EP2486118B1 - Wäscheweichspüler - Google Patents

Wäscheweichspüler Download PDF

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Publication number
EP2486118B1
EP2486118B1 EP10752341.7A EP10752341A EP2486118B1 EP 2486118 B1 EP2486118 B1 EP 2486118B1 EP 10752341 A EP10752341 A EP 10752341A EP 2486118 B1 EP2486118 B1 EP 2486118B1
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EP
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Prior art keywords
ester
fabric
composition
metal oxide
dyes
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EP10752341.7A
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English (en)
French (fr)
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EP2486118A1 (de
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Christopher Boardman
Lesley Ebbrell
David Andrew Ross Jones
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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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
    • C11D3/12—Water-insoluble compounds
    • C11D3/1213—Oxides or hydroxides, e.g. Al2O3, TiO2, CaO or Ca(OH)2
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • C11D3/0015—Softening compositions liquid

Definitions

  • the present invention relates to the use of fabric treatment compositions containing white metal oxide materials to achieve cool feel to the wearer of fabrics treated therewith.
  • Fabrics and fabric articles such as clothes can absorb significant amounts of heat, particularly on hot days and in hot climates, contributing to feelings of heat and discomfort for the wearer.
  • Laundry treatment compositions containing metal oxides are known, providing a variety of benefits.
  • WO2008/058831 discloses fabric softening compositions comprising a fabric softening compound and from 5 to 50 wt % of a material capable of changing its hydrophobic/hydrophilic properties, such as zinc oxide and titanium oxide, in response to an activation step, such as exposure to UV light. The transport of water through the fabric is thereby increased, thus leading to drier feel.
  • DE10159000 A1 (Henkel KGaA) discloses softener compositions comprising polyalkylene glycol diesters for improved fabric wettability, an optional further softening material and an optional UV absorber, which may be zinc oxide or titanium oxide, to improve the light-resistance of fibres and/or of other ingredients in the formulation.
  • DE102004 020015 A1 (Henkel KGaA) discloses textile care compositions comprising cellulose ether quats to reduce fluffing, pilling and creasing, an optional further softening material and an optional UV absorber, which may be zinc oxide or titanium oxide, to improve the light stability of the fibres and/or other ingredients in the composition.
  • XP002474825 & JP11061652 disclose an industrial coating for a fibre comprising a polyorganosiloxane and photocatalytically active inorganic particles to confer weather resistance, stain resistance, mildew proofing and antibacterial property to fibres.
  • US-A-5000937 discloses transparent cosmetic compositions for protecting the human epidermis against infrared radiation comprising an infrared reflecting agent such as a diatom, hollow glass microspheres, a bismuth oxychloride and zirconium powder.
  • Zinc oxide is stated to be a known pigment that reflects natural radiation.
  • Creams and gels suitable for direct application to human skin are exemplified.
  • EP-A-260751 discloses an infrared reflecting composition for topical application to the skin comprising an infrared reflecting effective amount of an infrared reflecting material, such as doped tin oxide, doped indium oxide, cadmium orthostannate, noble metals, copper, aluminium and mixtures thereof.
  • an infrared reflecting material such as doped tin oxide, doped indium oxide, cadmium orthostannate, noble metals, copper, aluminium and mixtures thereof.
  • EP-A-1075833 discloses barrier creams that are useful in protecting a user from bums during exposure to heat.
  • the barrier cream comprises a base cream and at least one of a melt additive and reflective additive.
  • the reflective additive is able to reflect radiation at infra red and visible wavelengths and may be zinc and titanium oxide.
  • WO-A-9534624 discloses a composition comprising an effective amount of a fluid, an effective amount of a polymer fro forming a film on a substrate and an effective amount of metal oxide particles for blocking transmission of radiation through the polymeric film selected from UV and IR radiation.
  • a cleaning agent such as glass cleaner, car polish, vinyl protectants, furniture polish and shoe polish and also in cosmetics such as lipstick, sun tan lotion, bug repellent and shampoo.
  • DE-A-10105143 claims a laundry conditioning composition comprising from 0.01-20 wt %, preferably from 0.1 - 10 wt % of zinc oxide and/or titanium oxide in combination with one or more organic UV absorber (i.e. a total amount of both actives).
  • WO-A-2006097207 discloses liquid softening compositions comprising (a) nanoparticles including silica, silicone resins, TiO 2 , ZnO, Al 2 O 3 and (b) a fabric softening compound, in which the wt ratio of (a):(b) is from 3:1 to 1:3. Silicas are highly preferred and exemplified.
  • a white metal oxide as an ingredient in a rinse added aqueous fabric conditioner composition to enable the fabric conditioner composition to render fabrics treated with the composition capable of delivering a cool feel benefit to the wearer of the treated fabric
  • the fabric conditioner composition comprises a softening active and the metal oxide is present in an amount of from 2.5 to 12 wt %, based on the weight of the total composition.
  • the metal oxide material is the metal oxide material
  • Any white metal oxide may be used, for example aluminium oxide, zinc oxide and titanium oxide. Mixtures of metal oxides and/or mixed oxides may be used, for example, a mixture of zinc oxide and titanium oxide.
