WO2010012590A1 - Improvements relating to fabric conditioners - Google Patents
Improvements relating to fabric conditioners Download PDFInfo
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- WO2010012590A1 WO2010012590A1 PCT/EP2009/059049 EP2009059049W WO2010012590A1 WO 2010012590 A1 WO2010012590 A1 WO 2010012590A1 EP 2009059049 W EP2009059049 W EP 2009059049W WO 2010012590 A1 WO2010012590 A1 WO 2010012590A1
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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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/645—Mixtures of compounds all of which are cationic
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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
- C11D1/66—Non-ionic compounds
- C11D1/835—Mixtures of non-ionic with cationic 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
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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
- C11D3/50—Perfumes
- C11D3/502—Protected perfumes
- C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/62—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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/662—Carbohydrates or derivatives
Definitions
- the present invention relates to stable fabric softener compositions containing encapsulates.
- WO2006/131846 discloses substantially non-aqueous cleaning or conditioning compositions comprising a fragrance encapsulated in aminoplast type microcapsules, and addresses the problem of instability of the perfume capsules themselves .
- EP1589092 discloses fabric conditioner compositions comprising encapsulated fragrances, and describes the stabilising effect of non-ionic surfactants on the encapsulate slurry itself.
- WO2008/016637 discloses fabric conditioner compositions comprising ester-linked quaternary ammonium compounds and particles having a polymeric wall material surrounding a benefit agent, which is a fragrance.
- US2006/252669 discloses a fabric softener composition comprising cationic or non-ionic softening compound, a cross-linked cationic polymer and at least one fabric or skin beneficiating ingredient contained within a microcapsule.
- Some known perfume encaps have weak acid groups present on the surface of the capsule wall or shell, for example, those disclosed in US2007/0138672, EP-A-1407754, EP-A-1533364, EP-A-1797946, EP-A-1797947 , EP-A-1407753, EP-A-1589092 (all International Flavours and Fragrances Inc) and WO2008/005693 (Colgate-Palmolive Company) . These mainly arise from the use of a carboxylate based polymeric cross-linker during production of the polymeric shell.
- the weak acid Once the weak acid is in the ionic form it can complex with metal ions, protons or active molecules (such as quaternary ammonium softening active) . This complexation results in a dynamic equilibrium forming between the minor ionic form and the major molecular form. This dynamic, ever shifting equilibrium between the two forms leads to an unstable system. This is particularly marked in the case where the weak acid groups complex with a quaternary ammonium compound as this forms a solid, the uncomplexed phase being a liquid. The problem is exacerbated by the fact that the weak acid equilibrium changes with pH and the pH of fabric conditioner compositions is known to change upon storage.
- This invention allows perfume encapsulates having surface weak acid groups to be incorporated into a fabric conditioner without loss of stability, thus enabling the use of a wider range of perfumes as well as extending the shelf life of the product.
- composition comprising:
- encapsulated perfume components ii) a fabric softening active, which is selected from an ester-linked quaternary ammonium compound and an oily sugar derivative and mixtures thereof; iii) a stabilising active selected from the group consisting of from 0.05 to 0.2 wt% by the total weight of the composition of water soluble non- ester-linked cationic quaternary ammonium compound (s), from 0.65 to 1.5 wt% by the total weight of the composition of non-ionic surfactant (s) and mixtures thereof, and iv) from 0.005 to 0.1 wt% by the total weight of the composition of salt,
- the encapsulates comprise a capsule wall having surface weak acid groups .
- a second aspect of the invention provides a method of stabilising a fabric conditioning composition
- a fabric softening active which is selected from an ester-linked quaternary ammonium compound and an oily sugar derivative and mixtures thereof and from 0.005 to 0.1 wt% by the total weight of the composition of salt, wherein the encapsulates comprise a capsule wall having surface weak acid groups or moieties, comprising the step of adding a stabilising active selected from the group consisting of water soluble non-ester-linked cationic quaternary ammonium compounds, non-ionic surfactants and mixtures thereof to the composition.
- the encaps for use in the present invention comprise a shell and a perfume core.
- the shell is comprised of materials having weak acid groups on the surface, such as surface carboxylic acid groups or moieties.
- surface carboxylate containing groups or moieties is meant that the encapsulate shell wall has a plurality of carboxylate containing groups on its outer surface, which can interact with species in the composition.
- weak acid groups is meant those proton donating groups that are found on weak acids, i.e. acids that only partially dissociate in aqueous solution, for example, the so-called “organic acids” .
- Fragrance capsules known in the art and suitable for use in the present invention comprise a wall or shell comprising a three-dimensional cross-linked network of an aminoplast resin, more specifically a substituted or un-substituted acrylic acid polymer or co-polymer cross-linked with a urea- formaldehyde pre-condensate or a melamine-formaldehyde pre- condensate; and having surface weak acid groups.
- Microcapsule formation suitable for use in the present invention, using (i) melamine-formaldehyde or urea- formaldehyde pre-condensates and (ii) polymers containing substituted vinyl monomeric units having carboxy-proton- donating functional group moieties (e.g. carboxylic acid anhydride groups) bonded thereto is disclosed in UK published Patent Application GB 2,006,709 A.
- Preferred cross-linking polymers include those given in the list above.
- the encaps are formed by reaction with a suitable monomer to form an insoluble shell.
- the encaps are formed from melamine formaldehyde or urea formaldehyde condensates, as well as similar types of monomers, with the cross-linking polymers given above.
- the shell comprises melamine formaldehyde.
- Encapsulation can provide pore vacancies or interstitial openings depending on the encapsulation techniques employed.
- the capsules for use in the invention have a perfume or perfume component core.
- a carrier oil may also be present in the encaps core, in addition to the fragrance compound (s).
