EP0856045A1 - Fabric softener compositions - Google Patents
Fabric softener compositionsInfo
- Publication number
- EP0856045A1 EP0856045A1 EP96933199A EP96933199A EP0856045A1 EP 0856045 A1 EP0856045 A1 EP 0856045A1 EP 96933199 A EP96933199 A EP 96933199A EP 96933199 A EP96933199 A EP 96933199A EP 0856045 A1 EP0856045 A1 EP 0856045A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- fabric softener
- perfume
- compound
- composition
- 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.)
- Granted
Links
Classifications
-
- 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
- C11D3/16—Organic compounds
- C11D3/36—Organic compounds containing phosphorus
- C11D3/364—Organic compounds containing phosphorus containing nitrogen
-
- 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
-
- 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
Definitions
- the present invention relates to fabric softener compositions having enhanced storage stability. More particularly, the present invention relates to a fabric softening composition comprising a fabric softening component, a heavy metal ion sequestrant and a component selected from a dye, a perfume, a compound having a fatty acid moiety of Iodine Value (IV) of at least 2 and mixtures thereof.
- a fabric softening composition comprising a fabric softening component, a heavy metal ion sequestrant and a component selected from a dye, a perfume, a compound having a fatty acid moiety of Iodine Value (IV) of at least 2 and mixtures thereof.
- Fabric softening compositions are known in the art and have been widely used by consumers during the rinse cycles of laundry operations. However, consumer acceptance of such compositions is determined not only by the performance achieved with these products but also by the aesthetics associated therewith.
- the perfume systems as well as the dye systems are therefore an important aspect of the successful formulation of such commercial products.
- fatty acids of IV of at least 2 and/or fatty acids compounds having fatty acid moiety of IV of at least 2 which include components such as N,N- di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride have been observed to degrade upon storage, resulting in a performance loss together with a strong odour characteristic of the degradation.
- the higher the IV value the higher the degradation.
- Co-pending application PCT/US95/05267 discloses a fabric softening composition
- a fabric softening composition comprising a fabric softening agent, a cellulase and a chelant wherein said chelant is present in amount of 10ppm to 0.5% by weight of the composition.
- the Iodine Value herein described (IV) is a method well known in the art for measuring the degree of unsaturation of a fatty acid compound or a fatty acid moiety. This is measured by titration of Iodine whereby the number of Iodine molecule which have disappeared is proportional to the number of unsaturation of the fatty acid compound or moiety.
- a fabric softener composition which is free of cellulase and which comprises:
- composition comprises a component selected from a dye, a perfume, a fatty acid compound of Iodine Value (IV) of at least 2, a compound having one or more fatty acid moieties of Iodine value (IV) of at least 2, and mixtures thereof.
- An essential component of the invention is a fabric softening compound.
- Fabric softening compositions in particular fabric softening compositions to be used in the rinse cycle of laundry washing processes, are well known.
- Compositions of the present invention preferably comprise from 1 to 80% by weight of fabric softening active, more preferably from 2 to 70% by weight, most preferably from 5 to 50% by weight of the composition.
- Conventional fabric softening materials may be used. These may be selected from cationic fabric softening materials such as di-long alkyl chain ammonium chloride and biodegradable fabric softening materials, nonionic, amphoteric or anionic fabric softening material. Disclosure of such materials may be found in US 4,327, 1 33; 4,421 ,792; 4,426,299; 4,460,485; 3,644,203 and 4,661 ,269.
- Preferred fabric softening materials are biodegradable quaternary ammonium compounds contain long chain alk(en)yl groups interrupted by functional groups such as carboxy groups.
- EPA 239 910 a pH range of from 2.5 to 4.2 provides optimum storage stability to said rapidly biodegradable ammonium compounds.
- 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)-, -C(O)-NR 4 -;
- R l is (CH 2 ) n -Q-T 2 or T3 ;
- R 2 is (CH 2 ) m -Q-T 4 or T 5 or R 3 ;
- R 3 is C1 -C4 alkyl or C1 -C4 hydroxyalkyl or H;
- R 4 is H or C 1 -C4 alkyl or C1 -C4 hydroxyalkyl
- T 1 , T 2 , T 3 , T 4 , T 5 are independently Ci 1 -C22 a,k y' 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 1 1 carbon atoms, preferably at least 1 6 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 T1 , 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 (II).
- N,N-di(tallowoyl-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.
- IV Iodine Value
- 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 claimed pH values.
- the pH of the 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 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 HCl, 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.
- the quaternary ammonium or amine precursors compounds herein are present at levels of from 1 % to 80% of compositions herein, depending on the composition execution which can be dilute with a preferred level of active biodegradable fabric softening components from 1 % to 5%, or concentrated, with a preferred level of active biodegradable fabric softening components from 5% to 80%, more preferably 10% to 50%, most preferably 15% to 35% by weight.
- Softening agents also useful in the present invention compositions are nonionic fabric softener materials, preferably in combination with cationic softening agents.
- such nonionic fabric softener materials have a HLB of from 2 to 9, more typically from 3 to 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.
- the level of optional nonionic softener in the compositions herein is typically from 0.1 % to 10%, preferably from 1 % to 5%.
- 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 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 1 2 to 30, preferably from 1 6 to 20, carbon atoms, typical examples of said fatty acids being lauric acid, myristic acid, palmitic acid, stearic acid, oleic 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 10:1 and 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.
