 is C1-C4 alkyl or C1-C4 hydroxyalkyl or H;
  • R 4 is H or C1-C alkyl or C1-C4 hydroxyalkyl
  • T 1 , T 2 , T 3 , T 4 , T 5 are independently C11 -C22 a,k V or alkenyl; n and m are integers from 1 to 4; and
  • X is a softener-compatible anion.
  • Non-limiting examples of softener-compatible anions include chloride or methyl sulfate.
  • the alkyl, or alkenyl, chain T 1 , T 2 , T 3 , T 4 , T ⁇ must contain at least 11 carbon atoms, preferably at least 16 carbon atoms.
  • the chain may be straight or branched.
  • Tallow is a convenient and inexpensive source of long chain alkyl and alkenyl material.
  • the compounds wherein T " l , T 2 , T 3 , T 4 , T ⁇ represents the mixture of long chain materials typical for tallow are particularly preferred.
  • quaternary ammonium compounds suitable for use in the aqueous fabric softening compositions herein include :
  • compounds 1-7 are examples of compounds of Formula (I); compound 8 is a compound of Formula (ll).
  • N,N-di(tallow ⁇ l-oxy-ethyl)-N,N-dimethyl ammonium chloride where the tallow chains are at least partially unsaturated.
  • the level of unsaturation of the tallow chain can be measured by the Iodine Value (IV) of the corresponding fatty acid, which in the present case should preferably be in the range of from 5 to 100 with two categories of compounds being distinguished, having a IV below or above 25.
  • the anion is merely present as a counterion of the positively charged quaternary ammonium compounds.
  • the nature of the counterion is not critical at all to the practice of the present invention.
  • the scope of this invention is not considered limited to any particular anion.
  • amine precursors thereof is meant the secondary or tertiary amines corresponding to the above quaternary ammonium compounds, said amines being substantially protonated in the present compositions due to the pH values.
  • Additional fabric softening materials may be used in addition or alternatively to the biodegradable fabric softener. These may be selected from nonionic, amphoteric or anionic fabric softening material. Disclosure of such materials may be found in US 4,327,133; US 4,421 ,792; US 4,426,299; US 4,460,485; US 3,644,203; US 4,661 ,269; U.S 4,439,335; U.S 3,861 ,870; US 4,308,151 ; US 3,886,075; US 4,233,164; US 4,401 ,578; US 3,974,076; US 4,237,016 and EP 472, 178.
  • nonionic fabric softener materials typically have a HLB of from about 2 to about 9, more typically from about 3 to about 7.
  • Such nonionic fabric softener materials tend to be readily dispersed either by themselves, or when combined with other materials such as single-long-chain alkyl cationic surfactant described in detail hereinafter. Dispersibility can be improved by using more single-long-chain alkyl cationic surfactant, mixture with other materials as set forth hereinafter, use of hotter water, and/or more agitation.
  • the materials selected should be relatively crystalline, higher melting, (e.g. >40°C) and relatively water-insoluble.
  • Preferred nonionic softeners are fatty acid partial esters of polyhydric alcohols, or anhydrides thereof, wherein the alcohol, or anhydride, contains from 2 to 18, preferably from 2 to 8, carbon atoms, and each fatty acid moiety contains from 12 to 30, preferably from 16 to 20, carbon atoms.
  • such softeners typically contain from one to 3, preferably 2 fatty acid groups per molecule.
  • the polyhydric alcohol portion of the ester can be ethylene glycol, glycerol, poly (e.g., di-, tri-, tetra, penta-, and/or hexa-) glycerol, xylitol, sucrose, erythritol, pentaerythritol, sorbitol or sorbitan. Sorbitan esters and polyglycerol monostearate are particularly preferred.
  • the fatty acid portion of the ester is normally derived from fatty acids having from 12 to 30, preferably from 16 to 20, carbon atoms, typical examples of said fatty acids being lauric acid, myristic acid, palmitic acid, stearic acid and behenic acid.
  • Highly preferred optional nonionic softening agents for use in the present invention are the sorbitan esters, which are esterified dehydration products of sorbitol, and the glycerol esters.
  • sorbitan monostearate is a suitable material. Mixtures of sorbitan stearate and sorbitan palmitate having stearate/palmitate weight ratios varying between about 10: 1 and about 1 :10, and 1 ,5-sorbitan esters are also useful.
  • Glycerol and polyglycerol esters especially glycerol, diglycerol, triglycerol, and polyglycerol mono- and/or di-esters, preferably mono-, are preferred herein (e.g. polyglycerol monostearate with a trade name of Radiasurf
  • Useful glycerol and polyglycerol esters include mono-esters with stearic, oleic, palmitic, lauric, isostearic, myristic, and/or behenic acids and the diesters of stearic, oleic, palmitic, lauric, isostearic, behenic, and/or myristic acids. It is understood that the typical mono-ester contains some di- and tri-ester, etc.
  • the "glycerol esters” also include the polyglycerol, e.g., diglycerol through octaglycerol esters.
  • the polyglycerol polyols are formed by condensing glycerin or epichlorohydrin together to link the glycerol moieties via ether linkages.
  • the mono- and/or diesters of the polyglycerol polyols are preferred, the fatty acyl groups typically being those described hereinbefore for the sorbitan and glycerol esters.
  • softening clays such as the low ion-exchange-capacity ones described in EP-A-0, 150,531.
