EP1590426B1 - Compositions de nettoyage et de conditionnement pour blanchisserie - Google Patents
Compositions de nettoyage et de conditionnement pour blanchisserie Download PDFInfo
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- EP1590426B1 EP1590426B1 EP04704608.1A EP04704608A EP1590426B1 EP 1590426 B1 EP1590426 B1 EP 1590426B1 EP 04704608 A EP04704608 A EP 04704608A EP 1590426 B1 EP1590426 B1 EP 1590426B1
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- European Patent Office
- Prior art keywords
- polymer
- softening
- composition
- sodium
- detergent
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
- C11D3/3742—Nitrogen containing silicones
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
-
- 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
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
- C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
- C11D3/3776—Heterocyclic compounds, e.g. lactam
Definitions
- This invention relates to laundry conditioning compositions. More particularly, the invention is directed to laundry compositions containing at least one cationic polymer and at least one anionic surfactant that deliver an unexpected level of fabric softening.
- Hsu discloses the use of polymer JR in an anionic -surfactant containing liquid detergent and further requires a polysaccharide polymer such as xanthan gum, which leads to an unstable product.
- Washer added fabric softening compositions have been disclosed in U.S. Pat. Nos. 4,913,828 and 5,073,274 .
- Fabric softener compositions have been disclosed in WO 00/70005 and U.S. Pat. No. 6,492,322 .
- Liquid detergent compositions comprising polymeric suds enhancers have been disclosed in U.S. Pat. Appl. No. 2002/0169097 .
- this invention is directed to a laundry composition
- a laundry composition comprising one or more cationic polymers selected from the group consisting of guar hydroxypropyl trimonium chloride, and hydroxyethyl cellulose derivatised with trimethyl ammonium substituted epoxide, and more than 5% of one or more anionic surfactants having an HLB of greater than about 4, wherein the composition additionally comprises non-ionic surfactant, and wherein the ratios of cationic polymer : total surfactant, cationic polymer : anionic surfactant, and cationic polymer : non-ionic surfactant are less than 1:10, and wherein the non-ionic surfactant comprises a fatty alcohol ethoxylate of formula: R'(EO) n wherein R' represents an alkyl chain of between 4 and 30 carbon atoms, (EO) represents one unit of ethylene oxide monomer and n has an average value between 0.5 and 20.
- R'(EO) n wherein R' represents
- this invention is directed to a method for conditioning textiles comprising, in no particular order, the steps of:
- the term “comprising” means including, made up of, composed of, consisting and/or consisting essentially of.
- a formula shall be considered physically "stable" when after 1 week at 21 degrees Celsius it exhibits no signs of phase separation.
- the present invention is directed to laundry compositions containing mixtures of one or more anionic surfactant and one or more cationic polymer that deliver an unexpectedly high level of conditioning to fabrics.
- the main objective of this invention is to render garments more pleasant to the touch, and provide other conditioning benefits.
- the compositions of the present invention yield softening parameters of greater than 40.
- compositions of this invention are intended to confer conditioning benefits to garments, home textiles, carpets and other fibrous or fibre-derived articles. These formulations are not to be limited to conditioning benefits, however, and will often be multi-functional. As such, in addition to conditioning fibre-derived articles, they may also clean, fragrance or otherwise treat them.
- Softening includes, but is not limited to, an improvement in the handling of a garment treated with the compositions of this invention relative to that of an article laundered under identical conditions but without the use of this invention. Consumers will often describe an article that is softened as “silky” or "fluffy", and generally prefer the feel of treated garments to those that are unsoftened. It is desirable that the formulae of this invention, when used as instructed, yield a softness parameter of more than 40. The preferred products give a softness parameter in excess of 55, however, while even more preferred products give a softness parameter of more than 70.
- the composition contain greater than about 5% anionic surfactant.
- compositions of these compositions are not limited to softening, however. They may, depending on the particular embodiment of the invention selected, also provide an antistatic benefit.
- the cationic polymer / anionic surfactant compositions of this invention are further believed to lubricate the fibres of textile articles, which can reduce wear, pilling and colour fading, and provide a shape-retention benefit.
- This lubricating layer may also, without wishing to be bound by theory, provide a substrate on the fabric for retaining fragrances and other benefit agents.
- the cationic polymers of this invention are also believed to inhibit the transfer, bleeding and loss of vagrant dyes from fabrics during the wash, further improving colour brightness over time.
- the present invention can take any of a number of forms. It can take the form of a dilutable fabric conditioner, that may be an isotropic liquid, a surfactant-structured liquid, a granular, spray-dried or dry-blended powder, a tablet, a paste, a molded solid or any other laundry detergent form known to those skilled in the art.
- a "dilutable fabric conditioning" composition is defined, for the purposes of this disclosure, as a product intended to be used by being diluted with water or a non-aqueous solvent by a ratio of more than 100:1, to produce a liquor suitable for treating textiles and conferring to them one or more conditioning benefits. Water soluble sheets or sachets, such as those described in U.S. Pat. Appl.
- compositions intended to be used as combination detergent / softeners, along with fabric softeners sold for application in the final rinse of a wash cycle and fabric softeners sold for application at the beginning of a wash cycle are all considered within the scope of this invention.
- these compositions are intended to be used by being diluted by a ratio of more than 100:1 with water or a non-aqueous solvent, to form a liquor suitable for treating fabrics.
- Particularly preferred forms of this invention include combination detergent / softener products, especially as a liquid or powder, and isotropic or surfactant-structured liquid products intended for application as a fabric softener during the wash cycle or the final rinse.
- fabric softener shall be understood to mean a consumer or industrial product added to the wash, rinse or dry cycle of a laundry process for the express or primary purpose of conferring one or more conditioning benefits.
- the preferred pH range of the composition is 2-12. Because many cationic polymers can decompose at high pH, especially when they contain amine or phosphine moieties, it is desirable to keep the pH of the composition below the pK a of the amine or phosphine group that is used to quaternise the selected polymer, below which the propensity for this to occur is greatly decreased. This reaction can cause the product to lose effectiveness over time and create an undesirable product odour. As such, a reasonable margin of safety, of 1-2 units of pH below the pK a should ideally be used in order to drive the equilibrium of this reaction to strongly favour polymer stability.
- wash liquor pH especially in the case of powdered softener and combination detergent / softener products, can often be less important, as the kinetics of polymer decomposition are often slow, and the time of one wash cycle is typically not sufficient to allow for this reaction to have a significant impact on the performance or odour of the product.
- a lower pH can also aid in the formulation of higher-viscosity products.
- the product depends on the presence of soluble anionic surfactants to provide softening, its pH should preferably be above the pK a of the surfactant acids used to formulate it.
- aqueous detergent products which are a highly preferred embodiment of this invention, are nearly impossible to formulate below the pK a of the surfactant acids used, as these molecules are rather insoluble in water when in acid form.
- the product pH should be above about 4, although in certain cases, such as when carboxylic acid salts, which often have a pK a around 4 or 5, are used, the pH of the product can need to be above about 7 or 8 to ensure effective softening. It is desirable to buffer the formulation at whatever the target pH of the composition is.
- Amounts of composition used will generally range between about 10g and about 300g total product per 3 kg of conditioned fibrous articles, depending on the particular embodiment chosen and other factors, such as consumer preferences, that influence product use behaviour.
- a consumer that would use the present invention could also be specifically instructed to contact the fabrics with the inventive composition with the purpose of simultaneously cleaning and softening the said fabrics. This approach would be recommended when the composition takes the form of a softening detergent to be dosed at the beginning of the wash cycle.
- compositions of this disclosure be formulated with low levels, if any at all, of any matter that is substantially insoluble in the solvent intended to be used to dilute the product.
- substantially insoluble shall mean that the material in question can individually be dissolved at a level of less than 0.001% in the specified solvent.
- substantially insoluble matter in aqueous systems include, but are not limited to aluminosilicates, pigments, clays and the like.
- solvent-insoluble inorganic matter can be attracted and coordinated to the cationic polymers of this invention, which are believed to attach themselves to the articles being washed. When this occurs, it is thought that these particles can create a rough effect on the fabric surface, which in turn reduces the perception of softness.
- liquid compositions are a preferred embodiment of this invention, and insoluble matter is often difficult to formulate into a liquid, it is further desirable to minimise its level in the product.
- the liquid compositions be substantially transparent for aesthetic reasons.
- a percent transmittance of light of greater than about 50 using a 1 centimetre cuvette at a wavelength of 570 nanometers wherein the composition is measured in the absence of dyes.
- transparency of the composition may be measured as having an absorbence (A) at 570 nanometers of less than about 0.3 which is in turn equivalent to percent transmittance of greater than about 50 using the same cuvette as above.
- insoluble and substantially insoluble matter will be limited to less than 10% of the composition, more preferably 5%. Most preferably, especially in the case of liquid conditioning compositions, the composition will be essentially free of substantially insoluble matter.