- These oils are hydrophobic materials that are miscible in the perfume materials used in the present invention. Suitable oils are those having reasonable affinity for the fragrance chemicals. Suitable materials include, but are not limited to triglyceride oil, mono and diglycerides, mineral oil, silicone oil, diethyl phthalate, polyalpha olefins, castor oil and isopropyl myristate.
- the oil is a triglyceride oil, most preferably a capric/caprylic triglyceride oil.
- the capsules may be used in the form of a slurry, which preferably comprises about 40 % solids.
- the amount of such a 40% capsule slurry to be used in a composition is up to 10%, preferably from 0.1 to 5%, more preferably from 1 to 2% by weight of the total composition .
- the level is in the range of from 0.1 to 0.7 wt%, by weight of the total composition .
- Particle size and average diameter of the capsules can vary from about 10 nanometers to about 1000 microns, preferably from about 50 nanometers to about 100 microns, more preferably from about preferably from about 2 to about 40 microns, even more preferably from about 4 to 15 microns. A particularly preferred range is from about 5 to 10 microns, for example 6 to 7 microns.
- the capsule distribution can be narrow, broad or multimodal. Multimodal distributions may be composed of different types of capsule chemistries.
- the capsules can be combined with the composition at any time during the preparation of the laundry treatment composition.
- the capsules can be added to the composition or vice versa.
- the capsules may be post dosed to a pre-made composition or may be combined with other ingredients such as water, during the preparation of the composition.
- the stabilising active of the present invention is a mobile species which is capable of binding with weak acid groups.
- the weak acid groups bind with the stabilising active in preference to the fabric conditioning active .
- the stabilising actives are selected from the group consisting of water soluble non-ester-linked cationic quaternary ammonium compounds, non-ionic surfactants and mixtures thereof, preferably non-ionic surfactants.
- Suitable water soluble cationic quaternary ammonium compounds include single long chain ethoxylated cationic surfactant with a counter ion which is preferably an alkyl sulphate, such as methyl sulphate and ethyl sulphate, and most preferably is a methylsulphate counter-ion.
- the chains are not linked via ester groups.
- the single long chain cationic surfactants alternatives are alkoxylated cationic quaternary ammonium surfactants.
- Those suitable for use in this invention are generally derived from fatty alcohols, fatty acids, fatty methyl esters, alkyl substituted phenols, alkyl substituted benzoic acids, and/or alkyl substituted benzoate esters, and/or fatty acids that are converted to amines which can optionally be further reacted with another long chain alkyl or alkyl-aryl group; this amine compound is then alkoxylated with one or two alkylene oxide chains each having less than or equal to about 50 moles alkylene oxide moieties (e.g. ethylene oxide and/or propylene oxide) per mole of amine.
- alkylene oxide moieties e.g. ethylene oxide and/or propylene oxide
- Typical of this class are products obtained from the quaternization of aliphatic saturated or unsaturated, primary, secondary, or branched amines having one hydrocarbon chain from about 12 to about 22 carbon atoms alkoxylated with one or two alkylene oxide chains on the amine atom each having less than or equal to about 50 alkylene oxide moieties.
- the amine hydrocarbons for use herein have from about 12 to about 22 carbon atoms, and are preferably in a straight chain configuration.
- Suitable quaternary ammonium surfactants are made with one or two alkylene oxide chains attached to the amine moiety, in average amounts of less than or equal to about 50 moles of alkylene oxide per alkyl chain, more preferably from about 3 to about 20 moles of alkylene oxide, and most preferably from about 5 to about 12 moles of alkylene oxide per hydrophobic, e.g., alkyl group.
- Suitable stabilizers of this type include Ethoquad® 18/25, C/25, and 0/25 from Akzo and Variquat®-66 (soft tallow alkyl bis (polyoxyethyl) ammonium ethyl sulfate with a total of about 16 ethoxy units) from Goldschmidt.
- the compounds of the ammonium alkoxylated cationic surfactants have the following general formula:
- Preferred examples are Benzalkonium Chloride (Barquat MB- 50) ; ex LONZA
- Water soluble quat are selected from mono-long chain quaternary ammonium compound of general formula R(Rl) 3N+X- or alkyl benzyl quaternary ammonium compound of a general formula R2R3 (R4) 2N+X-
- R is selected from C8-C22 alkyl or alkenyl group
- Rl is selected from C1-C3 alkyl group
- R2 is selected from C6-C18 alkyl or alkenyl group
- R3 is benzyl group
- R4 is selected from C1-C3 alkyl group
- X is an anion selected from chloride, bromide, iodide, nitrate, sulphate, methyl sulphate, ethyl sulphate, acetate and phosphate.
- the water soluble quat of the present invention is either the alkyl benzyl quaternary ammonium chloride or the mono-long chain quaternary ammonium compound and most preferable the alkyl benzyl quaternary ammonium chloride .
- the level of water soluble cationic ammonium compounds is suitably from 0.005 to 0.2 wt%.
- Suitable non-ionic surfactants include addition products of ethylene oxide and/or propylene oxide with fatty alcohols, fatty acids and fatty amines. Any of the alkoxylated materials of the particular type described hereinafter can be used as the nonionic surfactant.
- Suitable surfactants are substantially water soluble surfactants of the general formula:
- R is selected from the group consisting of primary, secondary and branched chain alkyl and/or acyl hydrocarbyl groups; primary, secondary and branched chain alkenyl hydrocarbyl groups; and primary, secondary and branched chain alkenyl-substituted phenolic hydrocarbyl groups; the hydrocarbyl groups having a chain length of from 8 to about 25, preferably 10 to 20, e.g. 14 to 18 carbon atoms.
- Y is typically:
- R has the meaning given above or can be hydrogen; and Z is at least about 8, preferably at least about 10 or 11.
