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
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/001—Softening compositions
  • C11D3/0015—Softening compositions liquid
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/62—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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
  • C11D17/0026—Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
• • 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
  • C11D3/18—Hydrocarbons

Definitions

• the present invention relates to fabric conditioning compositions.
• the present invention relates to fabric conditioning concentrates with less than 10% by weight of water that easily disperse and self-emulsify in cold water (10-25°C) and when emulsified give excellent perfume delivery and softening to laundry.
• Conventional rise conditioners are obtained by dispersing a cationic softening material and perfume into hot water.
• the problem with such conventional rinse conditioners is that although the rinse conditioners soften laundry they do not deliver perfume onto the fabric well because as much as one third of the perfume in the formulation remains in the rinse water.
• Rinse conditioners based on emulsions are known. We have found that such emulsion-based softeners perfume fabrics more effectively than these conventional rinse conditioners but subsequently have a loss in their softening performance.
• WO 92/18593 discloses a granular rinse conditioner, which can be added to water to form an aqueous dispersion, comprising a fatty alkyl ester of a polyhydric alcohol as the softening compound and a mono-long chain alkyl cationic surfactant.
• EP 404 474 discloses a clear, isotropic fabric softening compound comprising a cationic fabric softening material and a carboxylic acid having a total number of 8 carbon atoms.
• GB 2 007 734 (Cargo Fleet) discloses a liquid fabric softener concentrate which consists of a quaternary ammonium salt having at least one C 8 -C 30 long chain alkyl group and an oil.
• the concentrate can be dispersed or emulsified with water. No mention of improved perfume delivery is made.
• the present invention overcomes the problems associated with the prior art in that it provides a rinse conditioner with excellent perfume delivery and fabric softening properties.
• the present invention also provides rinse conditioners which are not detrimental to the absorbency of fabric and which also reduce the creasing of fabric.
• the present invention relates to a conditioning concentrate comprising a cationic fabric softening compound and oil in which the cationic fabric softening compound is suspended in the oil.
• the invention also relates to the use of a composition described above during the rinse cycle to reduce creasing or to improve the water absorbency of fabric.
• a process for perfuming and softening laundry is also described in which the composition described above is added directly to the rinse liquor.
• the present invention relates to a conditioning concentrate.
• concentrate in the context of the present invention means that little or no water is present in the formulation.
• the maximum level of water that can be present in the formulation is 10 % or less by weight of the total formulation, more preferably 5 % or less by weight, most preferably 2 % or less by weight. In some situations less than 0.5% by weight of water may be present.
• compositions of the invention can be described as having a physical state wherein a network of solid crystallites of controlled strength is formed to contain the liquid phase.
• the strength of the solid network is controlled such that composition does not undergo gravitational sedimentation under quiescent conditions but flows under agitation and stirring.
• a conventional emulsion comprises an oil emulsified by cationic active in the form of lamellar layers, said emulsion can yield to gravitational phase separation.
• the emulsified product when added to water the emulsified product has an oil droplet size (D 43 volume average droplet size) of under 5 ⁇ m and more preferably under under 3 ⁇ m.
• Droplet size (D 10 ) is typically in the range 0.2 ⁇ m-50 ⁇ m.
• compositions of the present invention comprise at least one oil.
• the oil may be a mineral oil, an ester oil or a sugar ester oil. Some natural oils, such as vegetable oils may be included if appropriate.
• oil is an ester oil, sugar ester oil or a mineral oil.
• suitable oils include those in the Sirius range of mineral oils (ex Silkolene).
• Suitable ester oils include the saturated ester oils (ex Unichema) and the unsaturated sugar ester oils (ex Mitsubishi Kagaku).
• ester oils of the invention are hydrophobic in nature. It is further preferred if the ester oil is saturated (hardened) in nature, unless it is a sugar ester oils for which unsaturation is preferred.