  • the pH of the liquid compositions herein is an essential parameter of the present invention, indeed, it influences the stability of the quaternary ammonium or amine precursors compounds, especially in prolonged storage conditions.
  • the pH as defined in the present context, is measured in the neat compositions at 20°C.
  • the neat pH measured in the above-mentioned conditions, must be in the range of from 2.0 to 4.5.
  • the pH of the neat composition is in the range of 2.0 to 3.5, while if it is in a diluted form, the pH of the neat composition is in the range of 2.0 to 3.0.
  • the pH of these compositions herein can be regulated by the addition of a Bronsted acid.
  • suitable acids include the inorganic mineral acids, carboxylic acids, in particular the low molecular weight (C1-C5) carboxylic acids, and alkylsulfonic acids.
  • Suitable inorganic acids include HCI, H2SO4, HNO3 and H3PO4.
  • Suitable organic acids include formic, acetic, citric, methylsulfonic and ethylsulfonic acid.
  • Preferred acids are citric, hydrochloric, phosphoric, formic, methylsulfonic acid, and benzoic acids.
  • composition may also optionally contain additional components such as surfactant concentration aids, electrolyte concentration aids, stabilisers, such as well known antioxidants and reductive agents, soil release polymers, emulsifiers, bacteriocides, colorants, perfumes, preservatives, optical brighteners, anti ionisation agents, antifoam agents and enzymes.
  • surfactant concentration aids such as sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfit
  • Surfactant concentration aids may also optionally be used.
  • Surfactant concentration aids are typically selected from single long chain alkyl cationic surfactants, nonionic surfactants, amine oxides, fatty acids, and mixtures thereof, typically used at a level of from 0 to 15% of the composition.
  • Such mono-long-chain-alkyl cationic surfactants useful in the present invention are, preferably, quaternary ammonium salts of the general formula :
  • R 2 group is C-
  • a fatty acid ester of choline preferably Ci 2" -]4 (coco) choline ester and/or C-
  • Each R is a C1-C4 alkyl or substituted (e.g., hydroxy) alkyl, or hydrogen, preferably methyl, and the counterion X" is a softener compatible anion, for example, chloride, bromide, methyl sulfate, etc.
  • cationic materials with ring structures such as alkyl imidazoiine, imidazolinium, pyridine, and pyridinium salts having a single Ci 2" 30 a ' k Y' chain can also be used. Very low pH is required to stabilize, e.g., imidazoiine ring structures.
  • alkyl imidazolinium salts and their imidazoiine precursors useful in the present invention have the general formula :
  • Y 2 is -C(O)-O-, -O-(O)C-, -C(O)-N(R 5 )-, or -N(R5)-C(0)- in which R ⁇ is hydrogen or a C1-C4 alkyl radical; R 6 is a C1-C4 alkyl radical or H (for imidazoiine precursors); R? and R ⁇ are each independently selected from R and R 2 as defined hereinbefore for the single-long-chain cationic surfactant with only one being R 2 .
  • alkyl pyridinium salts useful in the present invention have the general formula :
  • R 2 and X- are as defined above.
  • a typical material of this type is cetyl pyridinium chloride.
  • Nonionic Surfactant Alkoxylated Materials
  • Suitable nonionic surfactants for use herein include addition products of ethylene oxide and, optionally, propylene oxide, with fatty alcohols, fatty acids, fatty amines, etc.
  • Suitable compounds are substantially water-soluble surfactants of the general formula :
  • R 2 is selected from primary, secondary and branched chain alkyl and/or acyl hydrocarbyl groups; primary, secondary and branched chain alkenyl hydrocarbyl groups; and primary, secondary and branched chain alkyl- and alkenyl-substituted phenolic hydrocarbyl groups; said hydrocarbyl groups having a hydrocarbyl chain length of from 8 to 20, preferably from 10 to 18 carbon atoms.
  • Y is typically -O-, -C(O)O-, -C(O)N(R)-, or -C(O)N(R)R-, in which R 2 and R, when present, have the meanings given hereinbefore, and/or R can be hydrogen, and z is at least 8, preferably at least 10-1 1 .
  • the nonionic surfactants herein are characterized by an HLB (hydrophilic- lipophilic balance) of from 7 to 20, preferably from 8 to 15. Examples of particularly suitable nonionic surfactants include
  • Suitable amine oxides include those with one alkyl or hydroxyalkyl moiety of 8 to 28 carbon atoms, preferably from 8 to 16 carbon atoms, and two alkyl moieties selected from alkyl groups and hydroxyalkyl groups with 1 to 3 carbon atoms.
  • Examples include dimethyloctylamine oxide, diethyldecylamine oxide, bis- (2-hydroxyethyl)dodecylamine oxide, dimethyldodecyl-amine oxide, dipropyltetradecylamine oxide, methylethylhexadecylamine oxide, dimethyl- 2-hydroxyoctadecylamine oxide, and coconut fatty alkyl dimethylamine oxide.
  • Suitable fatty acids include those containing from 12 to 25, preferably from 16 to 20 total carbon atoms, with the fatty moiety containing from 10 to 22, preferably from 1 5 to 17 (mid cut), carbon atoms.
  • Inorganic viscosity control agents which can also act like or augment the effect of the surfactant concentration aids, include water-soluble, ionizable salts which can also optionally be incorporated into the compositions of the present invention. Incorporation of these components to the composition must be processed at a very slow rate.
  • ionizable salts can be used.