- the nonionic surfactant has an HLB of from about 7 to about 20, more preferably from 10 to 18, e.g. 12 to 16.
- Lutensol AT25 a non-ionic surfactant
- ex BASF and GenapolTM C200 (Clariant) , which is based on coco chain and 20 EO groups.
- the nonionic surfactant is present in an amount of from greater than 0.65 to 1.5%, more preferably from 0.7 to 1% by weight, most preferably from 0.7 to 0.9% based on the total weight of the composition.
- Salts suitable for use in the compositions of the invention generally include any of the alkaline metals or alkaline earth metal salts of the mineral acids. NaCl, CaCl2, MgCl2 and similar salts of alkaline and alkaline earth meals are preferred and CaCl2 is especially preferred. Generally, amounts of electrolyte salt needed are from 0.005 to 0.1 wt%, preferably from 0.01 to 0.07 wt%, by weight of the total composition. Unconfined Perfume
- compositions of the invention preferably comprise one or more unconfined perfume, by which is meant a non- encapsulated perfume. Any suitable perfume or mixture of perfumes may be used.
- the perfume must be compatible with the carrier oil as described above and must be able to permeate the shell of the capsule.
- the present invention may contain a single ingredient, but it is much more likely that the present invention will comprise at least eight or more fragrance chemicals, more likely to contain twelve or more and often twenty or more fragrance chemicals.
- the present invention also contemplates the use of complex fragrance formulations containing fifty or more fragrance chemicals, seventy five or more or even a hundred or more fragrance chemicals in a fragrance formulation.
- Suitable unconfined perfumes for use in the present invention include those disclosed in EP1533364A2 (IFF) .
- the perfume is preferably present in an amount from 0.01 to 10% by weight, more preferably from 0.05 to 5% by weight, even more preferably from 0.1 to 4.0%, most preferably from 0.2 to 4.0% by weight, based on the total weight of the composition.
- Useful components of the perfume include materials of both natural and synthetic origin. They include single compounds and mixtures. Specific examples of such components may be found in the current literature, e.g., in Fenaroli's
- perfume in this context is not only meant a fully formulated product fragrance, but also selected components of that fragrance, particularly those which are prone to loss, such as the so-called ⁇ top notes' .
- Top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2): 80 [1955]). Examples of well known top-notes include citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol . Top notes typically comprise 15-25%wt of a perfume composition and in those embodiments of the invention which contain an increased level of top-notes it is envisaged at that least 20%wt would be present within the encapsulate.
- perfume or pro-fragrance may be encapsulated, typical perfume components which it is advantageous to encapsulate, include those with a relatively low boiling point, preferably those with a boiling point of less than 300, preferably 100-250 Celsius and pro-fragrances which can produce such components. It is also advantageous to encapsulate perfume components which have a low Clog P (i.e. those which will be partitioned into water) , preferably with a Clog P of less than 3.0. These materials, of relatively low boiling point and relatively low Clog P have been called the "delayed blooming" perfume ingredients and include the following materials :
- Preferred non-encapsulated perfume ingredients are those hydrophobic perfume components with a ClogP above 3.
- ClogP means the logarithm to base 10 of the octanol/water partition coefficient (P) .
- the octanol/water partition coefficient of a PRM is the ratio between its equilibrium concentrations in octanol and water. Given that this measure is a ratio of the equilibrium concentration of a PRM in a non-polar solvent (octanol) with its concentration in a polar solvent (water) , ClogP is also a measure of the hydrophobicity of a material--the higher the ClogP value, the more hydrophobic the material.
- ClogP values can be readily calculated from a program called "CLOGP" which is available from Daylight Chemical Information Systems Inc., Irvine Calif., USA. Octanol/water partition coefficients are described in more detail in U.S. Pat. No. 5,578,563.
- Perfume components with a ClogP above 3 comprise: Iso E super, citronellol, Ethyl cinnamate, Bangalol, 2,4,6- Trimethylbenzaldehyde, Hexyl cinnamic aldehyde, 2,6-
- compositions of the present invention it is envisaged that there will be four or more, preferably five or more, more preferably six or more or even seven or more different perfume components from the list given of delayed blooming perfumes given above and/or the list of perfume components with a ClogP above 3 present in the perfume.
- perfumes with which the present invention can be applied are the so-called ⁇ aromatherapy' materials. These include many components also used in perfumery, including components of essential oils such as Clary Sage, Eucalyptus, Geranium, Lavender, Mace Extract, Neroli, Nutmeg, Spearmint, Sweet Violet Leaf and Valerian.
- the conditioning agents may be cationic, non-ionic, or mixtures thereof.
- the fabric conditioning compositions of the invention may be dilute or concentrated.
- Dilute products typically contain up to about 8%, preferably from 2 to 8% by weight of softening active, whereas concentrated products may contain from about 8 to about 50%, preferably from 8 to 25% by weight active.
- Compositions of more than about 25% by weight of active are defined as "super concentrated", depending on the active system, and are also intended to be covered by the present invention.
- the fabric conditioning agent may, for example, be used in amounts of from 0.5% to 35%, preferably from 2% to 30% more preferably from 5% to 25% and most preferably from 8% to 20% by weight of the composition.
- the preferred softening active for use in rinse conditioner compositions of the invention is a quaternary ammonium compound (QAC) .
- QAC quaternary ammonium compound
- the quaternary ammonium fabric conditioners for use in compositions of the present invention are the so called "ester quats”.
- Particularly preferred materials are the ester-linked triethanolamine (TEA) quaternary ammonium compounds comprising a mixture of mono-, di- and tri-ester linked components .