- the anionic surfactants used in this invention can be any anionic surfactant that is substantially water soluble.
- Water soluble surfactants are, unless otherwise noted, here defined to include surfactants which are soluble or dispersible to at least the extent of 0.01% by weight in distilled water at 25°C.
- “Anionic surfactants” are defined herein as amphiphilic molecules with an average molecular weight of less than about 10,000, comprising one or more functional groups that exhibit a net anionic charge when in aqueous solution at the normal wash pH of between 6 and 11. It is preferred that at least one of the anionic surfactants used in this invention be an alkali or alkaline earth metal salt of a natural or synthetic fatty acid containing between 4 and 30 carbon atoms. It is especially preferred to use a mixture of carboxylic acid salts with one or more other anionic surfactants.
- anionic compounds are the water soluble salts, particularly the alkali metal salts, of organic sulphur reaction products having in their molecular structure an alkyl radical containing from about 6 to 24 carbon atoms and a radical selected from the group consisting of sulphonic and sulphuric acid ester radicals.
- R 1 COOM where R 1 is a primary or secondary alkyl group of 4 to 30 carbon atoms and M is a solubilising cation.
- the alkyl group represented by R 1 may represent a mixture of chain lengths and may be saturated or unsaturated, although it is preferred that at least two thirds of the R 1 groups have a chain length of between 8 and 18 carbon atoms.
- suitable alkyl group sources include the fatty acids derived from coconut oil, tallow, tall oil and palm kernel oil. For the purposes of minimising odour, however, it is often desirable to use primarily saturated carboxylic acids.
- solubilising cation may be any cation that confers water solubility to the product, although monovalent such moieties are generally preferred.
- acceptable solubilising cations for use with this invention include alkali metals such as sodium and potassium, which are particularly preferred, and amines such as triethanolammonium, ammonium and morpholinium.
- R 2 OSO 3 M where R 2 is a primary alkyl group of 8 to 18 carbon atoms and M is a solubilising cation.
- the alkyl group R 2 may have a mixture of chain lengths. It is preferred that at least two-thirds of the R 2 alkyl groups have a chain length of 8 to 14 carbon atoms. This will be the case if R 2 is coconut alkyl, for example.
- the solubilising cation may be a range of cations which are in general monovalent and confer water solubility.
- An alkali metal, notably sodium, is especially envisaged.
- Other possibilities are ammonium and substituted ammonium ions, such as trialkanolammonium or trialkylammonium.
- R 3 O(CH 2 CH 2 O) n SO 3 M
- R 3 is a primary alkyl group of 8 to 18 carbon atoms
- n has an average value in the range from 1 to 6 and M is a solubilising cation.
- the alkyl group R 3 may have a mixture of chain lengths. It is preferred that at least two-thirds of the R 3 alkyl groups have a chain length of 8 to 14 carbon atoms. This will be the case if R 3 is coconut alkyl, for example.
- n has an average value of 2 to 5.
- Ether sulphates have been found to provide viscosity build in certain of the formulations of this invention, and thus are considered a preferred ingredient.
- R 4 CH(SO 3 M)CO 2 R 5 where R 4 is an alkyl group of 6 to 16 atoms, R 5 is an alkyl group of 1 to 4 carbon atoms and M is a solubilising cation.
- the group R 4 may have a mixture of chain lengths. Preferably at least two-thirds of these groups have 6 to 12 carbon atoms. This will be the case when the moiety R 8 CH(-)CO 2 (-) is derived from a coconut source, for instance. It is preferred that R 5 is a straight chain alkyl, notably methyl or ethyl.
- R 6 ArSO 3 M where R 6 is an alkyl group of 8 to 18 carbon atoms, Ar is a benzene ring ( C 6 H 4 ) and M is a solubilising cation.
- the group R 6 may be a mixture of chain lengths. A mixture of isomers is typically used, and a number of different grades, such as "high 2-phenyl” and “low 2-phenyl” are commercially available for use depending on formulation needs.
- Paraffin sulphonates having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms, in the alkyl moiety. They are usually produced by the sulphoxidation of petrochemically-derived normal paraffins. These surfactants are commercially available as, for example, Hostapur SAS from Clariant (Charlotte, N.C.).
- Olefin sulphonates having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms.
- U.S. Patent No. 3,332,880 contains a description of suitable olefin sulphonates, and is incorporated herein by reference. Such materials are sold as, for example, Bio-Terge AS-40, which can be purchased from Stepan (Northfield, Ill.)
- R 7 OOCCH 2 CH(SO 3 - M + ) COOR 8 are also useful in the context of this invention.
- R 7 and R 8 are alkyl groups with chain lengths of between 2 and 16 carbons, and may be linear or branched, saturated or unsaturated.
- a preferred sulphosuccinate is sodium bis (2-ethylhexyl) sulphosuccinate, which is commercially available under the tradename Aerosol OT from Cytec Industries (West Paterson, N.J.).
- Organic phosphate based anionic surfactants include organic phosphate esters such as complex mono- or diester phosphates of hydroxyl- terminated alkoxide condensates, or salts thereof. Included in the organic phosphate esters are phosphate ester derivatives of polyoxyalkylated alkylaryl phosphate esters, of ethoxylated linear alcohols and ethoxylates of phenol. Also included are nonionic alkoxylates having a sodium alkylenecarboxylate moiety linked to a terminal hydroxyl group of the nonionic through an ether bond. Counterions to the salts of all the foregoing may be those of alkali metal, alkaline earth metal, ammonium, alkanolammonium and alkylammonium types.
- fatty acid ester sulphonates with formula: R 9 CH(SO 3 M)CO 2 R 10 where the moiety R 9 CH(-)CO 2 (-) is derived from a coconut source and R 10 is either methyl or ethyl; primary alkyl sulphates with the formula: R 11 OSO 3 M wherein R 11 is a primary alkyl group of 10 to 18 carbon atoms and M is a sodium cation; and paraffin sulphonates, preferably with 12 to 16 carbon atoms to the alkyl moiety.
- anionic surfactants preferred for use with this formulation include isothionates, sulphated triglycerides, alcohol sulphates, ligninsulphonates, naphthelene sulphonates and alkyl naphthelene sulphonates and the like. Additional anionic surfactants, falling into the general definition but not specifically mentioned above, should also be considered within the scope of this invention.
- a water soluble cationic polymer is here defined to include polymers which, because of their molecular weight or monomer composition, are soluble or dispersible to at least the extent of 0.01% by weight in distilled water at 25°C.
- the cationic polymer is selected from the group consisting of guar hydroxypropyl trimonium chloride, and hydroxyethyl cellulose derivatised with trimethyl ammonium substituted epoxide.
- the cationic polymers of this invention are effective at surprisingly low levels.
- the ratio of cationic polymer to total surfactant in the composition is less than 1:10.
- the ratio of cationic polymer to anionic surfactant in the composition, on a mass basis, is less than 1:10, as well.
- the preferred compositions of this invention contain low levels, if any at all, of builder. Generally, these will comprise less than 10%, preferably less than 7% and most preferably less than 5% by weight of total phosphate and zeolite.
- compositions of this disclosure comprise less than 2%, more preferably less than 1% and most preferably less than 0.5% anionic polymer.
- anionic polymer is defined as a molecule with a molecular weight in excess of about 10,000 daltons comprised of monomer units where at least one of the monomer units making up the polymer contains a negative charge over a portion of the wash pH range of pH 6 to pH 11, those monomer units not containing anionic charges being nonionic in nature.
- the ratios of cationic polymer: total surfactant, cationic polymer : anionic surfactant and cationic polymer: non-ionic surfactant will be less than 1:10. In terms of absolute fraction, this often means that the concentration of cationic polymer will generally be less than about 5%, preferably less than about 2% and most preferably less than about 1% of the total product mass.
- compositions of this invention will comprise at least 5%, and preferably at least about 10% of one or more anionic surfactants with a hydrophilic/lipophilic balance (HLB) of more than about 4.
- HLB hydrophilic/lipophilic balance
- cationic polymers can be synthesised in, and are commercially available in, a number of different molecular weights.
- the water-soluble cationic or amphoteric polymer used in this invention be of an appropriate molecular weight.
- polymers that are too high in mass can entrap soils and prevent them from being removed.
- the use of cationic polymers with an average molecular weight of less than about 850,000 daltons, and especially those with an average molecular weight of less than 500,000 daltons can help to minimise this effect without significantly reducing the softening performance of properly formulated products.
- polymers with a molecular weight of about 10,000 daltons or less are believed to be too small to give an effective softening benefit.
- lower molecular weight polymers can even improve the softening performance of the product. This is believed to be due to dissolution kinetics; materials of too high a molecular weight can fail to dissolve fully during the wash cycle, rendering them unavailable for softening fabrics.