- suitable fabric softener agents useful herein may comprise one, two, or all three of the following fabric softening agents:
- Softening agents (actives) of the present invention may be the reaction products of higher fatty acids with a polyamine selected from hydroxyalkylalkylenediamines and dialkylenetriamines and mixtures thereof. These reaction products are mixtures of several compounds in view of the multi-functional structure of the polyamines.
- the preferred Component (a) is a nitrogenous compound selected from the reaction product mixtures or some selected components of the mixtures. More specifically, the preferred Component (a) is compounds selected from substituted imidazoline compounds having the formula:
- R 1 is an acyclic aliphatic C1 5-C21 hydrocarbon group and R 2 is a divalent C1 -C3 alkylene group.
- Component (a) materials are commercially available as: Mazamide® 6, sold by Mazer Chemicals, or Ceranine® HC, sold by Sandoz Colors & Chemicals; stearic hydroxyethyl imidazoline sold under the trade names of Alkazine® ST by Alkaril Chemicals, Inc., or Schercozoline® S by Scher Chemicals, Inc.; N,N"-ditallowalkoyldiethylenetriamine; 1 - tallowamidoethyl - 2 - tallowimidazoline (wherein in the preceeding structure R * ' is an aliphatic C1 5-C1 7 hydrocarbon group and R 2 is a divalent ethylene group).
- Certain of the Components (a) can also be first dispersed in a Bronsted acid dispersing aid having a pKa value of not greater than 4; provided that the pH of the final composition is not greater than 5.
- a Bronsted acid dispersing aid having a pKa value of not greater than 4; provided that the pH of the final composition is not greater than 5.
- Some preferred dispersing aids are hydrochloric acid, phosphoric acid, or methylsulfonic acid.
- Both N,N"-ditallowalkoyldiethylenetriamine and 1 -tallow(amidoethyl)-2- tallowimidazoline are reaction products of tallow fatty acids and diethylenetriamine, and are precursors of the cationic fabric softening agent methyl- 1 -tallowamidoethyl-2-tallowimidazolinium methylsulfate (see
- N,N"-ditallow alkoyldiethylenetriamine and 1 -tallowamidoethyl-2- tallowimidazoline can be obtained from Witco Chemical Company as experimental chemicals.
- Methyl-1 -tallowamidoethyl-2-tallowimidazolinium methylsulfate is sold by Witco Chemical Company under the tradename Varisoft® 475.
- Component fb) is a cationic nitrogenous salt containing one long chain acyclic aliphatic C1 5-C22 hydrocarbon group, preferably selected from acyclic quatemary ammonium salts having the formula:
- R 4 is an acyclic aliphatic C i 5-C22 hydrocarbon group
- R ⁇ and R ⁇ are C1 -C4 saturated alkyl or hydroxy alkyl groups
- A- is an anion.
- Component (b) are the monoalkyltrimethylammonium salts such as monotallowtrimethylammonium chloride, mono (hydrogenated tallow) trimethylammonium chloride, palmityltrimethyl ammonium chloride and soyatrimethylammonium chloride, sold by Sherex Chemical Company under the trade name Adogen® 47I, Adogen® 441 , Adogen® 444, and Adogen® 41 5, respectively.
- R 4 is an acyclic aliphatic C- ⁇ ⁇ - C-
- R 5 and R 6 are methyl groups.
- Mono (hydrogenated tallow) trimethylammonium chloride and monotallowtrimethylammonium chloride are preferred.
- Component (b) are behenyltrimethylammonium chloride wherein R 4 is a C22 hydrocarbon group and sold under the trade name Kemamine® Q2803-C by Humko Chemical Division of Witco Chemical Corporation; soyadimethylethylammonium eth lsulfate wherein R 4 is a C-
- Kemamine® Q2803-C by Humko Chemical
- Component (b) examples are 1 -ethyl- 1 -(2-hydroxy ethyl)-2- isoheptadecylimidazolinium ethylsulfate, available from Mona Industries, Inc. under the trade name Monaquat® ISIES; mono(tallowoyloxyethyl) hydroxyethyldimethylammonium chloride, i.e., monoester of tallow fatty acid with di(hydroxyethyl)dimethylammonium chloride, a by-product in the process of making diester of tallow fatty acid with di(hydroxyethyl)dimethylammonium chloride, i.e., di(tallowoyloxyethyl)dimethylammonium chloride.