  • suitable salts are the halides of the Group IA and IIA metals of the Periodic Table of the Elements, e.g., calcium chloride, magnesium chloride, sodium chloride, potassium bromide, and lithium chloride.
  • the ionizable salts are particularly useful during the process of mixing the ingredients to make the compositions herein, and later to obtain the desired viscosity.
  • the amount of ionizable salts used depends on the amount of active ingredients used in the compositions and can be adjusted according to the desires of the formulator. Typical levels of salts used to control the composition viscosity are from 20 to 20,000 parts per million (ppm), preferably from 20 to 1 1 ,000 ppm, by weight of the composition.
  • Alkylene polyammonium salts can be incorporated into the composition to give viscosity control in addition to or in place of the water-soluble, ionizable salts above.
  • these agents can act as scavengers, forming ion pairs with anionic detergent carried over from the main wash, in the rinse, and on the fabrics, and may improve softness performance. These agents may stabilise the viscosity over a broader range of temperature, especially at low temperatures, compared to the inorganic electrolytes.
  • alkylene polyammonium salts include l-lysine monohydrochloride and 1 ,5-diammonium 2-methyl pentane dihydrochloride.
  • Suitable liquid carriers are selected from water, organic solvents and mixtures thereof.
  • the liquid carrier employed in the instant compositions is preferably at least primarily water due to its low cost relative availability, safety, and environmental compatibility.
  • the level of water in the liquid carrier is preferably at least 50%, most preferably at least 60%, by weight of the carrier.
  • Mixtures of water and low molecular weight, e.g., ⁇ 200, organic solvent, e.g., lower alcohol such as ethanol, propanol, isopropanol or butanol are useful as the carrier liquid.
  • Low molecular weight alcohols include monohydric, dihydric (glycol, etc.) trihydric (glycerol, etc.), and higher polyhydric (polyols) alcohols.
  • the fabric softening composition can take a variety of physical forms including liquid such as aqueous or non-aqueous compositions and solid forms such as solid particulate forms. Such compositions may be applied onto a substrate such as a dryer sheet product, used as a rinse added product, or as a spray or foam product. Conveniently, when used as a spray or foam, the composition can either be sprayed onto the fabrics or even onto the drum surfaces such as the dryer drum surfaces. This will enable uniform dispersibility of the composition onto the fabrics.
  • the fabric softening composition can conveniently be made according to well known processes to the skilled person. An examplary disclosure is given in EP-A-0,668,902.
  • the benefit provided by the use of the present invention is that the loss in the fabric appearance is reduced or inhibited, e.g. it is meant that fabrics which are treated with a softening composition have a reduced or inhibited loss of appearance versus fabrics which were not treated with a softening composition. More preferably, the benefit is particularly on color fabrics where the treated fabrics show a reduced or inhibited fabric discoloration.
  • the resulting laundered fabrics were thereafter subjected to any one of the following treatments: a)- in the rinse cycle, 35ml of a fabric softening composition containing a fabric softener was added in the aqueous rinse bath. The treated terries were then tumble-dried. b)- in the rinse cycle, no fabric softening composition containing a fabric softener was added in the aqueous rinse bath. The fabric were then tumble-dried with a dryer-sheet containing a fabric softener. c)- in the rinse cycle, 35ml of a fabric softening composition containing a fabric softener was added in the aqueous rinse bath. The fabric were then tumble-dried with a dryer-sheet containing a fabric softener.
  • the dried fabric were then assessed for their loss of fabric appearance against a control by a grading panel of four persons using the Scheffe analysis to provide gradings (Panel Score Units-psu).
  • the control is a colored fabric washed with a conventional detergent composition but which has not been in contact with a fabric softener composition.
  • DTDMAMS Ditallow dimethyl ammonium methylsulfate
  • SDASA 1 :2 Ratio of stearyldimethyl amine:triple-pressed stearic acid
  • Glycosperse S-20 Polyethoxylated sorbitan monostearate available from Lonza Clay : Calcium Bentonite Clay, Bentonite L, sold by
  • the rinsed fabrics are thereafter tumble-dried and assessed for color appearance against laundered fabrics rinsed with no fabric softener and thereafter tumble-dried still without fabric softener using the fabric discoloration scale measurement.

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Abstract

The present invention relates to the use of a fabric softener composition, comprising at least one fabric softener component, for imparting fabric appearance benefits.

Description

USE OF A FABRIC SOFTENER COMPOSITION
Field of the invention
The present invention relates to fabric softener compositions. More particularly, it relates to the use of said fabric softening compositions for imparting fabric appearance benefits upon rinsing and/or drying of the fabrics.
Background of the invention
Processes such as wearing, washing, rinsing and/or tumble-drying of fabrics, e.g., clothing, beeding, household fabrics like table linens are normal part of the consumer's normal uses of fabrics. However, the Applicant has now found that such processes produce a loss of the fabric appearance; that is at least partly in the color fidelity and definition of the fabrics.
The problem has been found exacerbated at the location of the stress points such as seams and zippers but also influenced by the overall characteristics of the fabric, e.g., dye type, weave, thread count, fiber type, etc., and the composition of the laundry load, e.g., size, weight, and number of items. This problem has also been found further exacerbated after multiple washing cycles.
Whilst fabric softener compositions are known in the art for imparting benefits such as softness and/or antistatic properties and/or freshness impression, to the rinsed and/or dried fabric, as generally described in US 4,834,895 page 1 lines 19 to 32, the Applicant has now surprisingly found that the use of a fabric softening composition comprising a fabric softener component also ameliorates the problem of appearance loss, e.g., fuzziness and/or discoloration of the fabric.