- the preferred powdered compositions of this invention include materials that have a dissolution parameter of more than about 55.
- Cleaning performance can further be improved by selecting a polymer with an appropriate level of cationic moiety.
- polymers with excessive levels of cationic charge can contribute to soil deposition, hindering the cleaning performance of either the fully formulated 2-in-1 detergent / softener or any laundry detergent that is used in conjunction with the compositions of this invention if they are to be standalone fabric softeners.
- Particularly appropriate materials are those that comprise less than about 2 % by weight, preferably less than about 1.8 % by weight of cationic nitrogen or phosphorus.
- the composition additionally comprises non-ionic surfactant, which comprises a fatty alcohol ethoxylate of formula: R'(EO) n wherein R' represents an alkyl chain of between 4 and 30 carbon atoms, (EO) represents one unit of ethylene oxide monomer and n has an average value between 0.5 and 20.
- non-ionic surfactant which comprises a fatty alcohol ethoxylate of formula: R'(EO) n wherein R' represents an alkyl chain of between 4 and 30 carbon atoms, (EO) represents one unit of ethylene oxide monomer and n has an average value between 0.5 and 20.
- the formulation may include one or more optional ingredients. While it is not necessary for these elements to be present in order to practice this invention, the use of such materials is often very helpful in rendering the formulation acceptable for consumer use.
- optional components include, but are not limited to: amphoteric and zwitterionic surfactants, cationic surfactants, hydrotropes, fluorescent whitening agents, photobleaches, fibre lubricants, reducing agents, enzymes, enzyme stabilising agents, powder finishing agents, defoamers, builders, bleaches, bleach catalysts, soil release agents, antiredeposition agents, dye transfer inhibitors, buffers, colorants, fragrances, pro-fragrances, rheology modifiers, anti-ashing polymers, preservatives, insect repellents, soil repellents, water-resistance agents, suspending agents, aesthetic agents, structuring agents, sanitisers, solvents, fabric finishing agents, dye fixatives, wrinkle-reducing agents, fabric conditioning agents and deodorizers.
- amphoteric and zwitterionic surfactants include, but are not limited to: amphoteric and zwitterionic surfactants, cationic surfactants, hydrotropes, fluorescent whitening agents, photobleaches, fibre
- a soluble preservative may be added to this invention.
- Contamination of the product by microorganisms which can occur through both raw materials and consumer use, can have a number of undesirable effects. These include phase separation, the formation of bacterial and fungal colonies, the emission of objectionable odours and the like.
- the use of a preservative is especially preferred when the composition of this invention is a liquid, as these products tend to be especially susceptible to microbial growth.
- a broad-spectrum preservative which controls the growth of bacteria and fungi is preferred.
- Limited-spectrum preservatives which are only effective on a single group of microorganisms may also be used, either in combination with a broad-spectrum material or in a "package" of limited-spectrum preservatives with additive activities.
- biocidal materials i.e. substances that kill or destroy bacteria and fungi
- biostatic preservatives i.e. substances that regulate or retard the growth of microorganisms
- preservatives that are effective at low levels be used. Typically, they will be used only at an effective amount.
- the term "effective amount" means a level sufficient to control microbial growth in the product for a specified period of time, i.e., two weeks, such that the stability and physical properties of it are not negatively affected.
- an effective amount will be between about 0.00001% and about 0.5% of the total formula, based on weight. Obviously, however, the effective level will vary based on the material used, and one skilled in the art should be able to select an appropriate preservative and use level.
- Preferred preservatives for the compositions of this invention include organic sulphur compounds, halogenated materials, cyclic organic nitrogen compounds, low molecular weight aldehydes, quaternary ammonium materials, dehydroacetic acid, phenyl and phenoxy compounds and mixtures thereof.
- Examples of preferred preservatives for use in the compositions of the present invention include: a mixture of about 77% 5-chloro-2-methyl-4-isothiazolin-3-one and about 23% 2-methyl-4-isothiazolin-3-one, which is sold commercially as a 1.5% aqueous solution by Rohm & Haas (Philadelphia, Pa.) under the trade name Kathon; 1,2-benzisothiazolin-3-one, which is sold commercially by Avecia (Wilmington, Del.) as, for example, a 20% solution in dipropylene glycol sold under the trade name Proxel GXL; and a 95:5 mixture of 1,3 bis (hydroxymethyl)-5,5-dimethyl-2,4 imidazolidinedione and 3-butyl-2-iodopropynyl carbamate, which can be obtained, for example, as Glydant Plus from Lonza (Fair Lawn, N.J.).
- preservatives described above are generally only used at an effective amount to give product stability. It is conceivable, however, that they could also be used at higher levels in the compositions on this invention to provide a biostatic or antibacterial effect on the treated articles.
- Nonionic surfactant shall be defined as amphiphilic molecules with a molecular weight of less than about 10,000, unless otherwise noted, which are substantially free of any functional groups that exhibit a net charge at the normal wash pH of 6-11. Any type of nonionic surfactant may be used, although preferred materials are further discussed below.
- R'O(EO) n wherein R' represents an alkyl chain of between 4 and 30 carbon atoms, (EO) represents one unit of ethylene oxide monomer and n has an average value between 0.5 and 20. R may be linear or branched.
- Such chemicals are generally produced by oligomerizing fatty alcohols with ethylene oxide in the presence of an effective amount catalyst, and are sold in the market as, for example, Neodols from Shell (Houston, Tex.) and Alfonics from Sasol (Austin, Tex.).
- fatty alcohol starting materials which are marketed under trademarks such as Alfol, Lial and Isofol from Sasol (Austin, Tex.) and Neodol, from Shell, may be manufactured by any of a number of processes known to those skilled in the art, and can be derived from natural or synthetic sources or a combination thereof.
- Commercial alcohol ethoxylates are typically mixtures, comprising varying chain lengths of R' and levels of ethoxylation. Often, especially at low levels of ethoxylation, a substantial amount of unethoxylated fatty alcohol remains in the final product, as well.
- fatty alcohol ethoxylates wherein R' represents an alkyl chain from 10-18 carbons and n is an average number between 5 and 12 are highly preferred.
- R 19 represents a linear or branched alkyl chain ranging from 4 to 30 carbons
- Ar is a phenyl (C 6 H 4 ) ring and (EO) n is an oligomer chain comprised of an average of n moles of ethylene oxide.
- R 19 is comprised of between 8 and 12 carbons, and n is between 4 and 12.
- Such materials are somewhat interchangeable with alcohol ethoxylates, and serve much the same function.
- a commercial example of an alkylphenol ethoxylate suitable for use in this invention is Triton X-100, available from Dow Chemical (Midland, Mich.)
- EO represents an ethylene oxide unit
- PO represents a propylene oxide unit
- x and y are numbers detailing the average number of moles ethylene oxide and propylene oxide in each mole of product.
- Such materials tend to have higher molecular weights than most nonionic surfactants, and as such can range between 1,000 and 30,000 daltons.
- BASF Mount Olive, N.J. manufactures a suitable set of derivatives and markets them under the Pluronic and Pluronic-R trademarks.
- nonionic surfactants should also be considered within the scope of this invention. These include condensates of alkanolamines with fatty acids, such as cocamide DEA, polyol-fatty acid esters, such as the Span series available from Uniqema (Wlimington, Del.), ethoxylated polyol-fatty acid esters, such as the Tween series available from Uniqema (Wilmington, Del.), Alkylpolyglucosides, such as the APG line available from Cognis (Gulph Mills, Pa.) and n-alkylpyrrolidones, such as the Surfadone series of products marketed by ISP (Wayne, N.J). Furthermore, nonionic surfactants not specifically mentioned above, but within the definition, may also be used.
- Suitable fluorescent whitening agents include derivatives of diaminostilbenedisulphonic acid and their alkali metal salts. Particularly, the salts of 4,4'-bis(2-anilino4-morpholino-1,3,5-triazinyl-6-amino)stilbene-2,2'-disulphonic acid, and related compounds where the morpholino group is replaced by another nitrogen-comprising moiety, are preferred. Also preferred are brighteners of the 4,4'-bis(2-sulphostyryl) biphenyl type, which may optionally be blended with other fluorescent whitening agents at the option of the formulator.
- Typical fluorescent whitening agent levels in the preparations of this invention range between 0.001% and 1%, although a level between 0.1% and 0,3%, by mass, is normally used.
- Commercial supplies of acceptable fluorescent whitening agents can be sourced from, for example, Ciba Specialty Chemicals (High Point, N.C.) and Bayer (Pittsburgh, Pa.).
- Builders are often added to fabric cleaning compositions to complex and remove alkaline earth metal ions, which can interfere with the cleaning performance of a detergent by combining with anionic surfactants and removing them from the wash liquor.
- the preferred compositions of this invention especially when used as a combination detergent / softener, contain builders.