- Component (c): Preferred cationic nitrogenous salts having two or more long chain acyclic aliphatic C1 5-C22 hydrocarbon groups or one said group and an arylalkyl group which can be used either alone or as part of a mixture are selected from the group consisting of: (i) acyclic quaternary ammonium salts having the formula:
- R 4 is an acyclic aliphatic C1 5-C22 hydrocarbon group
- R ⁇ is a C1 -C4 saturated alkyl or hydroxyalkyl group
- R ⁇ is selected from R 4 and R ⁇ groups
- A- is an anion defined as above;
- R ⁇ is an acyclic aliphatic C1 5-C 1 hydrocarbon group
- each R 2 is the same or different divalent alkylene group having 1 to 3 carbon atoms
- R ⁇ and R ⁇ are C 1 -C4 saturated alkyl or hydroxyalkyl groups
- A- is an anion
- n is equal to 1 to 5, and R ⁇ , R 2 , R ⁇ and A- are as defined above;
- each R substituent is a short chain C " ⁇ -CQ, preferably C1 -C3 alkyl or hydroxyalkyl group, e.g., methyl (most preferred), ethyl, propyl, hydroxyethyl, and the like, benzyl, or mixtures thereof;
- each R 2 is a long chain C10-C22 hydrocarbyl, or substituted hydrocarbyl substituent, preferably C15-C19 alkyl and/or alkenyl, most preferably C15-C18 straight chain alkyl and/or alkenyl; and
- the counterion, A- can be any softener-compatible anion, for example, chloride, bromide, methylsulfate, formate, sulfate, nitrate and the like;
- Component (c) are the well-known dialkyldi methylammonium salts such as ditallowdimethylammonium chloride, ditallowdimethylammonium methylsulfate, di (hydrogenatedtallow) dimethylammonium chloride, distearyldimethylammonium chloride, dibehenyldimethylammonium chloride. Di(hydrogenatedtallow)di methylammonium chloride and ditallowdimethylammonium chloride are preferred.
- dialkyldimethyl ammonium salts examples include di(hydrogenatedtallow)dimethylammonium chloride (trade name Adogen® 442), ditallowdimethylammonium chloride (trade name Adogen® 470), distearyl dimethylammonium chloride (trade name Arosurf® TA-100), all available from Witco Chemical Company.
- Dibehenyldimethylammonium chloride is sold under the trade name Kemamine Q-2802C by Humko Chemical Division of Witco Chemical Corporation.
- Component (c) are methylbis(tallowamidoethyl)(2- hydroxyethyDammonium methylsulfate and methylbis(hydrogenated tallowamidoethyl)(2-hydroxyethyl)ammonium methylsulfate; these materials are available from Witco Chemical Company under the trade names Varisoft ® 222 and Varisoft® 1 10, respectively: dimethylstearylbenzyl ammonium chloride sold under the trade names Varisoft® SDC by Witco Chemical Company and Ammonyx® 490 by Onyx Chemical Company; 1 -methyl-1 - tallowamidoethyl-2-tallowimidazolinium methylsulfate and 1 -methyl-1 - (hydrogenatedtallowamidoethyl)-2-(hydrogenatedtallow)imidazolinium methylsulfate ; they are sold under the trade names Varisoft® 475 and Varisoft® 445, respectively, by Witco Chemical Company.
- stable liquid compositions herein are formulated at a pH in the range of 2 to 5, preferably from 2 to 4.5, more preferably from 2 to 4.
- the pH can be adjusted by the addition of a Bronsted acid.
- Ranges of pH for making stable softener compositions containing diester quaternary ammonium fabric softening compounds are disclosed in U.S 4,767,547. These types of compounds and general methods of making them are disclosed in U.S 4, 1 37, 180.
- a preferred composition contains Component (a) at a level of from 10% to 80%, Component (b) at a level of from 3% to 40%, and Component (c) at a level of from 10% to 80%, by weight of the fabric softening component of the present invention compositions.
- An even more preferred composition contains Component (a): the reaction product of 2 moles of hydrogenated tallow fatty acids with 1 mole of N-2- hydroxyethylethylenediamine and is present at a level of from 20% to 70% by weight of the fabric softening component of the present invention compositions; Component (b): mono(hydrogenated tallow)trimethyl ammonium chloride present at a level of from 3% to 30% by weight of the fabric softening component of the present invention compositions; Component (c): selected from di(hydrogenatedtallow)dimethylammonium chloride, ditallowdimethylammonium chloride, methyl- 1 -tallowamidoethyl-2- tallowimidazolinium methylsulfate, diethanol ester dimethylammonium chloride, and mixtures thereof; wherein Component (c) is present at a level of from 20% to 60% by weight of the fabric softening component of the present invention compositions; and wherein the weight ratio of said di(hydr
- the anion A- provides charge neutrality.
- the anion used to provide charge neutrality in these salts is a halide, such as chloride or bromide.
- other anions can be used, such as methylsulfate, ethylsulfate, hydroxide, acetate, formate, citrate, sulfate, carbonate, and the like. Chloride and methylsulfate are preferred herein as anion A-.
- the amount of fabric softening agent (fabric softener) in liquid compositions of this invention is typically from 2% to 50%, preferably from 4% to 30%, by weight of the composition.
- the lower limits are amounts needed to contribute effective fabric softening performance when added to laundry rinse baths in the manner which is customary in home laundry practice.
- the higher limits are suitable for concentrated products which provide the consumer with more economical usage due to a reduction of packaging and distributing costs.
- Heavy metal ion sequestrants are essential components herein for the purpose of the invention.
- heavy metal ion sequestrants it is meant components which act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferentially they bind heavy metal ions such as iron, manganese and copper.
- Heavy metal ion sequestrants are present at a level less than 0.5% (excluding 0.5%), preferably in amount from 0.001 % (10ppm) to 0.5%, more preferably from 0.005% to 0.1 %, most preferably from 0.01 % to 0.05% by weight of the compositions.
- Heavy metal ion sequestrants which are acidic in nature, having for example phosphonic acid or carboxylic acid functionalities, may be present either in their acid form or as a complex/salt with a suitable counter cation such as an alkali or alkaline metal ion, ammonium, or substituted ammonium ion, or any mixtures thereof.
- a suitable counter cation such as an alkali or alkaline metal ion, ammonium, or substituted ammonium ion, or any mixtures thereof.