An advantage of the invention is therefore to provide fabrics with effective color fidelity and definition. Such advantage is also seen to be greatly enhanced upon multiple washing cycle.
Not to be bound by theory, it is believed that by delivering the softener component in the rinse and/or drying cycle, the loss in the fabric appearance such as the fabric discoloration is inhibited or reduced in the next wash cycle.
Summary of the invention
The present invention relates to the use of a fabric softening composition, comprising at least one fabric softener component, for inhibiting or reducing loss of fabric appearance.
Detailed description of the invention
The present invention relates to the use of a fabric softener composition comprising at least one fabric softener component, for inhibiting or reducing loss of fabric appearance.
Fabric softener component
The essential component of the invention is a fabric softener component. Typical levels of said fabric softener components within the softener compositions are from 1 % to 99% by weight of the compositions. Depending on the composition execution for liquid compositions which can be dilute with a preferred level of fabric softening components from 1 % to 5%, or concentrated, with a preferred level of fabric softening components from 5% to 80%, more preferably 10% to 50%, most preferably 15% to 35% by weight. Where nonionic fabric softener components are present, the level of nonionic softener in the compositions will typically be from 0.1 % to 10%, preferably from 1 % to 5%.
Where the fabric softener composition is applied on a substrate such as a dryer-sheet, the preferred level of fabric softener components will preferably be from 20% to 99%, more preferably from 30% to 90% by weight, and even more preferably from 35% to 80% by weight..
Said fabric softening component may be selected from cationic, nonionic, amphoteric or anionic fabric softening component.
The preferred, typical cationic fabric softening components include the water-insoluble quaternary-ammonium fabric softening actives, the most commonly used having been di-long alkyl chain ammonium chloride or methyl sulfate. Preferred cationic softeners among these include the following:
1) ditallow dimethylammonium chloride (DTDMAC);
2) dihydrogenated tallow dimethylammonium chloride;
3) dihydrogenated tallow dimethylammonium methylsulfate;
4) distearyl dimethylammonium chloride;
5) dioleyl dimethylammonium chloride;
6) dipalmityl hydroxyethyl methylammonium chloride;
7) stearyl benzyl dimethylammonium chloride;
8) tallow trimethylammonium chloride;
9) hydrogenated tallow trimethylammonium chloride;
10) Ci2_1 a'kyl hydroxyethyl dimethylammonium chloride;
11) 12-I8 alkY' dihydroxyethyl methylammonium chloride;
12) di(stearoyloxyethyl) dimethylammonium chloride (DSOEDMAC);
13) di(tallowoyloxyethyl) dimethylammonium chloride;
14) ditallow imidazolinium methylsulfate;
15) 1-(2-tallowγlamidoethyl)-2-tallowyl imidazolinium methylsulfate. However, in recent years, the need has arisen for more environmentally-friendly materials, and rapidly biodegradable quaternary ammonium compounds have been presented as alternatives to the traditionally used di-long alkyl chain ammonium chlorides and methyl sulfates. Such quaternary ammonium compounds contain long chain alk(en)y) groups interrupted by functional groups such as carboxy groups. Said materials and fabric softening compositions containing them are disclosed in numerous publications such as EP-A-0,040,562, and EP-A- 0,239,910.
The quaternary ammonium compounds and amine precursors herein have the formula (I) or (II), below :
(I) (U)
wherein Q is selected from -O-C(O)-, -C(O)-O-, -O-C(O)-O-, -NR4-C(O)-, -
C(O)-NR4-;
R2 is (CH2)m-Q-T4 or Tδ or R3;
R3 is C1-C4 alkyl or C1-C4 hydroxyalkyl or H;
R4 is H or C1-C alkyl or C1-C4 hydroxyalkyl;
T1 , T2, T3, T4, T5 are independently C11 -C22 a,kV or alkenyl; n and m are integers from 1 to 4; and
X" is a softener-compatible anion.
Non-limiting examples of softener-compatible anions include chloride or methyl sulfate.
The alkyl, or alkenyl, chain T1 , T2, T3, T4, T^ must contain at least 11 carbon atoms, preferably at least 16 carbon atoms. The chain may be straight or branched. Tallow is a convenient and inexpensive source of long chain alkyl and alkenyl material. The compounds wherein T"l , T2, T3, T4, T^ represents the mixture of long chain materials typical for tallow are particularly preferred.
Specific examples of quaternary ammonium compounds suitable for use in the aqueous fabric softening compositions herein include :
1 ) N,N-di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride;
2) N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate;
3) N,N-di(2-tallowyl-oxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride;
4) N,N-di(2-tallowyl-oxy-ethylcarbonyl-oxy-ethyl)-N,N-dimethyl ammonium chloride;
5) N-(2-tallowyl-oxy-2-ethyl)-N-(2-tallowyl-oxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride;
6) N,N,N-tri(tallowyl-oxy-ethyl)-N-methyl ammonium chloride;
7) N-(2-tallowyl-oxy-2-oxo-ethyl)-N-(tallowyl-N,N-dimethyl-ammonium chloride; and
8) 1 ,2-ditallowyl-oxy-3-trimethylammoniopropane chloride; and mixtures of any of the above materials.
Of these, compounds 1-7 are examples of compounds of Formula (I); compound 8 is a compound of Formula (ll).