- Soluble builders such as alkali metal carbonates and alkali metal citrates, are particularly preferred, especially for the liquid embodiment of this invention.
- Other builders as further detailed below, may also be used, however. Often a mixture of builders, chosen from those described below and others known to those skilled in the art, will be used.
- Alkali and alkaline earth metal carbonates are suitable for use as builders in the compositions of this invention. They may be supplied and used either in anhydrous form, or including bound water. Particularly useful is sodium carbonate, or soda ash, which both is readily available on the commercial market and has an excellent environmental profile.
- the sodium carbonate used in this invention may either be natural or synthetic, and, depending on the needs of the formula, may be used in either dense or light form.
- Natural soda ash is generally mined as trona and further refined to a degree specified by the needs of the product it is used in.
- Synthetic ash is usually produced via the Solvay process or as a coproduct of other manufacturing operations, such as the synthesis of caprolactam. It is sometimes further useful to include a small amount of calcium carbonate in the builder formulation, to seed crystal formation and increase building efficacy.
- Organic detergent builders can also be used as nonphosphate builders in the present invention.
- organic builders include alkali metal citrates, succinates, malonates, fatty acid sulphonates, fatty acid carboxylates, nitrilotriacetates, oxydisuccinates, alkyl and alkenyl disuccinates, oxydiacetates, carboxymethyloxy succinates, ethylenediamine tetraacetates, tartrate monosuccinates, tartrate disuccinates, tartrate monoacetates, tartrate diacetates, oxidized starches, oxidized heteropolymeric polysaccharides, polyhydroxysulphonates, polycarboxylates such as polyacrylates, polymaleates, polyacetates, polyhydroxyacrylates, polyacrylate/polymaleate and polyacrylate/ polymethacrylate copolymers, acrylate/maleate/vinyl alcohol terpolymers, aminopolycarboxylates and polyacetal carboxylates,
- Such carboxylates are described in U.S. Patent Nos. 4,144,226 , 4,146,495 and 4,686,062 .
- Alkali metal citrates, nitrilotriacetates, oxydisuccinates, acrylate/maleate copolymers and acrylate/maleate/vinyl alcohol terpolymers are especially preferred nonphosphate builders.
- compositions of the present invention which utilise a water-soluble phosphate builder typically contain this builder at a level of from 1 to 90% by weight of the composition.
- water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerisation ranges from about 6 to 21, and salts of phytic acid. Sodium or potassium tripolyphosphate is most preferred.
- the preferred compositions of this invention comprise phosphates at a level of less than about 10% by weight, more preferably less than about 5% by weight.
- the most preferred compositions of this invention are formulated to be substantially free of phosphate builders.
- Zeolites may also be used as builders in the present invention.
- a number of zeolites suitable for incorporation into the products of this disclosure are available to the formulator, including the common zeolite 4A.
- zeolites of the MAP variety such as those taught in European Patent Application EP-B-384,070 , which are sold commercially by, for example, Ineos Silicas (UK), as Doucil A24, are also acceptable for incorporation.
- MAP is defined as an alkali metal aluminosilicate of zeolite P type having a silicon to aluminium ratio not exceeding 1.33, preferably within the range of from 0.90 to 1.33, more preferably within the range of from 0.90 to 1.20.
- zeolite MAP having a silicon to aluminium ratio not exceeding 1.07, more preferably about 1.00.
- the particle size of the zeolite is not critical. Zeolite A or zeolite MAP of any suitable particle size may be used. In any event, as zeolites are insoluble matter, it is advantageous to minimise their level in the compositions of this invention. As such, the preferred formulations contain less than about 10% of zeolite builder, while especially preferred compositions compress less than about 5% zeolite.
- enzyme stabiliser When enzymes, and especially proteases are used in liquid detergent formulations, it is often necessary to include a suitable quantity of enzyme stabiliser to temporarily deactivate it until it is used in the wash.
- suitable enzyme stabilisers are well-known to those skilled in the art, and include, for example, borates and polyols such as propylene glycol. Borates are especially suitable for use as enzyme stabilisers because in addition to this benefit, they can further buffer the pH of the detergent product over a wide range, thus providing excellent flexibility.
- a borate-based enzyme stabilisation system along with one or more cationic polymers that are at least partially comprised of carbohydrate moeities, stability problems can result if suitable co-stabilisers are not used. It is believed that this is the result of borates' natural affinity for hydroxyl groups, which can create an insoluble borate-polymer complex that precipitates from solution either over time or at cold temperatures. Incorporating into the formulation a co-stabiliser, which is normally a diol or polyol, sugar or other molecule with a large number of hydroxyl groups, can ordinarily prevent this.
- sorbitol used at a level that is at least about 0.8 times the level of borate in the system, more preferably 1.0 times the level of borate in the system and most preferably more than 1.43 times the level of borate in the system, is sorbitol, which is effective, inexpensive, biodegradable and readily available on the market.
- Similar materials including sugars such as glucose and sucrose, and other polyols such as propylene glycol, glycerol, mannitol, maltitol and xylitol, should also be considered within the scope of this invention.
- fibre lubricants in the formulation.
- Such ingredients are well known to those skilled in the art, and are intended to reduce the coefficient of friction between the fibres and yarns in articles being treated, both during and after the wash process. This effect can in turn improve the consumer's perception of softness, minimise the formation of wrinkles and prevent damage to textiles during the wash.
- "fibre lubricants” shall be considered non-cationic materials intended to lubricate fibres for the purpose of reducing the friction between fibres or yarns in an article comprising textiles which provide one or more wrinkle-reduction, fabric conditioning or protective benefit.
- suitable fibre lubricants include oily sugar derivatives, functionalised plant and animal-derived oils, silicones, mineral oils, natural and synthetic waxes and the like. Such ingredients often have low HLB values, less than about 10, although exceeding this level is not outside of the scope of this invention.
- Oily sugar derivatives suitable for use in this invention are taught in WO 98/16538 , which is incorporated herein by reference. These are especially preferred as fibre lubricants, due to their ready availability and favorable environmental profile. When used in the compositions of this invention, such materials are typically present at a level between about 1% and about 10% of the finished composition.
- Another class of acceptable ingredients includes hydrophilically-modified plant and animal oils and synthetic triglycerides. Suitable and preferred hydrophilically modified plant, animal, and synthetic triglyceride oils and waxes have been identified as effective fibre lubricants.
- Such suitable plant derived triglyceride materials include hydrophilically modified triglyceride oils, e.g.
- Suitable animal derived triglyceride materials include hydrophilically modified fish oil, tallow, lard, and lanolin wax, and the like.
- An especially preferred functionalised oil is sulphated castor oil, which is sold commercially as, for example, Freedom SCO-75, available from Noveon (Cleveland, Ohio).
- Various levels of derivatisation may be used provided that the derivatisation level is sufficient for the oil or wax derivatives to become soluble or dispersible in the solvent it is used in so as to exert a fibre lubrication effect during laundering of fabrics with a detergent containing the oil or wax derivative.
- this invention includes a functionalised oil of synthetic origin, preferably this oil is a silicone oil. More preferably, it is either a silicone poly ether or amino-functional silicone. If this invention incorporates a silicone polyether, it is preferably of one of the two general structures shown below:
- PE represents: CH 2 -CH 2 -CH 2 -O-(EO) m -(PO) n -Z
- Me represents methyl
- EO represents ethylene oxide
- PO represents 1,2 propylene oxide
- Z represents either a hydrogen or a lower alkyl radical
- x, y, m, n are constants and can be varied to alter the properties of the functionalised silicone.
- a molecule of either structure can be used for the purposes of this invention.
- this molecule contains more than 30% silicone, more than 20% ethylene oxide and less than 30% propylene oxide by weight, and has a molecular weight of more than 5,000.
- An example of a suitable, commercially available such material is L-7622, available from Crompton Corporation, (Greenwich, Ct.)
- Amino-functional silicones come in a wide variety of structures, which are well-known to those skilled in the art. These are also useful in the context of this invention, although over time many of these materials can oxidize on fabrics, leading to yellowing. As this is not a desirable property of a fabric care composition, if an amino-functional silicone is used, preferably it is a hindered amine light stabilised product, which exhibits a greatly reduced tendency to show this behavior.
- a commercially available example of such a silicone is Hydrosoft, available from Rhodia - US (Cranbury, N.J.)
- fibre lubricant When the use of a fibre lubricant is elected, it will generally be present as between 0.1% and 15% of the total composition weight.
- An effective amount of a bleach catalyst can also be present in the invention.
- a number of organic catalysts are available such as the sulphonimines as described in U.S. Patents 5,041,232 ; 5,047,163 and 5,463,115 .
- Transition metal bleach catalysts are also useful, especially those based on manganese, iron, cobalt, titanium, molybdenum, nickel, chromium, copper, ruthenium, tungsten and mixtures thereof. These include simple water-soluble salts such as those of iron, manganese and cobalt as well as catalysts containing complex ligands.