- any salts/complexes are water soluble.
- the molar ratio of said counter cation to the heavy metal ion sequestrant is preferably at least 1 : 1 .
- Suitable heavy metal ion sequestrants for use herein include the amino carboxylic acids such as ethylenediamine-N,N'-disuccinic acid (EDDS), ethylenediamine tetraacetic acid (EDTA), N-hydroxyethylenediamine triacetic acid, nitrilotriacetic acid (NTA), ethylene diamine tetrapropionic acid, ethylenediamine-N,N'-diglutamic acid, 2-hydroxypropylenediamine-N,N'- disuccinic acid, triethylenetetraamine hexacetic acid, diethylenetriamine pentaacetic acid (DETPA), trans 1 ,2 diaminocyclohexane-N,N,N',N'- tetraacetic acid or ethanoldiglycine.
- EDDS ethylenediamine-N,N'-disuccinic acid
- EDTA ethylenediamine tetraacetic acid
- NTA nitrilotri
- Suitable heavy metal ion sequestrants for use herein include the organo aminophosphonic acids such as ethylenediamine tetrakis (methylenephosphonic acid), diethylene triamine-N,N,N',N",N"-pentakis (methylene phosphonic acid) (DETMP), 1 -hydroxyethane 1 , 1 -diphosphonic acid (HEDP) or hydroxyethane dimethylenephosphonic acid.
- organo aminophosphonic acids such as ethylenediamine tetrakis (methylenephosphonic acid), diethylene triamine-N,N,N',N",N"-pentakis (methylene phosphonic acid) (DETMP), 1 -hydroxyethane 1 , 1 -diphosphonic acid (HEDP) or hydroxyethane dimethylenephosphonic acid.
- heavy metal ion sequestrants are gluconic acid, citric acid, tartaric acid, isopropyl citric acid, oxydisuccinic acid, dipicolinic acid, 4,5 dihydroxy-m-benzenesulfonic acid, 8-hydroxyquinoline, sodium dithiocarbamate, sodium tetraphenylboron or ammonium nitrosophenyl hydroxylamine.
- ethylenediamine-N,N'-disuccinic acid most preferably present in the form of its S,S isomer, which is preferred for its biodegradability profile.
- the heavy metal ion sequestrants can be added to the composition at any point during the processing including into the water seat, after the addition of electrolyte (hot) or post-addition to the cooled product or mixed with any other raw material prior to the addition into the final mix.
- the heavy metal ion sequestrants are incorporated into the water seat premix with minors before the softener active injection.
- a sensitive component selected from a perfume, a dye, a fatty acid compound of Iodine Value (IV) of at least 2, a compound having one or more fatty acid moieties of IV of at least 2, and mixtures thereof.
- a sensitive component selected from a perfume, a dye, a fatty acid compound of Iodine Value (IV) of at least 2, a compound having one or more fatty acid moieties of IV of at least 2, and mixtures thereof.
- perfume encompasses individual perfume components and compositions of perfume components. Selection of any perfume is based solely on aesthetic considerations.
- Perfume in the sense of perfume components or compositions of perfume components, can be any odoriferous materials or any materials which act as a malodour counteractent.
- the perfume will most often be liquid at ambient temperatures, but also can be liquified solid such as the various camphoraceous perfumes known in the art.
- the perfume can be relatively simple in composition or can comprise highly sophisticated, compact mixtures of natural or synthetic chemical components, all chosen to provide any desired odour.
- perfumes are those odorous materials that deposit on fabrics during the laundry process and are detectable by people with normal olfactory sensity. Many of the perfume ingredients along with their odor corrector and their physical and chemical properties are given in "Perfume and Flavor chemicals (aroma chemicals)", Stephen Arctender, Vols. I and II, Aurthor, Montclair, H.J. and the Merck Index, 8th Edition, Merck & Co., Inc. Rahway, N.J. Perfume components and compositions can also be found in the art, e.g. US Patent Nos. 4, 145, 1 84, 4, 1 52,272, 4,209,41 7 or 4,51 5,705.
- perfume use includes materials such as aldehydes, ketones, esters and the like. More commonly, naturally occurring plant and animal oils and exudates comprising complex mixtures of various chemical components are known for use as perfume, and such materials can be used herein.
- Typical perfumes can comprise e.g. woody/earthy bases containing exotic materials such as sandalwood oil, civet and patchouli oil.
- the perfume also can be of a light floral fragrance e.g. rose or violet extract. Further the perfume can be formulated to provide desirable fruity odours e.g. lime, lemon or orange.
- perfume components and compositions are anetole, benzaldehyde, benzyl acetate, benzyl alcohol, benzyl formate, iso ⁇ bomyl acetate, camphene, cis-citral (neral), citronellal, citronellol, citronellyl acetate, paracymene, decanal, dihydrolinalool, dihydromyrcenol, dimethyl phenyl carbinol, eucalyptol, geranial, geraniol, geranyl acetate, geranyl nitrile, cis-3-hexenyl acetate, hydroxycitronellal, d-limonene, linalool, linalool oxide, linalyl acetate, linalyl propionate, methyl anthranilate, alpha-methyl ionone, methyl nonyl acetaldehyde, methyl phen
- the perfume compound is included in the fabric softener compositions of the invention in a weight ratio of perfume to fabric softener of 1 :100 to 1 :2, preferably from 1 :70 to 1 :3, most preferably from 1 :40 to 1 :4.