- TAA ester-linked triethanolamine
- TEA-based fabric softening compounds comprise a mixture of mono, di- and tri-ester forms of the compound where the di-ester linked component comprises no more than 70% by weight of the fabric softening compound, preferably no more than 60%, e.g. no more than 55%, or even no more than 45% of the fabric softening compound and at least 10% of the monoester linked component.
- a first group of quaternary ammonium compounds (QACs) suitable for use in the present invention is represented by formula (I) :
- each R is independently selected from a C5-35 alkyl or alkenyl group;
- R 1 represents a C1-4 alkyl, C2-4 alkenyl or a Ci-4 hydroxyalkyl group;
- T is generally O-CO. (i.e. an ester group bound to R via its carbon atom) , but may alternatively be CO-O (i.e. an ester group bound to R via its oxygen atom) ;
- n is a number selected from 1 to 4;
- m is a number selected from 1, 2, or 3;
- X ⁇ is an anionic counter-ion, such as a halide or alkyl sulphate, e.g. chloride or methylsulphate .
- TEA ester quats preparations which are rich in the di-esters of triethanolammonium methylsulphate, otherwise referred to as "TEA ester quats".
- StepantexTM UL85 Ex Stepan, PrapagenTM TQL, ex Clariant, and TetranylTM AHT-I, ex Kao, (both di- [hardened tallow ester] of triethanolammonium methylsulphate), AT-I (di- [tallow ester] of triethanolammonium methylsulphate), and L5/90 (di- [palm ester] of triethanolammonium methylsulphate)
- Ex Kao Ex Kao
- RewoquatTM WE15 a di-ester of triethanolammonium methylsulphate having fatty acyl residues deriving from Cio ⁇ C20 and C16-C18 unsaturated fatty acids
- a second group of QACs suitable for use in the invention is represented by formula (II) :
- each R 1 group is independently selected from C1-4 alkyl, hydroxyalkyl or C 2 - 4 alkenyl groups; and wherein each R 2 group is independently selected from Cs- 2 8 alkyl or alkenyl groups; and wherein n, T, and X ⁇ are as defined above.
- Preferred materials of this second group include 1,2 bis [ tallowoyloxy] -3-trimethylammonium propane chloride, 1,2 bis [hardened tallowoyloxy] -3-trimethylammonium propane chloride, 1, 2-bis [oleoyloxy] -3-trimethylammonium propane chloride, and 1,2 bis [stearoyloxy] -3-trimethylammonium propane chloride.
- Such materials are described in US 4,137,180 (Lever Brothers).
- these materials also comprise an amount of the corresponding mono-ester.
- a third group of QACs suitable for use in the invention is represented by formula (III):
- each R 1 group is independently selected from C1-4 alkyl, or C2-4 alkenyl groups; and wherein each R 2 group is independently selected from Cs-28 alkyl or alkenyl groups; and n, T, and X ⁇ are as defined above.
- Preferred materials of this third group include bis (2-tallowoyloxyethyl) dimethyl ammonium chloride and hardened versions thereof.
- the iodine value of the quaternary ammonium fabric conditioning material is preferably from 0 to 80, more preferably from 0 to 60, and most preferably from 0 to 45.
- the iodine value may be chosen as appropriate.
- Essentially saturated material having an iodine value of from 0 to 5, preferably from 0 to 1 may be used in the compositions of the invention. Such materials are known as "hardened" quaternary ammonium compounds.
- a further preferred range of iodine values is from 20 to 60, preferably 25 to 50, more preferably from 30 to 45.
- a material of this type is a "soft" triethanolamine quaternary ammonium compound, preferably triethanolamine di-alkylester methylsulphate .
- Such ester-linked triethanolamine quaternary ammonium compound comprise unsaturated fatty chains.
- Typical ester quat ratios of these materials are in the range of from 25 to 45% mono ester quat, from 45 to 60% diester quat and from 5 to 20% triester quat, preferably from 30 to 40% mono ester quat, from 50 to 55% diester quat and from 10 to 15% triester quat.
- Iodine value refers to the measurement of the degree of unsaturation present in a material by a method of nmr spectroscopy as described in Anal. Chem., 3_£, 1136 (1962) Johnson and Shoolery .
- Iodine value is defined as the number of grams of iodine absorbed per lOOg of the test material. Olefinic materials absorb 1 gram of iodine per atom of olefinic hydrogen. Hence measurement can be converted to the equivalent Iodine Value.
- the hydrogen nmr spectrum at 360 MHz is obtained for the test material.
- the integral intensity, I 3 of the band derived from olefinic hydrogen in the alkyl chain and the integral intensity, I m , of the band derived from terminal methyl groups in the alkyl chains are measured.
- MMW is the mean molecular weight of the test material.
- compositions of the invention may contain a non-cationic softening material, which is an oily sugar derivative.
- An oily sugar derivative is a liquid or soft solid derivative of a cyclic polyol (CPE) or of a reduced saccharide (RSE) , said derivative resulting from 35 to 100% of the hydroxyl groups in said polyol or in said saccharide being esterified or etherified.
- the derivative has two or more ester or ether groups independently attached to a C8-C22 alkyl or alkenyl chain.
- the CPE or RSE does not have any substantial crystalline character at 2O 0 C. Instead it is preferably in a liquid or soft solid state as herein defined at 2O 0 C.
- liquid or soft solid (as hereinafter defined) CPEs or RSEs suitable for use in the present invention result from 35 to 100% of the hydroxyl groups of the starting cyclic polyol or reduced saccharide being esterified or etherified with groups such that the CPEs or RSEs are in the required liquid or soft solid state.
- These groups typically contain unsaturation, branching or mixed chain lengths.