Particularly preferred is N,N-di(tallowγl-oxy-ethyl)-N,N-dimethyl ammonium chloride, where the tallow chains are at least partially unsaturated. The level of unsaturation of the tallow chain can be measured by the Iodine Value (IV) of the corresponding fatty acid, which in the present case should preferably be in the range of from 5 to 100 with two categories of compounds being distinguished, having a IV below or above 25. Indeed, for compounds of Formula (I) made from tallow fatty acids having a IV of from 5 to 25, preferably 15 to 20, it has been found that a cis/trans isomer weight ratio greater than 30/70, preferably greater than 50/50 and more preferably greater than 70/30 provides optimal concentrability. For compounds of Formula (I) made from tallow fatty acids having a IV of above 25, the ratio of cis to trans isomers has been found to be less critical unless very high concentrations are needed.
Other examples of suitable quaternary ammoniums of Formula (I) and (II) are obtained by, e.g. :
- replacing "tallow" in the above compounds with, for example, coco, palm, lauryl, oleγl, ricinoleyi, stearyl, palmityl, or the like, said fatty acyl chains being either fully saturated, or preferably at least partly unsaturated;
- replacing "methyl" in the above compounds with ethyl, ethoxy, propyl, propoxy, isopropyl, butyl, isobutyl or t-butyl;
- replacing "chloride" in the above compounds with bromide, methylsulfate, formate, sulfate, nitrate, and the like.
In fact, the anion is merely present as a counterion of the positively charged quaternary ammonium compounds. The nature of the counterion is not critical at all to the practice of the present invention. The scope of this invention is not considered limited to any particular anion. By "amine precursors thereof" is meant the secondary or tertiary amines corresponding to the above quaternary ammonium compounds, said amines being substantially protonated in the present compositions due to the pH values.
Additional fabric softening materials may be used in addition or alternatively to the biodegradable fabric softener. These may be selected from nonionic, amphoteric or anionic fabric softening material. Disclosure of such materials may be found in US 4,327,133; US 4,421 ,792; US 4,426,299; US 4,460,485; US 3,644,203; US 4,661 ,269; U.S 4,439,335; U.S 3,861 ,870; US 4,308,151 ; US 3,886,075; US 4,233,164; US 4,401 ,578; US 3,974,076; US 4,237,016 and EP 472, 178.
Typically, such nonionic fabric softener materials have a HLB of from about 2 to about 9, more typically from about 3 to about 7. Such nonionic fabric softener materials tend to be readily dispersed either by themselves, or when combined with other materials such as single-long-chain alkyl cationic surfactant described in detail hereinafter. Dispersibility can be improved by using more single-long-chain alkyl cationic surfactant, mixture with other materials as set forth hereinafter, use of hotter water, and/or more agitation. In general, the materials selected should be relatively crystalline, higher melting, (e.g. >40°C) and relatively water-insoluble.
Preferred nonionic softeners are fatty acid partial esters of polyhydric alcohols, or anhydrides thereof, wherein the alcohol, or anhydride, contains from 2 to 18, preferably from 2 to 8, carbon atoms, and each fatty acid moiety contains from 12 to 30, preferably from 16 to 20, carbon atoms.
Typically, such softeners contain from one to 3, preferably 2 fatty acid groups per molecule.
The polyhydric alcohol portion of the ester can be ethylene glycol, glycerol, poly (e.g., di-, tri-, tetra, penta-, and/or hexa-) glycerol, xylitol, sucrose, erythritol, pentaerythritol, sorbitol or sorbitan. Sorbitan esters and polyglycerol monostearate are particularly preferred.
The fatty acid portion of the ester is normally derived from fatty acids having from 12 to 30, preferably from 16 to 20, carbon atoms, typical examples of said fatty acids being lauric acid, myristic acid, palmitic acid, stearic acid and behenic acid.
Highly preferred optional nonionic softening agents for use in the present invention are the sorbitan esters, which are esterified dehydration products of sorbitol, and the glycerol esters.
Commercial sorbitan monostearate is a suitable material. Mixtures of sorbitan stearate and sorbitan palmitate having stearate/palmitate weight ratios varying between about 10: 1 and about 1 :10, and 1 ,5-sorbitan esters are also useful.
Glycerol and polyglycerol esters, especially glycerol, diglycerol, triglycerol, and polyglycerol mono- and/or di-esters, preferably mono-, are preferred herein (e.g. polyglycerol monostearate with a trade name of Radiasurf
7248).
Useful glycerol and polyglycerol esters include mono-esters with stearic, oleic, palmitic, lauric, isostearic, myristic, and/or behenic acids and the diesters of stearic, oleic, palmitic, lauric, isostearic, behenic, and/or myristic acids. It is understood that the typical mono-ester contains some di- and tri-ester, etc.
The "glycerol esters" also include the polyglycerol, e.g., diglycerol through octaglycerol esters. The polyglycerol polyols are formed by condensing glycerin or epichlorohydrin together to link the glycerol moieties via ether linkages. The mono- and/or diesters of the polyglycerol polyols are preferred, the fatty acyl groups typically being those described hereinbefore for the sorbitan and glycerol esters.
Further fabric softening components suitable for use herein are the softening clays, such as the low ion-exchange-capacity ones described in EP-A-0, 150,531.