  • the white metal oxide is a transition metal oxide such as oxides of Scandium (III), Titanium (IV), Zinc (II), Yttrium (III), Zirconium (IV), Niobium (V), Lanthanum (III), Hafnium (IV), Tantalum (V) - oxidation states are shown in parentheses.
  • Hafnium (IV) Oxide and Zinc (II)Oxide are preferred.
  • the metal oxide is preferably used in the form of a fine dispersion in a solvent, which is preferably water.
  • the metal oxide is preferably added to the fabric conditioner base in the form of a nano dispersion, wherein the particles of metal oxide have sub-micron particle size.
  • the average particle size of the metal oxide is preferably less than 1 micron and is preferably in the range of from 1 to 400 nm, more preferably from 20 to 300 nm, most preferably from 60 to 250 nm.
  • a suitable method for measuring the average particle size is BET (nitrogen gas adsorption), which is used to determine the specific surface area (square meters per gram), and converts this to an Average Particle Diameter (APD). See for example, Particle Size Characterization of Ultrafine Tungsten Powder, LIAO JIQIAO; HUANG BAIYUN; International Journal of Refractory Metals & Hard Materials, ISSN 0958-0611, 2001, vol. 19, n°2, pp. 89-98 .
  • the metal oxide is present in an amount of from 2.5 to 12 wt %, and most preferably from 5 to 12wt %, based on the total weight of the composition. A particularly preferred amount is 10 wt %.
  • the conditioning agents may be cationic or non-ionic.
  • the fabric conditioning compositions for use in 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 9 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 preferred quaternary ammonium fabric conditioner 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. 55 %, or 45 % of the fabric softening compound and at least 10 % of the monoester linked component, for example 11 % monoester.
  • a preferred hardened type of active has a typical mono:di:tri ester distribution of from 18 to 22 mono: from 58 to 62 di: from 18 to 22 tri; for example 20:60:20.
  • a soft TEA quat may have a typical mono:di:tri ester distribution of from 25 to 45 %, preferably from 30 to 40 % mono: from 45 to 60 %, preferably from 50 to 55 % di: and from 5 to 25 %, preferably from 10 to 15 % tri; for example 40:60:10.
  • a first group of quaternary ammonium compounds (QACs) suitable for use in the present invention is represented by formula (I): wherein each R is independently selected from a C 5-35 alkyl or alkenyl group; R 1 represents a C 1-4 alkyl, C 2-4 alkenyl or a C 1-4 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.
  • 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-1
  • Ex Kao both di-[hardened tallow ester] of triethanolammonium methylsulphate
  • AT-1 di-[tallow ester] of triethanolammonium methylsulphate
  • L5/90 di-[palm ester] of triethanolammonium methylsulphate
  • Ex Kao and RewoquatTM WE15 (a di-ester of triethanolammonium methylsulphate having fatty acyl residues deriving from C 10 -C 20 and C 16 -C 18 unsaturated fatty acids), ex Witco Corporation.
  • soft quaternary ammonium actives such as Stepantex VK90, Stepantex VT90, SP88 (ex-Stepan), Ceca Noramine, Prapagen TQ (ex-Clariant), Dehyquart AU-57 (ex-Cognis), Rewoquat WE18 (ex-Degussa) and Tetranyl L190 P, Tetranyl L190 SP and Tetranyl L190 S (all ex-Kao) are suitable.
  • a second group of QACs suitable for use in the invention is represented by formula (II): wherein each R 1 group is independently selected from C 1-4 alkyl, hydroxyalkyl or C 2-4 alkenyl groups; and wherein each R 2 group is independently selected from C 8-28 alkyl or alkenyl groups; 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): (R 1 ) 2 -N + -[(CH 2 ) n -T-R 2 ] 2 X - (III) wherein each R 1 group is independently selected from C 1-4 alkyl, or C 2-4 alkenyl groups; and wherein each R 2 group is independently selected from C 8-28 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.
  • 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., 34, 1136 (1962) Johnson and Shoolery .
  • a further type of softening compound is a non-ester quaternary ammonium material represented by formula (IV):- wherein each R 1 group is independently selected from C 1-4 alkyl, hydroxyalkyl or C 2-4 alkenyl groups; R 2 group is independently selected from C 8-28 alkyl or alkenyl groups, and X - is as defined above.
  • compositions for use in the invention may contain a non-cationic softening material, which is preferably 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 C 8 -C 22 alkyl or alkenyl chain.
  • the CPE or RSE does not have any substantial crystalline character at 20°C. Instead it is preferably in a liquid or soft solid state as herein defined at 20°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 C 8 to C 22 alkyl or alkenyl chain.
  • the C 8 to C 22 alkyl or alkenyl groups may be branched or linear carbon chains.
  • the CPE or RSE contains at least 35 % tri or higher esters, e.g. 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.
  • CPEs or RSEs are those with monosaturated fatty acid chains, i.e. where any polyunsaturation has been removed by partial hydrogenation.
  • 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.
  • liquid CPEs or RSEs are any of the above but where the polyunsaturation has been removed through partial hydrogenation.
  • 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 C 1 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 C 12 -C 22 . It is possible to include one or more chains of C 1 -C 8 , 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 20°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.
  • Co-softeners may be used. When employed, they are typically present at from 0.1 to 20% and particularly at from 0.5 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 for use in the present invention may comprise a fatty complexing agent.
  • Suitable fatty complexing agents include fatty alcohols and fatty acids. Of these, fatty alcohols are most preferred.
  • 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 acids include hardened tallow fatty acid (available under the tradename PristereneTM, ex Uniqema).