• Suitable ester oils are the fatty ester of a mono or polyhydric alcohol having from 1 to about 24 carbon atoms in the hydrocarbon chain, and mono or polycarboxylic acids having from 1 to about 24 carbon atoms in the hydrocarbon chain with the proviso that the total number of carbon atoms in the ester oil is equal to or greater than 16 and that at least one of the hydrocarbon radicals in the ester oil has 12 or more carbon atoms.
• Ester oils most suitable for use in the present invention are the PRIOLUBES from Unichema.
• PRIOLUBE 1407, PRIOLUBE 1447, PRIOLUBE 1415, PRIOLUBE 1446, PRIOLUBE 1427, PRIOLUBE 1445, PRIOLUBE 2045, PRIOLUBE 3988, PRIOLUBE 3987, PRIOLUBE 2091, ESTOL 1545 and ESTOL 1527 are advantageously employed.
• PRIOLUBE 2045 which is a neopentyl glycol monomerate
• PRIOLUBE 1446 which is a neopentyl glycol dioleate
• Estol 1445 which is a 2-ethyl hexyl stearate
• the fatty acid mixture for this ester is called in the oleochemical industry "monomer fatty acid” and derives from the dimerisation of rape oil (eruca low) fatty acid or oleine from tallow. In the dimerisation process, dimer, trimer acids and so called monomeric acids are formed. After the dimerisation the "monomeric" part is separated via distillation.
• Suitable mineral oils include Esso Marcol technical type range of oils and particularly preferred is the Silkolene medicinal Sirius range.
• the molecular weight of the mineral oil is typically within the range 150 to 400.
• the viscosity of the ester oil or mineral oil is from 2 cP (mPa.s) to 400 cP (mPa.s) at a temperature of 25°C, more preferably a viscosity from 2 to 150 cP (mPa.s), most preferably a viscosity from 10 to 100 cP (mPa.s).
• the viscosity of the sugar ester oil is above 50,000 cP, preferably 5,000 to 20,000 cP, most preferably 6,000 to 20,000 cP. All viscosities are measured at 25°C.
• the density of the mineral oil is from 0.80 to 0.90 g/cm 3 , more preferably from 0.83 to 0.88g/cm 3 .
• the refractive index of the oil is from 1.445 to 1.490, more preferably from 1.460 to 1.485.
• the level of oil in the rinse conditioner is preferably from 20 to 80 wt% of the composition, most preferably from 50 to 70 wt%.
• crystal growth inhibitor it is also preferred if a crystal growth inhibitor is present. It is beneficial if the crystal growth inhibitor forms part of the melt.
• the crystal growth inhibitors are compounds that have highly polarisable hydrophilic groups .
• crystal growth inhibitors examples include (poly) carboxylates, fatty acids, (poly) ethylene oxides , hydroxylic organic acids, (poly) phosphates, organic phosphonates, amino phosphonates, poly acrylic acids, poly aspartic acid, poly propopylene glycols, polyethelene glycols and soil release polymers such as PET-POET (PERMALOSE TM ex ICI), SOKOLAN HP 22 (ex BASF), cationic decoupling polymers (ex National Starch) as disclosed in (EP 0 415 69842).
• PET-POET PROMALOSE TM ex ICI
• SOKOLAN HP 22 ex BASF
• cationic decoupling polymers ex National Starch
• Particularly preferred crystal growth modifiers are organic acids of alkyl chain length C 18 or less, and nonionic surfactants having an average alkyl chain length between C 10 and C 22 and from 10 to 30 ethoxylate groups.
• Particularly preferred crystal growth inhibitors are tallow and coco nonionic surfactants having from 15 to 20 ethoxylate groups, organic acids such as lactic acid (which contains about 20% linear polymeric self-esterified esters), stearic acid, and hardened or unhardened tallow acid. Mixtures of crystal growth inhibitors may also be used.
• compositions of the present invention are being produced by the melt process as herein described it is particularly preferred that the compositions comprise a fatty acid crystal growth modifier, especially hardened or non-hardened tallow fatty acid or lactic acid or a tallow ethoxylated alcohol.