- the higher ratios relate to diluted compositions while the lower ratios relate to concentrated compositions.
- the most appropriate ratio of perfume to fabric softner will easily be identified by knowing the dilution and the desired final amount in the fabric treatment composition.
- the dye(s) includes water soluble dye systems, conventional dyes and mixtures thereof.
- the dye will be present in amount of from 0.2 to 200ppm, preferably from 1 to 100ppm and most preferably from 2 to 60ppm by weight of the composition.
- Suitable water soluble dye systems include those which comprise a dye selected from:
- Still other suitable dyes are the conventional dyes selected from Acid Red 52 with color index no. 45100, Acid Yellow 3 with color index no. 47005, Acid Blue 1 27 with color index no. 61 135, Acid Blue 5 with color index no. 42051 , Acid Blue 80 with color index no. 61 585 and mixtures thereof.
- the dyes can be added to the composition at any point during the processing including into the water seat, after the addition of optional electrolyte (hot) or post-addition to the cooled product or mixed with any other raw material during the process or mixed with any other raw material prior to the addition into the final mix.
- optional electrolyte (hot) or post-addition to the cooled product or mixed with any other raw material during the process or mixed with any other raw material prior to the addition into the final mix.
- fatty acid compounds of IV of at least 2 and/or compounds having one or more fatty acid moieties of IV of at least 2 are fabric softener compounds.
- said fatty acid compound of IV of at least 2 and/or said compound having one or more fatty acid moieties of IV of at least 2 can be the only fabric softener actives, or said fatty acid compound of IV of at least 2 and/or said compound having one or more fatty acid moieties of IV of at least 2 can be a softener in addition to the fabric softener disclosed herein before.
- Such compounds having one or more fatty acid moieties of IV of at least 2 include the herein before described compounds in the quaternary ammonium compounds disclosure such as N,N-di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride; N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2- hydroxyethyl); N,N-di(2-tallowyl-oxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride; N,N-di(2-tallowyl-oxyethylcarbonyloxyethyl)-N,N- dimethylammonium chloride; N-(2-tallowyl-oxy-2-ethyl)-N-(2-tallowyloxy-2- oxo-ethyl)-N,N-dimethyl ammonium chloride; N,N,N-tri(tallowyl-oxy-e
- N,N-dimethyl-ammonium chloride 1 ,2-ditallowyl-oxy-3- trimethylammoniopropane chloride; and mixtures of any of the above materials, wherein said tallow moiety has a IV value of at least 2.
- Fully formulated fabric softening compositions can contain polymers having a partial or net cationic charge.
- Such polymers can be used at levels of from 0.001 % to 10%, preferably 0.01 % to 2% by weight of the compositions.
- Such polymers having a partial cationic charge can be polyamine N-oxide containing polymers which contain units having the following structure formula (A):
- P is a polymerisable unit, whereto the R-N- ⁇ O group can be attached to or wherein the R-N->O group forms part of the polymerisable unit or a combination of both.
- A is -NC-, -CO-, -C-, -O-, -S-, -N- ; x is 0 or 1 ;
- R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N- 0 group can be attached or wherein the nitrogen of the N- ⁇ O group is part of these groups.
- the N- O group can be represented by the following general structures :
- R ⁇ , R 2 , and R 3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N- O group can be attached or wherein the nitrogen of the N->O group forms part of these groups.
- the N- O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.
- Suitable polyamine N-oxides wherein the N->O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
- polyamine N-oxides comprises the group of polyamine N- oxides wherein the nitrogen of the N->O group forms part of the R-group.
- Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.
- Another class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N->O group is attached to the R-group.
- polyamine N-oxides are the polyamine oxides whereto the N -i>O group is attached to the polymerisable unit.
- Preferred class of these polyamine N-oxides are the polyamine N-oxides having the general formula (A) wherein R is an aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N->0 functional group is part of said R group.
- polyamine N-oxides are the polyamine oxides having the general formula (A) wherein R are aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-->O functional group is attached to said R groups.
- polyamine oxides wherein R groups can be aromatic such as phenyl.
- Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties.
- suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof.
- the amine N-oxide polymers useful herein typically have a ratio of amine to the amine N-oxide of 10:1 to 1 : 1000000.
- the amount of amine oxide groups present in the polyamine N-oxide containing polymer can be varied by appropriate copolymerization or by appropriate degree of N- oxidation.
- the ratio of amine to amine N-oxide is from 2:3 to 1 : 1000000. More preferably from 1 :4 to 1 : 1000000, most preferably from 1 :7 to 1 : 1 000000.
- the polymers of the present invention actually encompass random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is either an amine N-oxide or not.
- the amine oxide unit of the polyamine N-oxides has a PKa ⁇ 10, preferably PKa ⁇ 7, more preferred PKa ⁇ 6.
- the polyamine N-oxide containing polymer can be obtained in almost any degree of polymerisation.
- the degree of polymerisation is not critical provided the material has the desired water-solubility and dye-suspending power.
- the average molecular weight of the polyamine N-oxide containing polymer is within the range of 500 to 1 000,000; preferably from 1 ,000 to 50,000, more preferably from 2,000 to 30,000, most preferably from 3,000 to 20,000.