- the CPEs or RSEs have 3 or more ester or ether groups or mixtures thereof, for example 3 to 8, especially 3 to 5. It is preferred if two or more of the ester or ether groups of the CPE or RSE are independently of one another attached to a Cs to C22 alkyl or alkenyl chain.
- the Cs to C22 alkyl or alkenyl groups may be branched or linear carbon chains .
- 35 to 85% of the hydroxyl groups most preferably 40-80%, even more preferably 45-75%, such as 45-70% are esterified or etherified.
- the CPE or RSE contains at least 35% tri or higher esters, eg at least 40%.
- the CPE or RSE has at least one of the chains independently attached to the ester or ether groups having at least one unsaturated bond. This provides a cost effective way of making the CPE or RSE a liquid or a soft solid. It is preferred if predominantly unsaturated fatty chains, derived from, for example, rape oil, cotton seed oil, soybean oil, oleic, tallow, palmitoleic, linoleic, erucic or other sources of unsaturated vegetable fatty acids, are attached to the ester/ether groups.
- ester or ether chains of the CPE or RSE.
- the ester or ether chains of the CPE or RSE are preferably predominantly unsaturated.
- Preferred CPEs or RSEs include sucrose tetratallowate, sucrose tetrarapeate, sucrose tetraoleate, sucrose tetraesters of soybean oil or cotton seed oil, cellobiose tetraoleate, sucrose trioleate, sucrose triapeate, sucrose pentaoleate, sucrose pentarapeate, sucrose hexaoleate, sucrose hexarapeate, sucrose triesters, pentaesters and hexaesters of soybean oil or cotton seed oil, glucose tiroleate, glucose tetraoleate, xylose trioleate, or sucrose tetra-, tri-, penta- or hexa- esters with any mixture of predominantly unsaturated fatty acid chains.
- the most preferred CPEs or RSEs are those with monosaturated fatty acid chains, i.e. where any polyunsaturation has been removed by partial hydrogenation .
- some CPEs or RSEs based on polyunsaturated fatty acid chains e.g. sucrose tetralinoleate, may be used provided most of the polyunsaturation has been removed by partial hydrogenation.
- the most highly preferred liquid CPEs or RSEs are any of the above but where the polyunsaturation has been removed through partial hydrogenation .
- the fatty acid chains Preferably 40% or more of the fatty acid chains contain an unsaturated bond, more preferably 50% or more, most preferably 60% or more. In most cases 65% to 100%, e.g. 65% to 95% contain an unsaturated bond.
- CPEs are preferred for use with the present invention.
- Inositol is a preferred example of a cyclic polyol. Inositol derivatives are especially preferred.
- cyclic polyol encompasses all forms of saccharides. Indeed saccharides are especially preferred for use with this invention. Examples of preferred saccharides for the CPEs or RSEs to be derived from are monosaccharides and disaccharides .
- Examples of monosaccharides include xylose, arabinose, galactose, fructose, sorbose and glucose. Glucose is especially preferred.
- Examples of disaccharides include maltose, lactose, cellobiose and sucrose. Sucrose is especially preferred.
- An example of a reduced saccharide is sorbitan .
- the liquid or soft solid CPEs can be prepared by methods well known to those skilled in the art. These include acylation of the cyclic polyol or reduced saccharide with an acid chloride; trans-esterification of the cyclic polyol or reduced saccharide fatty acid esters using a variety of catalysts; acylation of the cyclic polyol or reduced saccharide with an acid anhydride and acylation of the cyclic polyol or reduced saccharide with a fatty acid. See for instance US 4 386 213 and AU 14416/88 (both P&G) .
- the CPE or RSE has 3 or more, preferably 4 or more ester or ether groups. If the CPE is a disaccharide it is preferred if the disaccharide has 3 or more ester or ether groups. Particularly preferred CPEs are esters with a degree of esterification of 3 to 5, for example, sucrose tri, tetra and penta esters.
- each ring of the CPE has one ether or ester group, preferably at the Ci position.
- Suitable examples of such compounds include methyl glucose derivatives.
- CPEs examples include esters of alkyl (poly) glucosides, in particular alkyl glucoside esters having a degree of polymerisation from 1 to 2.
- the length of the unsaturated (and saturated if present) chains in the CPE or RSE is C 8 -C 22 , preferably Ci 2 -C 22 . It is possible to include one or more chains of Ci-Cs, however these are less preferred.
- the liquid or soft solid CPEs or RSEs which are suitable for use in the present invention are characterised as materials having a solid: liquid ratio of between 50:50 and 0:100 at 2O 0 C as determined by T 2 relaxation time NMR, preferably between 43:57 and 0:100, most preferably between 40:60 and 0:100, such as, 20:80 and 0:100.
- the T 2 NMR relaxation time is commonly used for characterising solid: liquid ratios in soft solid products such as fats and margarines.
- any component of the signal with a T 2 of less than 100 ⁇ s is considered to be a solid component and any component with T 2 > 100 ⁇ s is considered to be a liquid component.
- the prefixes e.g. tetra and penta
- the compounds exist as a mixture of materials ranging from the monoester to the fully esterified ester. It is the average degree of esterification which is used herein to define the CPEs and RSEs.
- the HLB of the CPE or RSE is typically between 1 and 3.
- the CPE or RSE is preferably present in the composition in an amount of 0.5-50% by weight, based upon the total weight of the composition, more preferably 1-30% by weight, such as 2-25%, e.g. 2-20%.
- the CPEs and RSEs for use in the compositions of the invention include sucrose tetraoleate, sucrose pentaerucate, sucrose tetraerucate and sucrose pentaoleate.
- Optional shading dyes can be used. Preferred dyes are violet or blue. Suitable and preferred classes of dyes are discussed below. Moreover the unsaturated quaternary ammonium compounds are subject to some degree of UV light and/or transition metal ion catalysed radical auto- oxidation, with an attendant risk of yellowing of fabric. The present of a shading dye also reduces the risk of yellowing from this source.