• a fatty acid crystal growth modifier especially hardened or non-hardened tallow fatty acid or lactic acid or a tallow ethoxylated alcohol.
• the crystal growth inhibitor is a fatty acid or nonionic surfactant it is advantageous if the alkyl chain is not branched.
• the average alkyl chain length of the nonionic surfactant may, for example be between C 10 to C 14 . If a nonionic surfactant is used as the crystal growth inhibitor it is preferred if the HLB is from 14 to 17 especially from 15 to 17.
• Preferred crystal growth inhibitors have further advantages in that they control crystal agglomeration (and hence the viscosity) and aid emulsification of the oil. Furthermore, the preferred crystal growth inhibitors aid the dispersion of the melt in water.
• the crystal growth inhibitor can be cationic and nonionic in nature but not anionic.
• fatty acids if used (in presence of some water) as a crystal growth inhibitor should be used at a pH where they are not dissociated and are thus not anionic in nature.
• the crystal growth inhibitor or mixtures thereof should preferably be present at a level of from 1 wt% to 20 wt% of the composition, more preferably the crystal growth inhibitor should be present at a level from 2 wt% to 10 wt%. As described above a mixture of crystal growth inhibitors may be used, however the level of each individual crystal growth inhibitor is preferably between 1 wt% and 10 wt% , more preferably between 1 wt% and 6 wt% of the total composition.
• compositions comprise a co-emulsifier for rapid dispersion of the composition when it is added to water.
• a nonionic ethoxylated surfactant is used as the crystal growth inhibitor then this will function as both the inhibitor and as a co-emulsifier to provide good dispersion.
• compositions comprise a co-emulsifier which is a surfactant having a low HLB, preferably less than 14. It has been found that such surfactants provide excellent dispersion results.
• the preferred co-emulsifers are C 8 -C 22 alcohol alkoxylates with an average of 3 to 10 alkoxylate groups, preferably 5 to 7 alkoxylate groups.
• Ethoxylates are the preferred alkoxylates although mixed ethoxylates/propoxylates or propoxylates may also be used.
• compositions may comprise, as the co-emulsifer, a mixture of surfactants to provide good dispersibility.
• a mixture of surfactants having an HLB of less than 14 with surfactants having an HLB of greater than 15.5 also provides excellent dispersibility in water.
• Suitable surfactants with an HLB of less than 14 are disclosed hereinabove.
• Suitable surfactants with an HLB of greater than 15.5 include C 8 -C 22 alcohol alkoxylates with an average of 15 to 25 aloxylate groups, preferably 17 to 23.
• ethoxylates are preferred, although mixed ethoxylates/propoxylates and propoxylates may be used.
• the co-emulsifer mixture preferably comprises no more than 90% by weight of the higher HLB surfactant, preferably no more than 75%, especially no more than 65%.
• compositions of the present invention comprise at least one fabric softening compound.
• the fabric softening compound is preferably a quaternary ammonium material comprising a polar head group and two alkyl or alkenyl chains.
• the fabric softening compound of the invention has two long chain alkyl or alkenyl chains with an average chain length greater than C 14 , more preferably each chain has an average chain length greater than C 16 , more preferably at least 50% of each long chain alkyl or alkenyl group has a chain length of C 18 .
• the long chain alkyl or alkenyl groups of the fabric softening compound are predominantly linear.
• the fabric softening compounds of the invention are substantially water insoluble.
• Substantially insoluble fabric softening compounds in the context of this invention are defined as fabric softening compounds having a solubility less than 1 x 10 -3 Wt% in demineralised water at 20°C, preferably the fabric softening compounds have a solubility less than 1 x 10 -4 , most preferably the fabric softening compounds have a solubility at 20°C in demineralised water from 1 x 10 -8 to 1 x 10 -6 .
• R 1 and R 2 represent hydrocarbyl groups having from 12 to 24 carbon atoms
• R 3 and R 4 represent hydrocarbyl groups containing 1 to 4 carbon atoms
• X is an anion, preferably selected from halide, methyl sulphate and ethyl sulphate radicals are preferred.