For the preceding fabric softening agents, especially with biodegradable fabric softening agents, the pH of the liquid compositions herein is an essential parameter of the present invention, indeed, it influences the stability of the quaternary ammonium or amine precursors compounds, especially in prolonged storage conditions. The pH, as defined in the present context, is measured in the neat compositions at 20°C. For optimum hydrolytic stability of these compositions, the neat pH, measured in the above-mentioned conditions, must be in the range of from 2.0 to 4.5. Preferably, where the liquid fabric softening compositions of the invention are in a concentrated form, the pH of the neat composition is in the range of 2.0 to 3.5, while if it is in a diluted form, the pH of the neat composition is in the range of 2.0 to 3.0. The pH of these compositions herein can be regulated by the addition of a Bronsted acid. Examples of suitable acids include the inorganic mineral acids, carboxylic acids, in particular the low molecular weight (C1-C5) carboxylic acids, and alkylsulfonic acids. Suitable inorganic acids include HCI, H2SO4, HNO3 and H3PO4. Suitable organic acids include formic, acetic, citric, methylsulfonic and ethylsulfonic acid. Preferred acids are citric, hydrochloric, phosphoric, formic, methylsulfonic acid, and benzoic acids.
Additional components
The composition may also optionally contain additional components such as surfactant concentration aids, electrolyte concentration aids, stabilisers, such as well known antioxidants and reductive agents, soil release polymers, emulsifiers, bacteriocides, colorants, perfumes, preservatives, optical brighteners, anti ionisation agents, antifoam agents and enzymes. These ingredients, especially the minor ingredients, and especially perfume, can be usefully added with, and preferably protected by, "carrier materials" such as zeolites, starch, cyclodextrin, wax, etc. Surfactant concentration aids
Surfactant concentration aids may also optionally be used. Surfactant concentration aids are typically selected from single long chain alkyl cationic surfactants, nonionic surfactants, amine oxides, fatty acids, and mixtures thereof, typically used at a level of from 0 to 15% of the composition.
Single long chain alkyl cationic surfactants
Such mono-long-chain-alkyl cationic surfactants useful in the present invention are, preferably, quaternary ammonium salts of the general formula :
[R N + R31 X- wherein the R2 group is C-|0'C22 hydrocarbon group, preferably C12- 18 alkyl group of the corresponding ester linkage interrupted group with a short alkylene (C1-C4) group between the ester linkage and the N, and having a similar hydrocarbon group, e.g., a fatty acid ester of choline, preferably Ci 2" -]4 (coco) choline ester and/or C-| 6~Cl 8 ta'l°w choline ester at from 0.1 % to 20% by weight of the softener active. Each R is a C1-C4 alkyl or substituted (e.g., hydroxy) alkyl, or hydrogen, preferably methyl, and the counterion X" is a softener compatible anion, for example, chloride, bromide, methyl sulfate, etc.
Other cationic materials with ring structures such as alkyl imidazoiine, imidazolinium, pyridine, and pyridinium salts having a single Ci 2" 30 a'kY' chain can also be used. Very low pH is required to stabilize, e.g., imidazoiine ring structures.
Some alkyl imidazolinium salts and their imidazoiine precursors useful in the present invention have the general formula :
wherein Y2 is -C(O)-O-, -O-(O)C-, -C(O)-N(R5)-, or -N(R5)-C(0)- in which Rδ is hydrogen or a C1-C4 alkyl radical; R6 is a C1-C4 alkyl radical or H (for imidazoiine precursors); R? and R^ are each independently selected from R and R2 as defined hereinbefore for the single-long-chain cationic surfactant with only one being R2.
Some alkyl pyridinium salts useful in the present invention have the general formula :
wherein R2 and X- are as defined above. A typical material of this type is cetyl pyridinium chloride.
Nonionic Surfactant (Alkoxylated Materials)
Suitable nonionic surfactants for use herein include addition products of ethylene oxide and, optionally, propylene oxide, with fatty alcohols, fatty acids, fatty amines, etc.
Suitable compounds are substantially water-soluble surfactants of the general formula :
R2 - Y - (C2H4θ)2 - C2H4OH wherein R2 is selected from primary, secondary and branched chain alkyl and/or acyl hydrocarbyl groups; primary, secondary and branched chain alkenyl hydrocarbyl groups; and primary, secondary and branched chain alkyl- and alkenyl-substituted phenolic hydrocarbyl groups; said hydrocarbyl groups having a hydrocarbyl chain length of from 8 to 20, preferably from 10 to 18 carbon atoms.
Y is typically -O-, -C(O)O-, -C(O)N(R)-, or -C(O)N(R)R-, in which R2 and R, when present, have the meanings given hereinbefore, and/or R can be hydrogen, and z is at least 8, preferably at least 10-1 1 . The nonionic surfactants herein are characterized by an HLB (hydrophilic- lipophilic balance) of from 7 to 20, preferably from 8 to 15. Examples of particularly suitable nonionic surfactants include
- Straight-Chain, Primary Alcohol Alkoxylates such as tallow alcohol- EO(11 ), tallow alcohol-EO(18), and tallow alcohol-EO(25);
- Straight-Chain, Secondary Alcohol Alkoxylates such as 2-C-j 6EO(1 1 ); 2- C2oEO(1 1 ); and 2-C1 6EO(14); - Alkyl Phenol Alkoxylates, such as p-tridecylphenol EO(1 1 ) and p- pentadecylphenol EO(18), as well as
- Olefinic Alkoxylates, and Branched Chain Alkoxylates such as branched chain primary and secondary alcohols which are available from the well¬ known "OXO" process.