  • Preferred fatty alcohols include hardened tallow alcohol (available under the tradenames StenolTM and HydrenolTM, ex Cognis and LaurexTM CS, ex Albright and Wilson).
  • the fatty complexing agent is preferably present in an amount greater than 0.3 to 5% by weight based on the total weight of the composition. More preferably, the fatty component is present in an amount of from 0.4 to 4%.
  • the weight ratio of the mono-ester component of the quaternary ammonium fabric softening material to the fatty complexing agent is preferably from 5:1 to 1:5, more preferably 4:1 to 1:4, most preferably 3:1 to 1:3, e.g. 2:1 to 1:2.
  • compositions for use in the present invention may further comprise a nonionic surfactant. Typically these can be included for the purpose of stabilising the compositions. These are particularly suitable for compositions comprising hardened quaternary ammonium compounds.
  • Suitable nonionic 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-Y-(C 2 H 4 O) z -CH 2 -CH 2 -OH where 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: -O-, -C(O)O- , -C(O)N(R)- or -C(O)N(R)R- in which 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.
  • GenapolTM C200 (Clariant) based on coco chain and 20 EO groups is an example of a suitable nonionic surfactant.
  • the nonionic surfactant is present in an amount from 0.01 to 10%, more preferably 0.1 to 5 by weight, based on the total weight of the composition.
  • 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 presence 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: or wherein:
  • 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:
  • 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.
  • composition for use in the invention 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 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.
  • compositions for use in the present invention may comprise one or more perfumes if desired.
  • 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 0.15 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 Handbook of Flavor Ingredients, 1975, CRC Press ; Synthetic Food Adjuncts, 1947 by M. B. Jacobs, edited by Van Nostr and; or Perfume and Flavor Chemicals by S. Arctander 1969, Montclair, N.J. (USA ).
  • 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.
  • 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.
  • Clog P i.e. those which will be partitioned into water
  • 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-Dimethyl-2-heptanol, Diisobutylcarbinol, Ethyl salicylate, Phenethyl isobutyrate, Ethyl hexyl ketone, Propyl amyl ketone, Dibutyl ketone, Heptyl methyl ketone, 4,5-Dihydrotoluene, Caprylic aldehyde, Citral, Geranial, Isopropyl benzoate, Cyclohexanepropionic acid, Campholene aldehyde, Caprylic acid, Caprylic alcohol, Cuminaldehyde, 1-Ethyl-4-nitrobenzene, Heptyl formate, 4-I
  • compositions for use in 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.
  • compositions for use in 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, antioxidants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents, ironing aids pearlisers and/or opacifiers, natural oils/extracts, processing aids, e.g. electrolytes, hygiene agents, e.g. anti-bacterials and antifungals, thickeners and skin benefit agents.
  • compositions for use in the present invention are aqueous rinse-added softening compositions.
  • compositions typically have a pH ranging from about 2.5 to 6, preferably from about 2.5 to 4.5, most preferably about 2.5 to 2.8.
  • compositions for use in the invention may also contain pH modifiers such as hydrochloric acid or lactic acid.
  • a composition for use in the invention 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 watersoluble species, such as mineral salts or short chain (C 1-4 ) alcohols.
  • the composition 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 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 for use in the invention may typically be made by combining a melt comprising the fabric softening active with an aqueous phase. Further components may be combined with the water phase, or may be post dosed into the composition after combination of the melt and water phase.
  • Examples of the invention are represented by a number. Comparative examples are represented by a letter.
  • Example 1 - Preparation of Composition 1 and Comparative Example A
  • a fabric conditioner composition was prepared, for use in the present invention, which contained zinc oxide in an amount of 10 wt %.
  • a comparative fabric conditioner product was prepared using the same method, which did not comprise a metal oxide.
  • Table 1 Compositions of the liquid fabric softeners 1 and A Ingredient (wt %) 1
  • a Softening active 1 11.62 11.62 Tallow alcohol 2 0.38 0.38 Sequestrant 3 0.005 0.005 Acid 4 0.01 0.01 Perfume 2 2 ZnO 5 10 - Minors (anti-foam, salt & preservative) 0.02 0.02 Water to 100 to 100 1
  • Stepantex SP90 Ex Stepan
  • Stenol 1618L Ex Cognis
  • Dequest 2010 22 % HCl 5 NanoShield ZN-2000, ex Alfa Aesar.
  • the average particle size is 60nm (as determined by BET N 2 adsorption).
  • test composition (1 or A) was applied to 100 % knitted cotton using the following method that simulated a domestic machine wash:-
  • Heat transfer was determined using an IR heat lamp (Interhatch 470IR-456, 250 watt) and a data logging temperature recorder (Fluke 189 true RMS multimeter) attached to a surface mounted K type thermocouple.
  • thermocouple was taped to the under side ("non-exposed surface") of the fabric to enable temperature measurement on the upper side ("exposed surface”).
  • the lamp was used to radiate the upper side fabric for 5 minutes from a distance of 52 cm.
  • the temperature of the non-exposed surface was measured every 10 seconds until at least 200 measurements had been made.
  • the measurements were carried out in an air conditioned laboratory controlled to 20 °C and 65 % RH.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Claims (9)