• quaternary softeners include di(tallow alkyl)dimethyl ammonium chloride; di(tallow alkyl) dimethyl ammonium methyl sulphate; dihexadecyl dimethyl ammonium chloride; di(hydrogenated tallow alkyl) dimethyl ammonium chloride; dioctadecyl dimethyl ammonium chloride; di(hydrogenated tallow alkyl) dimethyl ammonium methyl sulphate; dihexadecyl diethyl ammonium chloride; di(coconut alkyl) dimethyl ammonium chloride. Ditallow alkyl dimethyl ammonium chloride, di(hydrogenated tallow alkyl) dimethyl ammonium chloride, and quats of this.
• esters or amide links for example those available under the tradenames Accosoft 580, Varisoft 222, and Stepantex.
• Particularly preferred fabric softening compounds are a water insoluble quaternary ammonium materials which comprises a compound having two C 12-18 alkyl or alkenyl groups connected to the molecule via at least one an ester link. It is more preferred if the quaternary ammonium material has two ester links present.
• the preferred ester-linked quaternary ammonium material for use in the invention can be represented by the formula: wherein each R 1 group is independently selected from C 1-4 alkyl, hydroxyalkyl or C 2 _ 4 alkenyl groups; and wherein each R 2 group is independently selected from C 8 _ 28 alkyl or alkenyl groups; T is X - is any suitable anion and n is an integer from 0-5.
• a second preferred type of quaternary ammonium material can be represented by the formula: wherein R 1 , n X - and R 2 are as defined above.
• the quaternary ammonium material is biologically degradable.
• Preferred materials of this class such as 1,2 bis[hardened tallowoyloxy]-3- trimethylammonium propane chloride and their method of preparation are, for example, described in US 4 137 180 (Lever Brothers).
• these materials comprise small amounts of the corresponding monoester as described in US 4 137 180 for example 1-hardened tallowoyloxy -2-hydroxy trimethylammonium propane chloride.
• the fabric softening agent may also be a polyol ester quat (PEQ) as described in EP 0 638 639 (Akzo).
• PEQ polyol ester quat
• the level of cationic softening compound is preferably from 3 wt% to 60 wt% of the total composition, more preferably from 10 wt% to 40 wt%.
• the ratio of cationic softening compound to oil is from 1:10 to 5:1 preferably from 1:5 to 1:1, and most preferably 1:3 to 1:1.
• the composition contains less than 25 wt% of the total composition of organic solvent, more preferably less than 20 wt%, most preferabley less than 10 wt%.
• the solvents are non-aqueous. In any case level of water must be kept below 10% of the total composition.
• organic solvents are included in the compositions. It is preferred that less than half of the amount of any solvent present is flammable solvent (i.e has a flash point of less than 25°C. The major proportion of the solvent should most preferably be a non-flammable solvent (i.e. have a flash point of higher than 25°C). Suitable examples include IPA, propylene glycol, and especially hexylene glycol and butyl digol for reasons of viscosity and appearance of the melt. A mixture of solvents may provide advantageous results, especially with respect to viscosity. In some compositions solvent may be present as a result of being a component of an ingredient of the composition.
• compositions which are more difficult to disperse.
• compositions of the invention when dispersed in water at use concentration preferably have a pH of more than 1.5, more preferably less than 5.
• composition is in the form of a concentrate, typically in the form of a paste or high viscosity liquid.
• the concentrate may be added either immediately or after standing, following addition to water by the consumer to form an emulsion which is then added to the rinse liquor.
• the concentrate is added directly to the rinse liquor.
• the composition can also contain one or more optional ingredients, selected from pH buffering agents, perfumes, perfume carriers, fluorescers, colorants, hydrotropes, antifoaming agents, antiredeposition agents, polymeric or other thickening agents, enzymes, optical brightening agents, opacifiers, anti-shrinking agents, anti-wrinkle agents, anti-spotting agents, germicides, fungicides, anti-corrosion agents, drape imparting agents, antistatic agents and ironing aids.