- Direct dyes are the class of water soluble dyes which have a affinity for fibres and are taken up directly. Direct violet and direct blue dyes are preferred.
- the dye are bis-azo or tris-azo dyes are used.
- the direct dye is a direct violet of the following structures:
- ring D and E may be independently naphthyl or phenyl as shown;
- Ri is selected from: hydrogen and Cl-C4-alkyl, preferably hydrogen;
- R2 is selected from: hydrogen, Cl-C4-alkyl, substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl, preferably phenyl;
- R3 and R4 are independently selected from: hydrogen and Cl-
- C4-alkyl preferably hydrogen or methyl
- Preferred dyes are direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51, and direct violet 99.
- Bis-azo copper containing dyes such as direct violet 66 may be used.
- the benzidene based dyes are less preferred.
- the direct dye is present at 0.00001 wt% to 0.0010 wt% of the formulation.
- the direct dye may be covalently linked to the photo-bleach, for example as described in WO2006/024612.
- Cotton substantive acid dyes give benefits to cotton containing garments.
- Preferred dyes and mixes of dyes are blue or violet.
- Preferred acid dyes are:
- R a , R b , R c and R d are selected from: H, an branched or linear Cl to C7-alkyl chain, benzyl a phenyl, and a naphthyl ; the dye is substituted with at least one SC>3 ⁇ or -COO ⁇ group; the B ring does not carry a negatively charged group or salt thereof; and the A ring may further substituted to form a naphthyl; the dye is optionally substituted by groups selected from: amine, methyl, ethyl, hydroxyl, methoxy, ethoxy, phenoxy,
- Preferred azine dyes are: acid blue 98, acid violet 50, and acid blue 59, more preferably acid violet 50 and acid blue 98.
- non-azine acid dyes are acid violet 17, acid black 1 and acid blue 29.
- the acid dye is present at 0.0005 wt% to 0.01 wt% of the formulation.
- the composition may comprise one or more hydrophobic dyes selected from benzodifuranes, methine, triphenylmethanes, napthalimides, pyrazole, napthoquinone, anthraquinone and mono-azo or di-azo dye chromophores .
- Hydrophobic dyes are dyes which do not contain any charged water solubilising group. Hydrophobic dyes may be selected from the groups of disperse and solvent dyes. Blue and violet anthraquinone and mono-azo dye are preferred.
- Preferred dyes include solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63 and disperse violet 77.
- the hydrophobic dye is present at 0.0001 wt% to 0.005 wt% of the formulation.
- Basic dyes are organic dyes which carry a net positive charge. They deposit onto cotton. They are of particular utility for used in composition that contain predominantly cationic surfactants. Dyes may be selected from the basic violet and basic blue dyes listed in the Colour Index International .
- Preferred examples include triarylmethane basic dyes, methane basic dye, anthraquinone basic dyes, basic blue 16, basic blue 65, basic blue 66, basic blue 67, basic blue 71, basic blue 159, basic violet 19, basic violet 35, basic violet 38, basic violet 48; basic blue 3, basic blue 75, basic blue 95, basic blue 122, basic blue 124, basic blue 141.
- Reactive dyes are dyes which contain an organic group capable of reacting with cellulose and linking the dye to cellulose with a covalent bond. They deposit onto cotton.
- the reactive group is hydrolysed or reactive group of the dyes has been reacted with an organic species such as a polymer, so as to the link the dye to this species.
- Dyes may be selected from the reactive violet and reactive blue dyes listed in the Colour Index International.
- Preferred examples include reactive blue 19, reactive blue 163, reactive blue 182 and reactive blue, reactive blue 96.
- Dye conjugates are formed by binding direct, acid or basic dyes to polymers or particles via physical forces.
- Particularly preferred dyes are: direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51, direct violet 99, acid blue 98, acid violet 50, acid blue 59, acid violet 17, acid black 1, acid blue 29, solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63, disperse violet 77 and mixtures thereof.
- Co-softeners may be used. When employed, they are typically present at from 0.1 to 20% and particularly at from 0.3 to 10%, based on the total weight of the composition.
- Preferred co-softeners include fatty esters, and fatty N- oxides.
- Fatty esters that may be employed include fatty monoesters, such as glycerol monostearate, fatty sugar esters, such as those disclosed WO 01/46361 (Unilever).
- compositions of the present invention will preferably comprise a fatty complexing agent.
- suitable fatty complexing agents include fatty alcohols.
- the fatty complexing material improves the viscosity profile of the composition by complexing with mono-ester component of the fabric conditioner material thereby providing a composition which has relatively higher levels of di-ester and tri-ester linked components.
- the di-ester and tri-ester linked components are more stable and do not affect initial viscosity as detrimentally as the mono-ester component.
- compositions comprising quaternary ammonium materials based on TEA may destabilise the composition through depletion flocculation .
- depletion flocculation is significantly reduced.
- the fatty complexing agent at the increased levels as required by the present invention, "neutralises" the mono-ester linked component of the quaternary ammonium material. This in situ di-ester generation from mono-ester and fatty alcohol also improves the softening of the composition .
- Preferred fatty alcohols include hardened tallow alcohol
- the fatty complexing agent is preferably present in an amount of greater than 0.1 to 10%, such as from 0.2 to 5% by weight based on the total weight of the composition. More preferably, the fatty component is present in an amount of from 0.3 to 4 weight %.
- the weight ratio of the mono-ester component of the quaternary ammonium fabric softening material to the fatty complexing agent is preferably from 10:1 to 1:10, more preferably from 20:1 to 1:20.