Amine Oxides
Suitable amine oxides include those with one alkyl or hydroxyalkyl moiety of 8 to 28 carbon atoms, preferably from 8 to 16 carbon atoms, and two alkyl moieties selected from alkyl groups and hydroxyalkyl groups with 1 to 3 carbon atoms.
Examples include dimethyloctylamine oxide, diethyldecylamine oxide, bis- (2-hydroxyethyl)dodecylamine oxide, dimethyldodecyl-amine oxide, dipropyltetradecylamine oxide, methylethylhexadecylamine oxide, dimethyl- 2-hydroxyoctadecylamine oxide, and coconut fatty alkyl dimethylamine oxide.
Fattv Acids
Suitable fatty acids include those containing from 12 to 25, preferably from 16 to 20 total carbon atoms, with the fatty moiety containing from 10 to 22, preferably from 1 5 to 17 (mid cut), carbon atoms.
Electrolyte Concentration Aids
Inorganic viscosity control agents which can also act like or augment the effect of the surfactant concentration aids, include water-soluble, ionizable salts which can also optionally be incorporated into the compositions of the present invention. Incorporation of these components to the composition must be processed at a very slow rate.
A wide variety of ionizable salts can be used. Examples of suitable salts are the halides of the Group IA and IIA metals of the Periodic Table of the Elements, e.g., calcium chloride, magnesium chloride, sodium chloride, potassium bromide, and lithium chloride. The ionizable salts are particularly useful during the process of mixing the ingredients to make the compositions herein, and later to obtain the desired viscosity. The amount of ionizable salts used depends on the amount of active ingredients used in the compositions and can be adjusted according to the desires of the formulator. Typical levels of salts used to control the composition viscosity are from 20 to 20,000 parts per million (ppm), preferably from 20 to 1 1 ,000 ppm, by weight of the composition.
Alkylene polyammonium salts can be incorporated into the composition to give viscosity control in addition to or in place of the water-soluble, ionizable salts above. In addition, these agents can act as scavengers, forming ion pairs with anionic detergent carried over from the main wash, in the rinse, and on the fabrics, and may improve softness performance. These agents may stabilise the viscosity over a broader range of temperature, especially at low temperatures, compared to the inorganic electrolytes.
Specific examples of alkylene polyammonium salts include l-lysine monohydrochloride and 1 ,5-diammonium 2-methyl pentane dihydrochloride.
Another ingredient is a liquid carrier. Suitable liquid carriers are selected from water, organic solvents and mixtures thereof. The liquid carrier employed in the instant compositions is preferably at least primarily water due to its low cost relative availability, safety, and environmental compatibility. The level of water in the liquid carrier is preferably at least 50%, most preferably at least 60%, by weight of the carrier. Mixtures of water and low molecular weight, e.g., < 200, organic solvent, e.g., lower alcohol such as ethanol, propanol, isopropanol or butanol are useful as the carrier liquid. Low molecular weight alcohols include monohydric, dihydric (glycol, etc.) trihydric (glycerol, etc.), and higher polyhydric (polyols) alcohols.
Form of the composition
The fabric softening composition can take a variety of physical forms including liquid such as aqueous or non-aqueous compositions and solid forms such as solid particulate forms. Such compositions may be applied onto a substrate such as a dryer sheet product, used as a rinse added product, or as a spray or foam product. Conveniently, when used as a spray or foam, the composition can either be sprayed onto the fabrics or even onto the drum surfaces such as the dryer drum surfaces. This will enable uniform dispersibility of the composition onto the fabrics.
Process
The fabric softening composition can conveniently be made according to well known processes to the skilled person. An examplary disclosure is given in EP-A-0,668,902.
Reduction or inhibition of the loss of fabric appearance
The benefit provided by the use of the present invention is that the loss in the fabric appearance is reduced or inhibited, e.g. it is meant that fabrics which are treated with a softening composition have a reduced or inhibited loss of appearance versus fabrics which were not treated with a softening composition. More preferably, the benefit is particularly on color fabrics where the treated fabrics show a reduced or inhibited fabric discoloration.
Loss in fabric appearance method
2 replicates of colored fabrics were washed with a conventional detergent composition.
The resulting laundered fabrics were thereafter subjected to any one of the following treatments: a)- in the rinse cycle, 35ml of a fabric softening composition containing a fabric softener was added in the aqueous rinse bath. The treated terries were then tumble-dried. b)- in the rinse cycle, no fabric softening composition containing a fabric softener was added in the aqueous rinse bath. The fabric were then tumble-dried with a dryer-sheet containing a fabric softener. c)- in the rinse cycle, 35ml of a fabric softening composition containing a fabric softener was added in the aqueous rinse bath. The fabric were then tumble-dried with a dryer-sheet containing a fabric softener.
Loss fabric appearance scale measurement
The dried fabric were then assessed for their loss of fabric appearance against a control by a grading panel of four persons using the Scheffe analysis to provide gradings (Panel Score Units-psu). The control is a colored fabric washed with a conventional detergent composition but which has not been in contact with a fabric softener composition. A positive PSU value indicates a better performance (PSU scale: 0 = no difference, 1 = I think there is a difference, 2 = I know there is a difference, 3 = I know there is a lot of difference, 4 = I know there is a whole lot of difference).
The invention is illustrated in the following non limiting examples, in which all percentages are on a weight basis unless otherwise stated.