- Such polymers having a net cationic charge include polyvinylpyrrolidone (PVP) as well as copolymers of N-vinylimidazole N-vinyl pyrrolidone, having an average molecular weight range in the range 5,000 to 100,000, preferably 5,000 to 50,000; said copolymers having a molar ratio of N- vinylimidazole to N-vinylpyrrolidone from 1 to 0.2, preferably from 0.8 to 0.3.
- PVP polyvinylpyrrolidone
- copolymers of N-vinylimidazole N-vinyl pyrrolidone having an average molecular weight range in the range 5,000 to 100,000, preferably 5,000 to 50,000; said copolymers having a molar ratio of N- vinylimidazole to N-vinylpyrrolidone from 1 to 0.2, preferably from 0.8 to 0.3.
- Concentrated compositions of the present invention may require organic and/or inorganic concentration aids to go to even higher concentrations and/or to meet higher stability standards depending on the other ingredients.
- 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 1 5% 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 C-
- Each R is a C1 -C4 alkyl or substituted (e.g., hydroxy) alkyl, or hydrogen, preferably methyl
- the counterion X" is a softener compatible anion, for example, chloride, bromide, methyl sulfate, etc.
- Other cationic materials with ring structures such as alkyl imidazoline, imidazolinium, pyridine, and pyridinium salts having a single C-J 2- 30 alkyl chain can also be used. Very low pH is required to stabilize, e.g., imidazoline ring structures.
- alkyl imidazolinium salts and their imidazoline 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
- R5 is hydrogen or a C-1 -C4 alkyl radical
- R 6 is a C- j - C4 alkyl radical or H (for imidazoline 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 - Y - (C 2 H4 ⁇ ) z - C2H4OH
- 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 1 0 to 1 8 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 1 5.
- nonionic surfactants examples include buthionic surfactants
- Alkyl Phenol Alkoxylates such as p-tridecylphenol EO(1 1 ) and p- pentadecylphenol EO(1 8), 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.
- 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- hydroxyethyDdodecylamine 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 1 2 to 25, preferably from 1 6 to 20 total carbon atoms, with the fatty moiety containing from 10 to 22, preferably from 1 5 to 1 7 (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.
- 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 1 5,000 parts per million (ppm), preferably from 50 to 10,000 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 stabilize 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.
- Suitable liquid carriers for the present invention are selected from water, organic solvents and mixtures thereof.
- the liquid carrier employed in the instant compositions is at least primarily water due to its low cost, safety, and environmental compatibility.
- the level of water in the liquid carrier is preferably at least 10%, most preferably at least 50%, by weight of the carrier.
- Mixtures of water and low molecular weight, e.g., ⁇ 200, organic solvent, e.g., lower alcohols 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.
- Still other optional ingredients are stabilizers, such as well known antioxidants and reductive agents, dye transfer inhibiting agents, Soil Release Polymers, thickeners, emulsifiers, bacteriocides, colorants, preservatives, optical brighteners, dye fixative agents, anti ionisation agents, antifoam agents, builders and enzymes excluding cellulase.
- stabilizers such as well known antioxidants and reductive agents, dye transfer inhibiting agents, Soil Release Polymers, thickeners, emulsifiers, bacteriocides, colorants, preservatives, optical brighteners, dye fixative agents, anti ionisation agents, antifoam agents, builders and enzymes excluding cellulase.
- composition of the present invention may be provided in any suitable forms for use in the rinse cycle of a laundry washing process or as a pre ⁇ treatment product or in a spray product.
- suitable forms of the compositions include the liquid compositions such as aqueous or non-aqueous compositions, or solid compositions such as solid particulate fabric softener compositions or solid compositions in dryer-added sheet products.
- Example 1 The invention is illustrated in the following non limiting examples, in which all percentages are on a weight basis unless otherwise stated.
- composition A is a prior art composition
- B and C are in accord with the invention:
- compositions were made according to known process for preparing fabric softener compositions by injecting into the hot water seat (60-70°C) containing minors the molten DEQA, followed by slowly adding the electrolyte to the desired viscosity and thereafter the perfume before leaving the product to cool.
- the heavy metal ion sequestrant was added to the waterseat prior to the fabric softener compound injection. Storage stability results
- compositions A to C were then assessed for their storage stability with regard to the dye and/or perfume stability.
- the dye stability was assessed by the determination of the Delta-E values measured by a Spectraflash (Data color int.) and defined for example in ASTM D2244. The lower the value, the better the dye stability.