- a preferred composition in accordance with the present invention comprises,
- encapsulated perfume components ii) from 8 to 50 wt %, preferably from 8 to 20 wt % of a fabric softening active, which is an ester- linked triethanolamine quaternary ammonium compound comprising unsaturated fatty chains, i ⁇ ) from 0.65 to 1.5 wt %, preferably from 0.7 to 1 wt %, most preferably from 0.7 to 0.9 wt % of a stabilising active, which is a non-ionic surfactant, iv) from 0.005 to 0.1 wt % of salt, which is CaCl2 and v) from greater than 0.3 to 5 % of tallow alcohol, wherein the encapsulates comprise a capsule wall having surface weak acid groups or moieties (and where weights are by the total weight of the composition) .
- compositions of the invention may contain one or more other ingredients.
- ingredients include further preservatives (e.g. bactericides), pH buffering agents, perfume carriers, hydrotropes, anti-redeposition agents, soil-release agents, polyelectrolytes, anti-shrinking agents, anti-wrinkle agents, anti-oxidants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents and ironing aids.
- the products of the invention preferably contain pearlisers and/or opacifiers.
- cationic polymeric deposition aids include cationic guar polymers such as JaguarTM (ex Rhone Poulenc) , cationic cellulose derivatives such as CelquatsTM (ex National Starch) , FlocaidTM (ex National Starch) , cationic potato starch such as SoftGelTM (ex Aralose) , cationic polyacrylamides such as PCG (ex Allied Colloids) .
- compositions of the present invention are rinse-added softening compositions suitable for use in a laundry process .
- compositions are preferably liquids.
- the liquid compositions preferably have a pH ranging of about 2.5.
- the formaldehyde level in the final product should be below 70 ppm, preferably below 15 ppm and most preferable below 10 ppm.
- the active ingredient in the compositions is a fabric softening agent. More than one active ingredient may be included.
- a composition for use in the invention is in liquid form.
- the composition may be a concentrate to be diluted in a solvent, including water, before use.
- the composition may also be a ready-to-use (in-use) composition.
- the composition is provided as a ready to use liquid comprising an aqueous phase.
- the aqueous phase may comprise water- soluble species, such as mineral salts or short chain (Ci_ 4 ) alcohols .
- compositions of the invention may also contain pH modifiers such as hydrochloric acid or lactic acid.
- the short chain alcohols include primary alcohols, such as ethanol, propanol, and butanol, and secondary alcohols such as isopropanol.
- the short chain alcohol may be added with the cationic softening agent during the preparation of the composition.
- the composition is preferably a fabric softener or fabric conditioner composition, and is preferably for use in the rinse cycle of a home textile laundering operation, where, it may be added directly in an undiluted state to a washing machine, e.g. through a dispenser drawer or, for a top- loading washing machine, directly into the drum. Alternatively, it can be diluted prior to use.
- the compositions may also be used in a domestic hand-washing laundry operation. It is also possible, though less desirable, for the compositions of the present invention to be used in industrial laundry operations, e.g. as a finishing agent for softening new clothes prior to sale to consumers.
- compositions of the invention may be made by combining a melt comprising the fabric softening active with an aqueous phase comprising the encapsulated perfume components.
- the stabilising active may be melted with the fabric softening active, or it may be post dosed into the composition after combination of the melt and water phase. Salt is then added to obtain the desired viscosity.
- Examples of the invention are represented by a number. Comparative examples are represented by a letter.
- Example 1 - Preparation of Compositions 1 , 2 and 3 in accordance with the invention, Comparative Examples A , B and C , and a control .
- Table 1 Compositions (wt%) of the liquid fabric softeners 1-3, A, B and Control (Cont) .
- Table 2 Difference and percent difference between the viscosities at the end of the first low shear and at the end of the second low shear regions of the liquid fabric softeners 1, 2 and A-D.
- nonionic surfactant in combination with salt is critical for the stabilization of the encapsulate containing compositions. It will further be seen that the correct level of nonionic surfactant is also essential for successful stabilization to be achieved.
- Example 2 - Preparation of Composition 3 in accordance with the invention, and Comparative Example F.
- BKC Benzalkonium Chloride
- Table 3 Compositions of the liquid fabric softeners 4 and E.
- compositions were measured as described above.