- Suitable examples of manganese catalysts containing organic ligands are described in U.S. Pat. 4,728,455 , U.S. Pat. 5,114,606 , U.S. Pat 5,153,161 , U.S. Pat. 5,194,416 , U.S. Pat. 5,227,084 , U.S. Pat. 5,244,594 , U.S. Pat.5,246,612 , U.S. Pat. 5,246,621 , U.S. Pat. 5,256,779 , U.S. Pat. 5,274,147 , U.S. Pat. 5,280,117 and European Pat. App. Pub. Nos.
- Preferred examples of these catalysts include Mn IV 2 (u-O) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (PF 6 ) 2 , Mn III 2(u-O) 1 (u-OAc) 2 (1,4,7- trimethyl-1,4,7-triazacyclononane) 2 (CIO 4 ) 2 , Mn IV 4 (u-O) 6 (1,4,7-triazacyclononane) 4 (CIO 4 ) 4 , Mn III Mn IV 4 (u-O) 1 (u-OAc) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (ClO 4 ) 3 , Mn IV (1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH 3 ) 3 (PF 6 ), and mixtures thereof.
- metal-based bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611 .
- complexes of transition metals include Mn gluconate, Mn(CF 3 SO 3 ) 2 , and binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands, including [bipy 2 Mn III (u-O) 2 Mn IV bipy 2 ]-(CIO 4 ) 3 .
- Iron and manganese salts of aminocarboxylic acids in general are useful herein including iron and manganese aminocarboxylate salts disclosed for bleaching in the photographic colour processing arts.
- a particularly useful transition metal salt is derived from ethylenediaminedisuccinate and any complex of this ligand with iron or manganese.
- Another type of bleach catalyst is a water soluble complex of manganese (II), (III), and/or (IV) with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups.
- Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylitol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose and mixtures thereof. Especially preferred is sorbitol.
- bleach catalysts are described, for example, in European Pat. App. Pub. Nos. 408,131 (cobalt complexes), 384,503 and 306,089 (metallo-porphyrins), U.S. Pat. 4,728,455 (manganese/multidenate ligand), U.S. Pat. 4,711,748 (absorbed manganese on aluminosilicate), U.S. Pat. 4,601,845 (aluminosilicate support with manganese, zinc or magnesium salt), U.S. Pat. 4,626,373 (manganese/ligand), U.S. Pat. 4,119,557 (ferric complex), U.S. Pat. 4,430.243 (Chelants with manganese cations and non-catalytic metal cations), and U.S. Pat. 4,728,455 (manganese gluconates).
- WO 96/23860 describe cobalt catalysts of the type [Co n L m X p ] z Y z , where L is an organic ligand molecule containing more than one heteroatom selected from N, P, O and S; X is a co-ordinating species; n is preferably 1 or 2; m is preferably 1 to 5; p is preferably 0 to 4 and Y is a counterion.
- cobalt catalysts described in these applications are based on Co(III) complexes with ammonia and mono-, bi-, tri- and tetradentate ligands such as [Co(NH 3 ) 5 OAc] 2+ with Cl - , OAc - , PF 6 - , SO 4 - , and BF 4 - anions.
- transition-metal containing bleach catalysts can be prepared in the situ by the reaction of a transition-metal salt with a suitable chelating agent, for example, a mixture of manganese sulphate and ethylenediaminedisuccinate. Highly coloured transition metal-containing bleach catalysts may be co-processed with zeolites to reduce the colour impact.
- a suitable chelating agent for example, a mixture of manganese sulphate and ethylenediaminedisuccinate.
- Highly coloured transition metal-containing bleach catalysts may be co-processed with zeolites to reduce the colour impact.
- the bleach catalyst is typically incorporated at a level of about 0.0001 to about 10% by wt., preferably about 0.001 to about 5% by weight.
- hydrotropes Two types are typically used in detergent formulations and are applicable to this invention.
- the first of these are short-chain functionalised amphiphiles.
- short-chain amphiphiles include the alkali metal salts of xylenesulphonic acid, cumenesulphonic acid and octyl sulphonic acid, and the like.
- organic solvents and monohydric and polyhydric alcohols with a molecular weight of less than about 500 such as, for example, ethanol, isoporopanol, acetone, propylene glycol and glycerol, may also be used as hydrotropes.
- soil release agents may also be added to the products of this invention.
- Many different types of soil release agents are known to those skilled in the art, depending on the formulation in use and the desired benefit.
- the soil release agents useful in the context of this invention are typically either antiredeposition aids or stain-repelling finishes.
- anti-redeposition agents include soil release polymers, such as those described in WO 99/03963 , which is incorporated herein by reference.
- the cationic polymers of this invention are particularly advantageous when used in conjunction with a stain-repelling finish.
- Such materials are typically either fluoropolymers or fluorosurfactants, although the use of other amphiphilic materials with extremely hydrophobic lyophobes, such as silicone surfactants, is also conceivable.
- suitable anionic fluorosurfactants are taught in U.S. Patent No. 6,040,053 , which is incorporated herein by reference. Without wishing to be bound by theory, it is believed that the cationic polymers of this invention coordinate to the fabric surface and act as a substrate and deposition aid for the stain-repelling finish.
- an antiredeposition aid or stain-repelling finish When used, it is typically applied as 0.05% to 10% of the finished composition.
- Fabric was washed with a variety of products, the formulations for which are set forth hereinbelow.
- the washed fabric was then tested by consumer panels for perceived softening.
- product was added to a top loading Whirlpool washing machine that contained 17 gallons of water and 6 pounds of fabric. There were several 86% cotton/14% polyester hand towels in each machine along with 100% cotton sheets to bring the total weight of the fabric to 6 pounds.
- the temperature of the water for the washes was 32°C and the fabrics were washed for 12 minutes. After the rinse cycle, the fabrics were tumble dried. Two washes were done with each product.
- Model Liquid Detergent Ingredient Percent in Formula (based on 100% active) Sodium linear alkylbenzenesulphonate 10.2 Alcohol ethoxylate 9.5 Sodium silicate 3.3 Hydrotrope 0.5 Sodium stearate 0.4 Fluorescent whitening agent 0.1 Water to 100 TABLE 2: Model Powdered Detergent Ingredient Percent in Formula (based on 100% active) sodium linear alkylbenzenesulphonate 13.0 alcohol ethoxylate 4.9 sodium silicate 0.5 Zeolite (anhydrous basis) 26.5 Anti-ashing polymer 1.5 Sodium carbonate 23.1 Sodium sulphate 19.4 Protease enzyme 0.4 Fluorescent whitening agent 0.3 Water (bound in the formula) To 100
- Model Liquid Fabric Softener Ingredient Percent in Formula (based on 100% active) Dihydrogenated tallow dimethyl ammonium chloride 3.5 lactic acid 0.015 Calcium chloride 0.015 Water to 100
- SP Softening Parameter
- Detergency experiments were carried out via a modification of ATSM Method D 3050-87 using a Terg-O-Tometer (available from SCS, Fairfield, N.J.) set to 100 RPM in 1000 ml of 90F water standardised to 120ppm hardness with a Ca/Mg ratio of 2:1. Cloths were washed for 10 minutes with 2.21g of detergent, followed by a 2 minute rinse and then tumble dried. Two types of standard soil cloth were used for each experiment: pigment / synthetic sebum on cotton (WFK-10d, available from WFK Testgewebe Gmbh, Bruggen-Bracht Germany) and pigment / oil on poly-cotton (PC-9, Available from C.F.T, Vlaardingen, Holland).
- WFK-10d available from WFK Testgewebe Gmbh, Bruggen-Bracht Germany
- PC-9 Available from C.F.T, Vlaardingen, Holland.
- Formulation 1 Ingredient Percent in Formula (based on 100% active) Alcohol ethoxylate 11.0 linear alkyl benzene sulphonic acid 4.2 coconut fatty acid 3.5 oleic acid 5.3 propylene glycol 9.0 sodium hydroxide 1.8 Triethanolamine 3.0 sodium citrate 5.0 sodium borate 3.0 fluorescent whitening agent 0.16 Water to 100 *Not according to the invention. TABLE 5.
- Formulation 2 Ingredient Percent in Formula (based on 100% active) alcohol ethoxylate 12.0 propylene glycol 9.0 Triethanolamine 3.0 sodium citrate 5.0 sodium borate 3.0 Polymer JR 30M 1 0.3 fluorescent whitening agent 0.16 Water to 100 1 Available from the Amerchol division of Dow Chemical, Edison, N.J. Is an example of polyquaternium 10.