- the intensity of the perfume has been evaluated by trained perfumers and allocated an intensity rating varying between 1 (no odour detected) and 10 (perfection). The higher the rating, the stronger the odour. Grades below 5 indicate to varying degrees, an odor unlike that intended for the product. In this instance, a trained perfumer is defined as a person having at least 6 months training with demonstrated evidence of olfactive sensitivity.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP96933199A EP0856045B1 (en) | 1995-10-11 | 1996-10-01 | Fabric softener compositions |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP95870115A EP0768369A1 (en) | 1995-10-11 | 1995-10-11 | Fabric softener compositions |
EP95870115 | 1995-10-11 | ||
EP96933199A EP0856045B1 (en) | 1995-10-11 | 1996-10-01 | Fabric softener compositions |
PCT/US1996/015655 WO1997013828A1 (en) | 1995-10-11 | 1996-10-01 | Fabric softener compositions |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0856045A1 true EP0856045A1 (en) | 1998-08-05 |
EP0856045A4 EP0856045A4 (en) | 1999-06-09 |
EP0856045B1 EP0856045B1 (en) | 2005-02-16 |
Family
ID=8222161
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95870115A Withdrawn EP0768369A1 (en) | 1995-10-11 | 1995-10-11 | Fabric softener compositions |
EP96933199A Revoked EP0856045B1 (en) | 1995-10-11 | 1996-10-01 | Fabric softener compositions |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95870115A Withdrawn EP0768369A1 (en) | 1995-10-11 | 1995-10-11 | Fabric softener compositions |
Country Status (13)
Country | Link |
---|---|
EP (2) | EP0768369A1 (en) |
JP (1) | JPH11513437A (en) |
AR (1) | AR003853A1 (en) |
AT (1) | ATE289346T1 (en) |
BR (1) | BR9610917A (en) |
CA (1) | CA2234674A1 (en) |
CZ (1) | CZ105298A3 (en) |
DE (1) | DE69634362T2 (en) |
EG (1) | EG21264A (en) |
ES (1) | ES2238696T3 (en) |
TR (1) | TR199800650T1 (en) |
WO (1) | WO1997013828A1 (en) |
ZA (1) | ZA968285B (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19756434A1 (en) * | 1997-12-18 | 1999-06-24 | Witco Surfactants Gmbh | Aqueous fabric softener with improved soft feel |
AU1358801A (en) * | 1999-11-05 | 2001-06-06 | Procter & Gamble Company, The | Aqueous fabric softener compositions containing highly unsaturated active and chelant |
US20040097395A1 (en) † | 2002-11-14 | 2004-05-20 | Andre Crutzen | Fabric softening composition containing esterquat with specific ester distribution and sequestrant |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0006268A1 (en) * | 1978-06-20 | 1980-01-09 | THE PROCTER & GAMBLE COMPANY | Washing and softening compositions and processes for making them |
EP0052517A1 (en) * | 1980-11-18 | 1982-05-26 | THE PROCTER & GAMBLE COMPANY | Concentrated fabric softening compositions |
EP0534009A1 (en) * | 1991-09-27 | 1993-03-31 | The Procter & Gamble Company | Concentrated fabric-softening compositions |
WO1994020597A1 (en) * | 1993-03-01 | 1994-09-15 | The Procter & Gamble Company | Concentrated biodegradable quaternary ammonium fabric softener compositions and compounds containing intermediate iodine value unsaturated fatty acid chains |
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 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0345842A3 (en) * | 1988-05-27 | 1990-04-11 | The Procter & Gamble Company | Fabric softening compositions containing mixtures of substituted imidazoline esters and quartenized ester-ammonium salts |
US5427697A (en) * | 1993-12-17 | 1995-06-27 | The Procter & Gamble Company | Clear or translucent, concentrated fabric softener compositions |
US5399272A (en) * | 1993-12-17 | 1995-03-21 | The Procter & Gamble Company | Clear or translucent, concentrated biodgradable quaternary ammonium fabric softener compositions |
-
1995
- 1995-10-11 EP EP95870115A patent/EP0768369A1/en not_active Withdrawn
-
1996
- 1996-10-01 JP JP9515076A patent/JPH11513437A/en not_active Ceased
- 1996-10-01 CA CA002234674A patent/CA2234674A1/en not_active Abandoned
- 1996-10-01 CZ CZ981052A patent/CZ105298A3/en unknown
- 1996-10-01 AT AT96933199T patent/ATE289346T1/en not_active IP Right Cessation
- 1996-10-01 BR BR9610917A patent/BR9610917A/en not_active IP Right Cessation
- 1996-10-01 ES ES96933199T patent/ES2238696T3/en not_active Expired - Lifetime
- 1996-10-01 TR TR1998/00650T patent/TR199800650T1/en unknown
- 1996-10-01 WO PCT/US1996/015655 patent/WO1997013828A1/en active IP Right Grant
- 1996-10-01 DE DE69634362T patent/DE69634362T2/en not_active Revoked
- 1996-10-01 EP EP96933199A patent/EP0856045B1/en not_active Revoked
- 1996-10-02 ZA ZA968285A patent/ZA968285B/en unknown
- 1996-10-08 EG EG90896A patent/EG21264A/en active
- 1996-10-11 AR ARP960104698A patent/AR003853A1/en not_active Application Discontinuation
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0006268A1 (en) * | 1978-06-20 | 1980-01-09 | THE PROCTER & GAMBLE COMPANY | Washing and softening compositions and processes for making them |
EP0052517A1 (en) * | 1980-11-18 | 1982-05-26 | THE PROCTER & GAMBLE COMPANY | Concentrated fabric softening compositions |
EP0534009A1 (en) * | 1991-09-27 | 1993-03-31 | The Procter & Gamble Company | Concentrated fabric-softening compositions |
WO1994020597A1 (en) * | 1993-03-01 | 1994-09-15 | The Procter & Gamble Company | Concentrated biodegradable quaternary ammonium fabric softener compositions and compounds containing intermediate iodine value unsaturated fatty acid chains |
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 |
Non-Patent Citations (1)
Title |
---|
See also references of WO9713828A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE69634362T2 (en) | 2005-12-29 |
DE69634362D1 (en) | 2005-03-24 |
JPH11513437A (en) | 1999-11-16 |
AR003853A1 (en) | 1998-09-09 |
EG21264A (en) | 2001-05-30 |
CZ105298A3 (en) | 1998-10-14 |
ES2238696T3 (en) | 2005-09-01 |
ATE289346T1 (en) | 2005-03-15 |
EP0856045B1 (en) | 2005-02-16 |
ZA968285B (en) | 1997-05-13 |
EP0856045A4 (en) | 1999-06-09 |
WO1997013828A1 (en) | 1997-04-17 |