In the examples, the abbreviated component identifications have the following meanings:
DEQA Di-(tallowyl-oxy-ethyl) dimethyl ammonium chloride
DHEQA Di-(soft-tallowyl-oxy-ethyl) hydroxyethyl methyl ammonium methylsulfate
Fatty acid Stearic acid of IV = 0
Electrolyte Calcium chloride
Digeranyl : 1 ,4-Butandioic acid, 3,7-dimethyl-2,6-octadienyl
Succinate ester
DTDMAMS : Ditallow dimethyl ammonium methylsulfate
SDASA : 1 :2 Ratio of stearyldimethyl amine:triple-pressed stearic acid Glycosperse S-20 : Polyethoxylated sorbitan monostearate available from Lonza Clay : Calcium Bentonite Clay, Bentonite L, sold by
Southern Clay Products Neodol 45-13 : C1 -C15 linear primary alcohol ethoxylate, sold by
Shell Chemical Co PEG Polyethylene Glycol 4000
Example 1
Colored fabrics are washed with a conventional laundry detergent composition and thereafter rinsed with a fabric softener composition as stated in the fabric discoloration measurement method. The formulations of the fabric softening compositions are as follows:
Component A B C D E
DEQA 2.6 2.9 18.0 19.0 19.0
Fatty acid 0.3 . 1.0 _ .
Hydrochloride acid 0.02 0.02 0.02 0.02 0.02
PEG - . 0.6 0.6 0.6
Perfume 1.0 1.0 1.0 1.0 1.0
Silicone antifoam 0.01 0.01 0.01 0.01 0.01
Electrolyte - - 600ppm 600ppm 1200pp m
Dye 10ppm 10ppm 50ppm 50ppm 50ppm
Water and minors to balance to 100
The rinsed fabrics are thereafter tumble-dried and assessed for color appearance against laundered fabrics rinsed with no fabric softener and thereafter tumble-dried still without fabric softener using the fabric discoloration scale measurement.
The results show that fabrics rinsed with a fabric softener exhibit a better overall appearance, especially for colored fabrics, than non treated fabrics.
Example 2
Colored fabrics are washed with a conventional laundry detergent composition, rinsed and thereafter tumble-dried in presence of a dryer added fabric softener product. Similar results as for example 1 were observed.
Example 3
Similar results are observed where a fabric conditioner bar is used.

Claims

Claims
1- Use of a fabric softening composition, comprising at least one fabric softener component, for inhibiting or reducing loss of fabric appearance.
2-Use according to Claim 1 , wherein said fabric softener component is selected from cationic, nonionic, amphoteric, anionic and clay fabric softening components.
3-Use according to Claim 2, wherein said fabric softener is a biodegradable cationic component.
4-Use according to Claim 3, wherein said biodegradable cationic component has the formula:
(I) (II)
wherein Q is selected from -O-C(O)-, -C(O)-O-, -O-C(O)-O-, -NR4-C(O)-,
C(O)-NR4-;
R1 is (CH2)n-Q-T2 or T3;
R2 is (CH2)m-Q-T4 or Tδ or R3;
R3 is C1-C4 alkyl or C1-C4 hydroxyalkyl or H;
R4 is H or C1 -C4 alkyl or C1-C4 hydroxyalkyl;
T1 , T2, T3, T4, T5 are independently Ci 1"C22 a,kY| or alkenyl; n and m are integers from 1 to 4; and
X" is a softener-compatible anion.
5- Use according to any one of Claims 1-4, wherein said fabric softener component is incorporated in a liquid composition. 6- Use according to any one of Claims 1-4, wherein said fabric softener component is incorporated in a solid particulate composition.
7- Use according to any one of Claims 1 -6, wherein said fabric softener component is applied on a substrate.
8-Use according to Claim 7, wherein said substrate is a dryer sheet.
EP96910640A 1996-03-29 1996-03-29 Use of a fabric softener composition Withdrawn EP0891408A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CA002250225A CA2250225A1 (en) 1996-03-29 1996-03-29 Use of a fabric softener composition
PCT/US1996/004315 WO1997036976A1 (en) 1996-03-29 1996-03-29 Use of a fabric softener composition
CN 96180310 CN1219952A (en) 1996-03-29 1996-03-29 Use of fabric softener composition

Publications (1)

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GB0200151D0 (en) * 2002-01-04 2002-02-20 Unilever Plc Fabric conditioning compositions

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GB8504733D0 (en) * 1985-02-23 1985-03-27 Procter & Gamble Ltd Detergent compositions
US4834895A (en) * 1987-08-17 1989-05-30 The Procter & Gamble Company Articles and methods for treating fabrics in clothes dryer
US5183580A (en) * 1990-11-27 1993-02-02 Lever Brothers Company, Division Of Conopco Inc. Liquid fabric conditioner containing fabric softener and green colorant
GB9026050D0 (en) * 1990-11-30 1991-01-16 Unilever Plc Process and composition for treating fabrics
GB9218342D0 (en) * 1992-08-28 1992-10-14 Unilever Plc Use of fabric softening composition
GB9319567D0 (en) * 1993-09-22 1993-11-10 Unilever Plc Fabric conditioner
US5474690A (en) * 1994-11-14 1995-12-12 The Procter & Gamble Company Concentrated biodegradable quaternary ammonium fabric softener compositions containing intermediate iodine value fatty acid chains
EP0719856B1 (en) * 1994-12-29 2002-10-16 The Procter & Gamble Company Softening-through-the-wash laundry detergent compositions

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