• optional ingredients selected from pH buffering agents, perfumes, perfume carriers, fluorescers, colorants, hydrotropes, antifoaming agents, antiredeposition agents, polymeric or other thickening agents, enzymes, optical brightening agents, opacifiers, anti-shrinking agents, anti-wrinkle agents, anti-spotting agents, germicides, fungicides, anti-corrosion agents, drape imparting agents, antistatic agents and ironing aids.
• the concentrated compositions according to the present invention may be produced according to any suitable method. Two methods are particularly preferred namely the melt process and the cold grinding (milling) process.
• a melt as referred to herein is a homogeneous liquid mixture of two or more substances that would individually solidify on cooling to ambient temperature. In our melts typically one or two of the components solidify on cooling (usually cationic and nonionic).
• the fabric softening compound is heated until it is mobile, preferably liquid, followed by addition to an oil phase (which may contain a perfume) to produce a melt.
• the additional components of the composition may be incorporated into the composition via a mobile fabric conditioning compound, via the oil, or they may be added after the fabric conditioning compound and the oil have been mixed together.
• the melt is formed at a temperature of at least 35°C, preferably of at least 40°C, e.g. at a temperature of 45°C to 70°C.
• the fabric softening compound and nonionic(s) are mixed with the oil and then heated to form a liquid to which upon cooling to a lower temperature perfume may be added.
• compositions of the present invention may be produced by a cold grinding (milling) method wherein the fabric softening compound and the oil are mixed together, at ambient temperature typically at high shear rates, without the fabric softening composition being heated prior to mixing.
• the cold grinding process typically produces compositions of lower viscosities than the corresponding compositions produced by the melt route.
• Examples 1 to 5 were prepared by heating the cationic softener until liquid and adding it to a blend of oil and perfume or adding the cationic to the oil and heating the mixture. Additional components were added to the oil and warmed or added to the cationic softener and warmed or added to the blend of cationic and oil while cooling. This method is referred to herein as the melt process.
• Examples A to H were prepared by stepwise addition of components to hot water.
• Softening performance was evaluated by adding O.lg of fabric softening compound to 1 litre of demineralised water at ambient temperature containing in a tergotometer. It should be noted that the level of actives was equal in the rinse liquor for the examples of the invention and the comparative examples. Three pieces of terry towelling (19cm x 19.5cm) were added to the tergotometer pot (The terry towelling was previously rinsed with 0.001% (w/w) sodium alkyl benzene sulphonate (ABS))to simulate carryover of anionic detergent from the main wash.)
• ABS sodium alkyl benzene sulphonate
• the cloths were treated for 5 minutes at 65 rpm, spin dried to remove excess liquor and line dried overnight. Softness was evaluated by a trained panel of four people ranked the cloths against set standards. A low number indicates a greater degree of softening.
• Perfume delivery was evaluated by rinsing three pieces of terry towelling (7.75 by 7.5"), per product in a similar manner to that previously described for softening evaluation above. Instead of being line-dried the cloths were immediately assessed for perfume intensity by a trained group of eighteen panellists who ranked each cloth on a scale of zero to five corresponding to descriptors ranging from no perfume to very strong perfume. Further assessments were made after five hours when the cloths were dry and again after twenty-four hours. The level of product was 0.1g/l active matter with a perfume level in the rinse liquor of 4.76mg/l.
• Example 6 was prepared as for Examples 1 to 5.
• Example 7 was prepared by adding Example 6 to hot water (60 °C to give an emulsion comprising 20% active.
• Example I a conventional softener dispersion, was prepared by stepwise addition of the components to hot water.