- Formulation 3 Ingredient Percent in Formula (based on 100% active) alcohol ethoxylate 11.0 linear alkyl benzene sulphonic acid 4.2 coconut fatty acid 3.5 oleic acid 5.3 propylene glycol 9.0 sodium hydroxide 1.8 Triethanolamine 3.0 sodium citrate 5.0 sodium borate 3.0 Polymer JR 30M 1 0.3 fluorescent whitening agent 0.16 Water to 100 1 Available from the Amerchol division of Dow Chemical, Edison N.J.
- the softening results show that many of the cationic polymers tested yielded superior softening through the wash when used in combination with anionic surfactants. Specifically, the cationic polymers used in experimental formulations 8-19 were deemed to be superior.
- Comparative Formulation 1 Ingredient Percent in Formula (as is) linear alkyl benzene sulphonate (95.5% active in water) 5 coconut fatty acid 2 alcohol ethoxylate - average of 12 carbon, 7 mole ethoxylate 3 zeolite 4A 25 Jaguar C-17 1 5 Sokolan CP-5 2 5 Gelwhite GP 3 5 PVP (powder) 0.5 NaOH (50% in water) 3 light soda ash 15 sodium silicate 3 sodium sulphate 28.5 1 Available from Rhodia - US, Carnbury N.J. 2 Available from BASF, Mount Olive N.J.; 3 Available from Southern Clay Products, Gonzales Tex.
- the Softening parameter of the Comparative Formulation 1 was determined to be 35.
- Comparative formulation 3 employs ratios taught in U.S. Pat. Appl. Nos. 2002/0151454 , 2002/0155981 , 2002/0055451 and 2002/0058604 . TABLE 13.
- Comparative Formulation 3 Ingredient Percent in Formula (based on 100% active) Phase A alcohol ethoxylate 6 fluorescent whitening agent 0.158 sodium xylene sulphonate 2 Main Mix Water 55 sodium tetraborate pentahydrate 2 Polymer JR 30M 1 4 sodium hydroxide 1.91 Monoethanolamine 1 alkylbenzenesulphonic acid 6 coconut oil fatty acid 3 oleic acid 5 Phase A Added Water to 100 1 Available from Amerchol division of Dow Chemical, Edison N.J.
- the cationic polymer : surfactant ratio of comparative formulation 3 is 1:5; the cationic polymer : anionic surfactant ratio is 2:7; the cationic polymer : nonionic surfactant ratio is 1:3.
- Formulation 20 Ingredient Percent in Formula (based on 100% active) Phase A alcohol ethoxylate 6 fluorescent whitening agent 0.158 sodium xylene sulphonate (40%) 2 Main Mix water 55 sodium tetraborate pentahydrate 2 Polymer JR 30M 1 0.3 sodium hydroxide (50%) 1.91 monoethanolamine 1 Alkylbenzenesulphonic acid 6 coconut oil fatty acid 3 oleic acid 5 Phase A Added water to 100 1 Available from Amerchol division of Dow Chemical, Edison N.J.
- the cationic polymer : surfactant ratio of formulation 20 is 1:66.7; the cationic polymer: anionic surfactant ratio is 1: 46.7; the cationic polymer : nonionic surfactant ratio is 1: 20.
- the viscosity of each formula was measured with a Brookfield LV Viscometer (available from Brookfield Engineering, Stoughton, MA).
- the viscosity of comparative formulation 3 could not be measured, as the product was sufficiently thick to be out of the range (1,000,000 cP) of the viscometer.
- the viscosity of formulation 20 was measured as 430 cP with a #1 spindle at 12 rpm, which is well within the accepted range for consumer liquid laundry detergents (50-1000 cP).
- liquid laundry detergent formulations comprising zeolites, layered silicates and phosphates, along with cationic polymers tend to be unstable and aesthetically unacceptable for commercial sale.
- U.S. Pat. Appl. Nos. 2002/0151454 , 2002/0155981 , 2002/0055451 and 2002/0058604 teach the use of one or more of zeolite, layered silicate and phosphate. TABLE 15.
- Formulation 21 No zeolite, phosphate or layered silicate Ingredient Percent in Formula (based on 100% active) PHASE A Alcohol ethoxylate 6 Fluorescent whitening agent 0.158 Sodium xylene sulphonate (40%) 2 MAIN MIX Water 55 Sodium tetraborate pentahydrate 2 Polymer JR 30M 1 0.3 Sodium hydroxide (50%) 1.91 Triethanolamine 3 Alkylbenzenesulphonic acid 6 Coconut oil fatty acid 3 oleic acid 5 Phase A Added Water to 100 1 Available from Amerchol division of Dow Chemical, Edison N.J.
- Formulation 21 is according to the invention. TABLE 16. Comparative Formulation 4 - Comprises zeolite Ingredient Percent in Formula (based on 100% active) PHASE A Alcohol ethoxylate 6 Fluorescent whitening agent 0.158 Sodium xylene sulphonate (40%) 2 MAIN MIX Water 55 sodium tetraborate pentahydrate 2 Polymer JR 30M 2 0.3 sodium hydroxide (50%) 1.91 Triethanolamine 3 Alkylbenzenesulphonic acid 6 coconut oil fatty acid 3 oleic acid 5 zeolite 4A 1 3 Phase A Added Water to 100 1 Available from INESO Silicas, Joliet, IL. 2 Available from Amerchol division of Dow Chemical, Edison N.J.
- Comparative Formulation 4 is according to the invention. TABLE 17. Comparative Formulation 5 - Comprises phosphate Ingredient Percent in Formula (based on 100% active) PHASE A alcohol ethoxylate 6 Fluorescent whitening agent 0.158 sodium xylene sulphonate (40%) 2 MAIN MIX Water 55 sodium tetraborate pentahydrate 2 Polymer JR 30M 1 0.3 sodium hydroxide (50%) 1.91 Triethanolamine 3 Alkylbenzenesulphonic acid 6 coconut oil fatty acid 3 oleic acid 5 sodium Phosphate 10 Phase A Added Water to 100 1 Available from Amerchol division of Dow Chemical, Edison N.J.
- Comparative Formulation 5 is according to the invention. TABLE 18. Comparative Formulation 6 - comprises layered silicate Ingredient Percent in Formula (based on 100% active) PHASE A alcohol ethoxylate 6 Fluorescent whitening agent 0.158 sodium xylene sulphonate (40%) 2 MAIN MIX Water 55 sodium tetraborate pentahydrate 2 Polymer JR 30M 2 0.3 sodium hydroxide (50%) 1.91 Triethanolamine 3 Alkylbenzenesulphonic acid 6 Coconut oil fatty acid 3 oleic acid 5 Gelwhite GP 1 5 Phase A Added Water to 100 1 A bentonite-type layered silicate; available from Southern Clay Products, Gonzales, Tex.; 2 Available from Amerchol division of Dow Chemical, Edison N.J.
- Comparative Formulation 6 is according to the invention.
- Phase A in each was made and kept at 140F (60°C) until it was added at the point designated in the formula. Between additions, 5 minutes of constant mixing using an IKA RW 20 DZM.n mechanical stirrer equipped with a double-blade impeller took place to allow uniform blending to take place.
- Table 22 Cleaning Performance of Prototype Formulations Formulation Soil Cloth Cleaning Parameter, ⁇ R d 22 WFK-10D 2.8925 22 PC-9 9.1125 23 WFK-10D 7.6125 23 PC-9 13.2325 24 WFK-10D 10.2800 24 PC-9 14.0525
- Table 24 Formulation 25*: Powdered Detergent comprising high molecular-weight cationic polymer Ingredient Percent in Formula (based on 100% active) Base Powder Sodium Carbonate 32.94 Sodium Sulphate 18.83 Alkylbenzenesulphonic Acid 9.63 Sodium Silicate 16.47 Fluorescent Whitening Agent 0.1 Water 4.40 Post-Dose Polymer JR 30M 1 0.62 Sodium Cocoate 17.01 1 Available from the Amerchol division of Dow Chemical, Edison N.J.*Not according to the invention.
- Formulation 26* Powdered Detergent comprising low molecular-weight cationic polymer Ingredient Percent in Formula (based on 100% active) Base Powder Sodium Carbonate 32.94 Sodium Sulphate 18.83 Alkylbenzenesulphonic Acid 9.63 Sodium Silicate 16.47 Fluorescent Whitening Agent 0.1 Water 4.40 Post-Dose Polymer LR 400 1 0.62 Sodium Cocoate 17.01 1 Available from the Amerchol division of Dow Chemical, Edison N.J. *Not according to the invention
- the ingredients were first combined and spraydried into a base powder. Following this, the sodium cocoate and polymer were post-dosed, and all components were agitated for 60 seconds in a Waring Laboratory Blender on the low speed. For each formulation, the powder was dosed at 66.79g/wash.
- the following example illustrates how the odour profile of fabric softening compositions comprising cationic polymers can be improved without negatively impacting their conditioning properties by selecting a pH value between the pK a of coconut oil fatty acid, one of the anionic surfactant acids and the pK a of the amino or phosphino group that is used to quaternise the selected polymer.