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Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
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PL09802479T PL2310480T3 (en) | 2008-07-29 | 2009-07-15 | Improvements relating to fabric conditioners |
EP09802479A EP2310480B1 (en) | 2008-07-29 | 2009-07-15 | Improvements relating to fabric conditioners |
CN2009801296772A CN102112591B (en) | 2008-07-29 | 2009-07-15 | Improvements relating to fabric conditioners |
ES09802479T ES2402487T3 (en) | 2008-07-29 | 2009-07-15 | Improvements related to fabric conditioners |
BRPI0916561A BRPI0916561B1 (en) | 2008-07-29 | 2009-07-15 | liquid softener composition and method of stabilizing a composition |
ZA2011/00170A ZA201100170B (en) | 2008-07-29 | 2011-01-06 | Improvements relating to fabric conditioners |
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EP08161377 | 2008-07-29 |
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EP (1) | EP2310480B1 (en) |
CN (1) | CN102112591B (en) |
AR (1) | AR072841A1 (en) |
BR (1) | BRPI0916561B1 (en) |
ES (1) | ES2402487T3 (en) |
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ZA (1) | ZA201100170B (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011139578A1 (en) | 2010-05-06 | 2011-11-10 | The Procter & Gamble Company | Process of making liquid fabric softening compositions |
WO2013040115A1 (en) * | 2011-09-13 | 2013-03-21 | The Procter & Gamble Company | Fluid fabric enhancer compositions |
WO2013087364A1 (en) | 2011-12-16 | 2013-06-20 | Unilever Plc | Improvements relating to fabric treatment compositions |
WO2013189661A1 (en) * | 2012-06-21 | 2013-12-27 | Unilever Plc | Improvements relating to fabric conditioners |
WO2014166686A1 (en) * | 2013-04-12 | 2014-10-16 | Unilever Plc | Improvements relating to fabric conditioners |
GB2513361A (en) * | 2013-04-24 | 2014-10-29 | Intelligent Fabric Technologies Plc | Fabric softener |
WO2022219109A1 (en) * | 2021-04-15 | 2022-10-20 | Unilever Ip Holdings B.V. | Fabric conditioner compositions |
WO2022219111A1 (en) * | 2021-04-15 | 2022-10-20 | Unilever Ip Holdings B.V. | Fabric spray composition |
EP4247925B1 (en) * | 2020-11-18 | 2024-09-04 | Unilever IP Holdings B.V. | Fabric conditioner |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20220248670A1 (en) * | 2019-07-30 | 2022-08-11 | Conopco, Inc., D/B/A Unilever | Fabric spray compositions |
EP4150038B1 (en) * | 2020-05-14 | 2024-06-19 | Unilever IP Holdings B.V. | Laundry composition |
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EP1589092A1 (en) * | 2004-04-13 | 2005-10-26 | INTERNATIONAL FLAVORS & FRAGRANCES INC. | Stable Fragrance microcapsule suspension and process for using same |
US20060252669A1 (en) * | 2005-05-06 | 2006-11-09 | Marija Heibel | Fabric care composition comprising polymer encapsulated fabric or skin beneficiating ingredient |
WO2006131846A1 (en) * | 2005-06-08 | 2006-12-14 | Firmenich Sa | Near anhydrous consumer products comprising fragranced aminoplast capsules |
WO2008016637A1 (en) * | 2006-08-01 | 2008-02-07 | Appleton Papers Inc. | Benefit agent containing delivery particle |
-
2009
- 2009-07-15 WO PCT/EP2009/059049 patent/WO2010012590A1/en active Application Filing
- 2009-07-15 CN CN2009801296772A patent/CN102112591B/en active Active
- 2009-07-15 PL PL09802479T patent/PL2310480T3/en unknown
- 2009-07-15 BR BRPI0916561A patent/BRPI0916561B1/en active IP Right Grant
- 2009-07-15 EP EP09802479A patent/EP2310480B1/en active Active
- 2009-07-15 ES ES09802479T patent/ES2402487T3/en active Active
- 2009-07-27 AR ARP090102846A patent/AR072841A1/en active IP Right Grant
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2011
- 2011-01-06 ZA ZA2011/00170A patent/ZA201100170B/en unknown
Patent Citations (4)
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EP1589092A1 (en) * | 2004-04-13 | 2005-10-26 | INTERNATIONAL FLAVORS & FRAGRANCES INC. | Stable Fragrance microcapsule suspension and process for using same |
US20060252669A1 (en) * | 2005-05-06 | 2006-11-09 | Marija Heibel | Fabric care composition comprising polymer encapsulated fabric or skin beneficiating ingredient |
WO2006131846A1 (en) * | 2005-06-08 | 2006-12-14 | Firmenich Sa | Near anhydrous consumer products comprising fragranced aminoplast capsules |
WO2008016637A1 (en) * | 2006-08-01 | 2008-02-07 | Appleton Papers Inc. | Benefit agent containing delivery particle |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011139578A1 (en) | 2010-05-06 | 2011-11-10 | The Procter & Gamble Company | Process of making liquid fabric softening compositions |
WO2013040115A1 (en) * | 2011-09-13 | 2013-03-21 | The Procter & Gamble Company | Fluid fabric enhancer compositions |
US8835373B2 (en) | 2011-09-13 | 2014-09-16 | The Procter & Gamble Company | Fluid fabric enhancer compositions |
WO2013087364A1 (en) | 2011-12-16 | 2013-06-20 | Unilever Plc | Improvements relating to fabric treatment compositions |
CN103987829A (en) * | 2011-12-16 | 2014-08-13 | 荷兰联合利华有限公司 | Improvements relating to fabric treatment compositions |
CN103987829B (en) * | 2011-12-16 | 2017-04-26 | 荷兰联合利华有限公司 | Improvements relating to fabric treatment compositions |
WO2013189661A1 (en) * | 2012-06-21 | 2013-12-27 | Unilever Plc | Improvements relating to fabric conditioners |
WO2014166686A1 (en) * | 2013-04-12 | 2014-10-16 | Unilever Plc | Improvements relating to fabric conditioners |
GB2513361A (en) * | 2013-04-24 | 2014-10-29 | Intelligent Fabric Technologies Plc | Fabric softener |
EP4247925B1 (en) * | 2020-11-18 | 2024-09-04 | Unilever IP Holdings B.V. | Fabric conditioner |
WO2022219109A1 (en) * | 2021-04-15 | 2022-10-20 | Unilever Ip Holdings B.V. | Fabric conditioner compositions |
WO2022219111A1 (en) * | 2021-04-15 | 2022-10-20 | Unilever Ip Holdings B.V. | Fabric spray composition |
Also Published As
Publication number | Publication date |
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CN102112591A (en) | 2011-06-29 |
BRPI0916561B1 (en) | 2018-11-06 |
BRPI0916561A2 (en) | 2015-11-10 |
ES2402487T3 (en) | 2013-05-06 |
EP2310480A1 (en) | 2011-04-20 |
ZA201100170B (en) | 2012-03-28 |
EP2310480B1 (en) | 2013-01-02 |
PL2310480T3 (en) | 2013-06-28 |
AR072841A1 (en) | 2010-09-22 |
CN102112591B (en) | 2013-02-13 |
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