• Example 6 Example I Sirius M70 53.23 - Arquad 2HT 36.92 7.3 Coco20EO 5.91 - Hardened Tallow fatty acid - 0.4 Perfume 3.9 0.3 Water 0.0 91.6
• Cotton poplin cloth was soaked in a solution of fabric softening compound (0.1g/l in demineralised water) at room temperature and then wrung using an Atlas Laboratory wringer. After line drying, the cloth was left at 20°C and 65% humidity for 24 hours. The cloth was then cut to 25mm to 50mm. The cloth was folded in half (short ends together) and placed on a plate. A 2kg load was placed on the crease of the cloth a using a "Shirley Crease Recovery Tester (SDL 003A)". One half of the cloth was secured to the tester, the other half being left suspended in the air. The angle of the free end was measured relative to secured end after 2 minutes 30 seconds.
• SDL 003A Standard Crease Recovery Tester
• Example 6 73.0
• Example 7 63.28
• Example I 57.2
• HEQ is a mixture of 66.2% 1,2 bis[hardened tallowoyloxy]-3-trimethylammonium propane chloride, 11.03% tallow fatty acid and isopropyl alcohol
• DEEDMAC is a mixture of di(hardened tallowoyloxyethyl)dimethyl ammonium chloride 83% quat, 2% tallow fatty acid and isopropyl alcohol.
• Example 17 had same composition as Example 15 (above) and Example 18 had the same composition as Example 16 except the oil was Estol 1545.
• the fabric softening compound HEQ or Deedmac
• the compositions produced were dispersions with relatively low viscosities. This method is referred to herin as the cold-grinding route.
• the cold-grinding route produces products with typically lower viscosities than those produced by the melt route of the present invention.
• the cold-grinding route provides a particularly advantageous route for the preparation of products comprising high melting point fabric softening compounds.
• Examples 15 and 16 as prepared by the melt route were substantially solid and difficult to disperse at ambient temperature.
• Examples 17 and 18 as prepared by the cold grinding route were soft solids/pastes.
• Sirius M70 and Sirius M180 are mineral oils.
• Pristerine 4716 is a fatty acid (hardened Tallow).
• Genapol C200 and Tergitol 15-S-7, are nonionic surfactants. Examples 25 26 27 Wt.% Wt. % Wt.
• compositions comprising a co-emulsifier or a mixture of co-emulsifier were prepared by the melt process as according to Example see Table 9 and 10.
• the dispersion characteristic of the compositions in water was assessed as given below.
• Dispersion was assessed by turbidity. Equal weights of the compositions were added to stirred water at 10°C and the change in turbidity measured with time. A turbidity curve was achieved which initially rose as dispersion took place, then reached a plateau when dispersion was complete. To assess the rate of dispersion the turbidity after 12s compared to the plateau turbidity was measured expressed as % dispersion after 12s.
• Example Mineral oil Petroleum Jelly Softness Score Perfume Wet Perfume 24 hours 38 25:75 5.25 3.33 1.69 39 50:50 4.37 3.57 1.88 40 75:25 - 3.67 1.98 41 0:100 4.87 3.52 1.64 42 100:0 4.62 3.50 2.42

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• Engineering & Computer Science (AREA)
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• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Crystallography & Structural Chemistry (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Detergent Compositions (AREA)

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Cited By (33)

Citations (4)

• 1996
  • 1996-08-22 GB GBGB9617612.8A patent/GB9617612D0/en active Pending
• 1997
  • 1997-08-08 ES ES97306076T patent/ES2216111T3/es not_active Expired - Lifetime
  • 1997-08-08 EP EP19970306076 patent/EP0829531B1/de not_active Expired - Lifetime
  • 1997-08-08 DE DE69727870T patent/DE69727870T2/de not_active Expired - Lifetime
  • 1997-08-18 IN IN486BO1997 patent/IN189800B/en unknown
  • 1997-08-21 BR BR9704481A patent/BR9704481A/pt not_active IP Right Cessation
  • 1997-08-21 ID IDP972919A patent/ID18064A/id unknown
  • 1997-08-21 AR ARP970103794 patent/AR011504A1/es active IP Right Grant
  • 1997-09-15 TW TW086113492A patent/TW375668B/zh not_active IP Right Cessation

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