- Table 28 Formulation 27: Formulated to a pH of 10.0 Ingredient Percent in Formula (based on 100% active) Phase A Alcohol ethoxylate 6 Fluorescent whitening agent 0.158 Main Mix Water 55 Sodium tetraborate pentahydrate 3.0 Sorbitol 5.0 Polymer LR 400 1 0.3 Sodium hydroxide (50%) 1.91 Triethanolamine 1.0 Alkylbenzenesulphonic acid 6.0 Alkyl ethoxysulphate 3.0 Coconut oil fatty acid 8 Phase A Added Water to 100 pH Adjusted to 10.0 with NaOH Table 29: Formulation 28: Formulated to a pH of 8.0 Ingredient Percent in Formula (based on 100% active) Phase A Alcohol ethoxylate 6 Fluorescent whitening agent 0.158 Main Mix Water 55 Sodium tetraborate pentahydrate 3.0 Sorbitol 5.0 Polymer LR 400 1 0.3 Sodium hydroxide (50%) 1.91 Triethanolamine 1.0 Alkylbenzenesulphonic acid 6.0 Alkyl ethoxysulphate 3.0
- the pK a of trimethylamine, the amino group used to quaternise Polymer LR 400 is 9.8. Prior to pH adjustment, when the pH of the formulations was approximately 5, they were physically unstable, as the pK a of the fatty acid had not been reached.
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Claims (8)
- Composition de lessive comprenant un ou plusieurs polymères cationiques choisis dans le groupe constitué par le chlorure d'hydroxypropyl-trimonium de guar et l'hydroxyéthylcellulose dérivatisé avec un époxyde à substitution tri-méthylammonium, et plus de 5 % d'un ou plusieurs tensioactifs anioniques ayant un HLB supérieur à environ 4, dans laquelle la composition comprend en outre un tensioactif non ionique, et dans laquelle les rapports polymère cationique : tensio-actif total, polymère cationique : tensioactif anionique et polymère cationique : tensioactif non ionique sont inférieurs à 1:10,
et dans laquelle le tensioactif non ionique comprend un éthoxylate d'alcool gras de formule : R'(EO)n où R' représente une chaîne alkyle comprenant entre 4 et 30 atomes de carbone, (EO) représente un motif de monomère d'oxyde d'éthylène et n a une valeur moyenne comprise entre 0,5 et 20. - Composition selon la revendication 1, dans laquelle un ou plusieurs des polymères cationiques ont une teneur en azote inférieure à environ 2 %.
- Composition selon la revendication 1 ou la revendication 2, dans laquelle un ou plusieurs polymères cationiques ont un poids moléculaire inférieur à environ 850 000 daltons.
- Composition selon la revendication 1, dans laquelle ladite composition est un liquide ou une pâte ayant un pH inférieur au pKa d'une amine de phosphate utilisée pour quaterniser un des polymères cationiques.
- Procédé de conditionnement de textiles comprenant, sans ordre particulier, les étapes de :a. fournir une composition détergente de lessive ou une composition assouplissante selon la revendication 1 à une concentration suffisante pour assouplir et conditionner de manière efficace les tissus dans des conditions de lavage prédéterminées ;b. mettre en contact un ou plusieurs articles avec la composition à un ou plusieurs moments pendant le procédé de lavage ; etc. laisser les articles sécher ou les sécher mécaniquement en tambour.
- Procédé selon la revendication 5, dans lequel un ou plusieurs polymères cationiques ont un poids moléculaire inférieur à environ 850 000 daltons.
- Procédé selon la revendication 5, dans lequel la composition détergente ou assouplissante est diluée par un rapport pondéral de plus d'environ 1:100 avec de l'eau ou un solvant.
- Procédé selon la revendication 5, dans lequel au moins un tensioactif anionique est choisi dans le groupe constitué par les sels alcalins et de métaux alcalino-terreux d'acide carboxylique gras, les sels alcalins et de métaux alcalino-terreux de sulfonates d'alkylbenzène.
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/357,248 US20040152616A1 (en) | 2003-02-03 | 2003-02-03 | Laundry cleansing and conditioning compositions |
US357248 | 2003-02-03 | ||
US10/446,202 US6949498B2 (en) | 2003-02-03 | 2003-05-27 | Laundry cleansing and conditioning compositions |
US446202 | 2003-05-27 | ||
PCT/EP2004/000668 WO2004069979A2 (fr) | 2003-02-03 | 2004-01-23 | Compositions de nettoyage et de conditionnement pour blanchisserie |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1590426A2 EP1590426A2 (fr) | 2005-11-02 |
EP1590426B1 true EP1590426B1 (fr) | 2014-01-08 |
Family
ID=32853092
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP04704608.1A Revoked EP1590426B1 (fr) | 2003-02-03 | 2004-01-23 | Compositions de nettoyage et de conditionnement pour blanchisserie |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1590426B1 (fr) |
BR (1) | BRPI0407114B1 (fr) |
CA (1) | CA2514766C (fr) |
WO (1) | WO2004069979A2 (fr) |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102004020015A1 (de) * | 2004-04-21 | 2005-11-10 | Henkel Kgaa | Textilpflegemittel |
US8529927B2 (en) | 2004-04-30 | 2013-09-10 | Allergan, Inc. | Alpha-2 agonist polymeric drug delivery systems |
US20060030513A1 (en) * | 2004-08-03 | 2006-02-09 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Softening laundry detergent |
US20060223739A1 (en) * | 2005-04-05 | 2006-10-05 | Unilever Home And Personal Care Usa, Division Of Conopco, Inc. | Fabric softening composition with cationic polymer, soap, and amphoteric surfactant |
GB0605512D0 (en) * | 2006-03-18 | 2006-04-26 | Unilever Plc | Fabric treatment composition and process for preparation thereof |
ES2406948T5 (es) † | 2007-03-20 | 2019-10-15 | Procter & Gamble | Composición tratante líquida |
MX2011002152A (es) | 2008-08-28 | 2011-03-29 | Procter & Gamble | Composiciones y metodos para suministrar un beneficio. |
EP2857489A3 (fr) | 2008-08-28 | 2015-04-29 | The Procter and Gamble Company | Procédé de fabrication d'une composition de soin du linge |
CN102257115B (zh) * | 2008-12-22 | 2013-02-06 | 荷兰联合利华有限公司 | 洗衣组合物 |
BRPI0923571A2 (pt) * | 2008-12-22 | 2016-08-23 | Unilever Nv | composição detergente líquida, e, método para proporcionar maciez a um tecido |
EP2449078A1 (fr) * | 2009-06-30 | 2012-05-09 | The Procter & Gamble Company | Compositions d entretien de textile comprenant des polymères cationiques et un amphotère |
WO2011121073A1 (fr) | 2010-03-31 | 2011-10-06 | Henkel Ag & Co. Kgaa | Agent détergent pour textiles délicats |
PL2399980T3 (pl) | 2010-06-24 | 2013-01-31 | Procter & Gamble | Trwałe kompozycje zawierające polimer celulozy oraz celulazę |
US10507176B2 (en) | 2014-11-25 | 2019-12-17 | Dow Global Technologies Llc | Hair care compositions containing cationic polymers |
WO2016085707A1 (fr) | 2014-11-25 | 2016-06-02 | The Dow Chemical Company | Compositions de soin personnel contenant des polymères cationiques |
US20210395655A1 (en) | 2020-06-18 | 2021-12-23 | The Procter & Gamble Company | Water-soluble unit dose article comprising a polyvinylalcohol film and a cationic poly alpha-1,6-glucan ether compound |
Family Cites Families (60)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3332880A (en) | 1965-01-04 | 1967-07-25 | Procter & Gamble | Detergent composition |
US3472840A (en) | 1965-09-14 | 1969-10-14 | Union Carbide Corp | Quaternary nitrogen-containing cellulose ethers |
CA992832A (en) | 1972-04-28 | 1976-07-13 | The Procter And Gamble Company | Crystallization seed-containing composition |
GB1565807A (en) | 1975-12-18 | 1980-04-23 | Uilever Ltd | Process and compositions for cleaning fabrics |
US4146495A (en) | 1977-08-22 | 1979-03-27 | Monsanto Company | Detergent compositions comprising polyacetal carboxylates |
US4144226A (en) | 1977-08-22 | 1979-03-13 | Monsanto Company | Polymeric acetal carboxylates |