EP0768369A1 (en) | 1997-04-16 |
TR199800650T1 (en) | 1998-06-22 |
CA2234674A1 (en) | 1997-04-17 |
BR9610917A (en) | 1999-03-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5721205A (en) | Cellulase fabric-conditioning compositions | |
US5445747A (en) | Cellulase fabric-conditioning compositions | |
CA2209934C (en) | Chelating agents for improved color fidelity | |
US5958870A (en) | Betaine ester compounds of active alcohols | |
EP0713523B1 (en) | Cellulase fabric-conditioning compositions | |
WO1999029823A1 (en) | Process for making a liquid fabric softening composition | |
AU765389B2 (en) | Rinse-added fabric care compositions comprising low molecular weight linear and cyclic polyamines | |
EP0856045B1 (en) | Fabric softener compositions | |
CA2232413C (en) | Stabilised fabric softening compositions | |
US6218354B1 (en) | Process for making a liquid fabric softening composition | |
US5929025A (en) | Stabilized fabric softening compositions comprising a fabric softening compound, fatty acid, and perfume | |
CA2227341A1 (en) | Fabric softeners containing water soluble dyes for reduced staining | |
GB2375356A (en) | Cationic fabric softening compositions | |
MXPA96005219A (en) | Compositions of cellulasa conditioners of te | |
MXPA00005759A (en) | Process for making a liquid fabric softening composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19980415 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI LU NL PT SE |
|
D17P | Request for examination filed (deleted) | ||
R17P | Request for examination filed (corrected) |
Effective date: 19980415 |
|
A4 | Supplementary search report drawn up and despatched |
Effective date: 19990428 |
|
AK | Designated contracting states |
Kind code of ref document: A4 Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI LU NL PT SE |
|
RIC1 | Information provided on ipc code assigned before grant |
Free format text: 6C 11D 3/00 A, 6C 11D 3/36 B |
|
17Q | First examination report despatched |
Effective date: 20020506 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI LU NL PT SE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050216 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050216 Ref country code: CH Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050216 Ref country code: BE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050216 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050216 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REF | Corresponds to: |
Ref document number: 69634362 Country of ref document: DE Date of ref document: 20050324 Kind code of ref document: P |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050516 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050516 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050516 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050718 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2238696 Country of ref document: ES Kind code of ref document: T3 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20050916 Year of fee payment: 10 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20051003 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20051006 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20051014 Year of fee payment: 10 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20051031 |
|
PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
PLAX | Notice of opposition and request to file observation + time limit sent |
Free format text: ORIGINAL CODE: EPIDOSNOBS2 |
|
26 | Opposition filed |
Opponent name: UNILEVER N.V. / UNILEVER PLC Effective date: 20051116 |
|
ET | Fr: translation filed | ||
NLR1 | Nl: opposition has been filed with the epo |
Opponent name: UNILEVER N.V. / UNILEVER PLC |
|
PLBB | Reply of patent proprietor to notice(s) of opposition received |
Free format text: ORIGINAL CODE: EPIDOSNOBS3 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20061031 Year of fee payment: 11 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070501 |
|
PLAB | Opposition data, opponent's data or that of the opponent's representative modified |
Free format text: ORIGINAL CODE: 0009299OPPO |
|
R26 | Opposition filed (corrected) |
Opponent name: UNILEVER N.V. / UNILEVER PLC Effective date: 20051116 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20070501 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20070629 |
|
RDAF | Communication despatched that patent is revoked |
Free format text: ORIGINAL CODE: EPIDOSNREV1 |
|
APAH | Appeal reference modified |
Free format text: ORIGINAL CODE: EPIDOSCREFNO |
|
APBP | Date of receipt of notice of appeal recorded |
Free format text: ORIGINAL CODE: EPIDOSNNOA2O |
|
APBQ | Date of receipt of statement of grounds of appeal recorded |
Free format text: ORIGINAL CODE: EPIDOSNNOA3O |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20061002 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20061031 Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20061002 |
|
PLAB | Opposition data, opponent's data or that of the opponent's representative modified |
Free format text: ORIGINAL CODE: 0009299OPPO |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20071001 |
|
PLAB | Opposition data, opponent's data or that of the opponent's representative modified |
Free format text: ORIGINAL CODE: 0009299OPPO |
|
R26 | Opposition filed (corrected) |
Opponent name: UNILEVER N.V. / UNILEVER PLC Effective date: 20051116 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20091030 Year of fee payment: 14 |
|
APBU | Appeal procedure closed |
Free format text: ORIGINAL CODE: EPIDOSNNOA9O |
|
RDAG | Patent revoked |
Free format text: ORIGINAL CODE: 0009271 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: PATENT REVOKED |
|
27W | Patent revoked |
Effective date: 20100728 |
|
GBPR | Gb: patent revoked under art. 102 of the ep convention designating the uk as contracting state |
Effective date: 20100728 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20100923 Year of fee payment: 15 |