US4299817A (en) | 1977-08-24 | 1981-11-10 | Union Carbide Corporation | Hair care compositions |
GR76237B (fr) | 1981-08-08 | 1984-08-04 | Procter & Gamble | |
GB8329762D0 (en) | 1983-11-08 | 1983-12-14 | Unilever Plc | Manganese adjuncts |
GB8504733D0 (en) | 1985-02-23 | 1985-03-27 | Procter & Gamble Ltd | Detergent compositions |
US4601845A (en) | 1985-04-02 | 1986-07-22 | Lever Brothers Company | Bleaching compositions containing mixed metal cations adsorbed onto aluminosilicate support materials |
US4711748A (en) | 1985-12-06 | 1987-12-08 | Lever Brothers Company | Preparation of bleach catalyst aggregates of manganese cation impregnated aluminosilicates by high velocity granulation |
US4728455A (en) | 1986-03-07 | 1988-03-01 | Lever Brothers Company | Detergent bleach compositions, bleaching agents and bleach activators |
US4913828A (en) | 1987-06-10 | 1990-04-03 | The Procter & Gamble Company | Conditioning agents and compositions containing same |
GB8720863D0 (en) | 1987-09-04 | 1987-10-14 | Unilever Plc | Metalloporphyrins |
US5073274A (en) | 1988-02-08 | 1991-12-17 | The Procter & Gamble Co. | Liquid detergent containing conditioning agent and high levels of alkyl sulfate/alkyl ethoxylated sulfate |
US4844821A (en) | 1988-02-10 | 1989-07-04 | The Procter & Gamble Company | Stable liquid laundry detergent/fabric conditioning composition |
CA2001927C (fr) | 1988-11-03 | 1999-12-21 | Graham Thomas Brown | Aluminosilicates et detergents |
EP0384503B1 (fr) | 1989-02-22 | 1995-06-28 | Unilever N.V. | Métalloporphyrines pour l'utilisation comme catalyseur de blanchiment |
GB8908416D0 (en) | 1989-04-13 | 1989-06-01 | Unilever Plc | Bleach activation |
GB8915781D0 (en) | 1989-07-10 | 1989-08-31 | Unilever Plc | Bleach activation |
GB9003741D0 (en) | 1990-02-19 | 1990-04-18 | Unilever Plc | Bleach activation |
US5047163A (en) | 1990-03-16 | 1991-09-10 | Lever Brothers Company, Division Of Conopco, Inc. | Activation of bleach precursors with sulfonimines |
US5041232A (en) | 1990-03-16 | 1991-08-20 | Lever Brothers Company, Division Of Conopco, Inc. | Sulfonimines as bleach catalysts |
ES2100925T3 (es) | 1990-05-21 | 1997-07-01 | Unilever Nv | Activacion de blanqueador. |
GB9108136D0 (en) | 1991-04-17 | 1991-06-05 | Unilever Plc | Concentrated detergent powder compositions |
US5274147A (en) | 1991-07-11 | 1993-12-28 | Lever Brothers Company, Division Of Conopco, Inc. | Process for preparing manganese complexes |
GB9118242D0 (en) | 1991-08-23 | 1991-10-09 | Unilever Plc | Machine dishwashing composition |
GB9124581D0 (en) | 1991-11-20 | 1992-01-08 | Unilever Plc | Bleach catalyst composition,manufacture and use thereof in detergent and/or bleach compositions |
US5153161A (en) | 1991-11-26 | 1992-10-06 | Lever Brothers Company, Division Of Conopco, Inc. | Synthesis of manganese oxidation catalyst |
CA2083661A1 (fr) | 1991-11-26 | 1993-05-27 | Rudolf J. Martens | Compositions pour detersif |
US5194416A (en) | 1991-11-26 | 1993-03-16 | Lever Brothers Company, Division Of Conopco, Inc. | Manganese catalyst for activating hydrogen peroxide bleaching |
CA2085642A1 (fr) | 1991-12-20 | 1993-06-21 | Ronald Hage | Activation de blanchiment |
GB9127060D0 (en) | 1991-12-20 | 1992-02-19 | Unilever Plc | Bleach activation |
US5256779A (en) | 1992-06-18 | 1993-10-26 | Lever Brothers Company, Division Of Conopco, Inc. | Synthesis of manganese oxidation catalyst |
US5280117A (en) | 1992-09-09 | 1994-01-18 | Lever Brothers Company, A Division Of Conopco, Inc. | Process for the preparation of manganese bleach catalyst |
WO1996023861A1 (fr) | 1995-02-02 | 1996-08-08 | The Procter & Gamble Company | Compositions pour le lavage automatique de la vaisselle comprenant des catalyseurs cobalteux |
DE69608541T2 (de) | 1995-02-02 | 2001-01-18 | The Procter & Gamble Company, Cincinnati | Maschinengeschirrspülmittel zusammensetzungen mit kobalt chelatkatalysatoren |
CA2212115C (fr) | 1995-02-02 | 2001-04-24 | The Procter & Gamble Company | Compositions de lavage automatique de la vaisselle comprenant des catalyseurs a base de cobalt |
US6148644A (en) | 1995-03-06 | 2000-11-21 | Lever Brothers Company, Division Of Conopco, Inc. | Dry cleaning system using densified carbon dioxide and a surfactant adjunct |
US5559261A (en) | 1995-07-27 | 1996-09-24 | The Procter & Gamble Company | Method for manufacturing cobalt catalysts |
US6040053A (en) | 1996-07-19 | 2000-03-21 | Minnesota Mining And Manufacturing Company | Coating composition having anti-reflective and anti-fogging properties |
GB9615630D0 (en) | 1996-07-25 | 1996-09-04 | Procter & Gamble | Shampoo compositions |
GB9615631D0 (en) | 1996-07-25 | 1996-09-04 | Procter & Gamble | Shampoo compositions |
US6492322B1 (en) * | 1996-09-19 | 2002-12-10 | The Procter & Gamble Company | Concentrated quaternary ammonium fabric softener compositions containing cationic polymers |
AU723907B2 (en) | 1996-10-16 | 2000-09-07 | Unilever Plc | Fabric softening composition |
US5733854A (en) * | 1996-10-25 | 1998-03-31 | Rhone-Poulenc Inc. | Cleaning compositions including derivatized guar gum composition including nonionic and cationic groups which demonstrate excellent solution clarity properties |
US6090372A (en) | 1997-07-15 | 2000-07-18 | Lever Brothers Company, Division Of Conopco, Inc. | Liquid detergent compositions and process for their preparation |
WO1999027057A1 (fr) | 1997-11-21 | 1999-06-03 | The Procter & Gamble Company | Compositions detergentes liquides comprenant des activateurs polymeres de mousse |
US6258771B1 (en) * | 1998-12-16 | 2001-07-10 | Unilever Home & Personal Care, Usa Division Of Conopco | Process for preparing pourable, transparent/translucent liquid detergent with non-continuous suspending system |
GB9911437D0 (en) * | 1999-05-17 | 1999-07-14 | Unilever Plc | Fabric softening compositions |
US6533873B1 (en) * | 1999-09-10 | 2003-03-18 | Unilever Home & Personal Care Usa Division Of Conopco, Inc. | Suspending clear cleansing formulation |
GB0009029D0 (en) * | 2000-04-12 | 2000-05-31 | Unilever Plc | Laundry wash compositions |
US6903061B2 (en) * | 2000-08-28 | 2005-06-07 | The Procter & Gamble Company | Fabric care and perfume compositions and systems comprising cationic silicones and methods employing same |
DE10044496A1 (de) | 2000-09-08 | 2002-03-21 | Cognis Deutschland Gmbh | Waschmitteltabletten |
DE10044473A1 (de) | 2000-09-08 | 2002-03-21 | Cognis Deutschland Gmbh | Waschmitteltabletten |
DE10044471A1 (de) * | 2000-09-08 | 2002-03-21 | Cognis Deutschland Gmbh | Waschmittel |
DE10044472A1 (de) | 2000-09-08 | 2002-03-21 | Cognis Deutschland Gmbh | Waschmittel |
GB0104979D0 (en) | 2001-02-28 | 2001-04-18 | Unilever Plc | Unit dose cleaning product |
US7067499B2 (en) * | 2002-05-06 | 2006-06-27 | Hercules Incorporated | Cationic polymer composition and its use in conditioning applications |
-
2004
- 2004-01-23 WO PCT/EP2004/000668 patent/WO2004069979A2/fr active Application Filing
- 2004-01-23 BR BRPI0407114A patent/BRPI0407114B1/pt not_active IP Right Cessation
- 2004-01-23 CA CA2514766A patent/CA2514766C/fr not_active Expired - Fee Related
- 2004-01-23 EP EP04704608.1A patent/EP1590426B1/fr not_active Revoked
Also Published As
Publication number | Publication date |
---|---|
EP1590426A2 (fr) | 2005-11-02 |
WO2004069979A2 (fr) | 2004-08-19 |
CA2514766A1 (fr) | 2004-08-19 |
BRPI0407114B1 (pt) | 2018-09-11 |
WO2004069979A3 (fr) | 2005-11-24 |
BRPI0407114A (pt) | 2006-01-24 |
CA2514766C (fr) | 2012-09-25 |
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