  1. Verwendung eines weißen Metalloxids als Bestandteil in einer Spülung, der eine wässrige Weichspülerzusammensetzung zugesetzt wird, damit mit der Zusammensetzung behandelte Textilerzeugnisse durch die Weichspülerzusammensetzung für den Träger des behandelten Textilerzeugnisses einen Vorteil in Form eines Kältegefühls bieten können, wobei die Weichspülerzusammensetzung einen weichmachenden Wirkstoff aufweist und das weiße Metalloxid in einer Menge von 2,5 bis 12 Gew.-% vorliegt, und zwar auf das Gewicht der gesamten Zusammensetzung bezogen.
  2. Verwendung nach Anspruch 1,
    wobei das Metalloxid eine mittlere Teilchengröße im Bereich von 1 bis 400 nm aufweist.
  3. Verwendung nach Anspruch 1,
    wobei das Metalloxid eine mittlere Teilchengröße im Bereich von 60 bis 250 nm aufweist.
  4. Verwendung nach einem der vorstehenden Ansprüche,
    wobei das Metalloxid in einer Menge von 5 bis 10 Gew.-% vorliegt, und zwar auf das Gewicht der gesamten Zusammensetzung bezogen.
  5. Verwendung nach einem der vorstehenden Ansprüche,
    wobei der weichmachende Wirkstoff eine quaternäre Ammoniumverbindung ist.
  6. Verwendung nach Anspruch 5,
    wobei die quaternäre Ammoniumverbindung eine Ester-gebundene Verbindung ist, die eine Verteilung von Monoester-, Diester- und Triesterverbindungen aufweist.
  7. Verwendung nach Anspruch 6,
    wobei die Ester-gebundene Verbindung eine Ester-gebundene, auf Triethanolamin basierende quaternäre Ammoniumverbindung ist.
  8. Verwendung nach einem der vorstehenden Ansprüche,
    wobei der weichmachende Wirkstoff für Textilerzeugnisse in einer Menge von 2 bis 50 Gew.-% der gesamten Zusammensetzung vorliegt.
  9. Verwendung nach einem der vorstehenden Ansprüche,
    wobei das Metalloxid aus Zinkoxid oder Titanoxid ausgewählt ist.
EP10752341.7A 2009-10-07 2010-09-07 Wäscheweichspüler Not-in-force EP2486118B1 (de)

Priority Applications (1)

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Applications Claiming Priority (3)

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EP09172405 2009-10-07
EP10752341.7A EP2486118B1 (de) 2009-10-07 2010-09-07 Wäscheweichspüler
PCT/EP2010/063128 WO2011042275A1 (en) 2009-10-07 2010-09-07 Fabric conditioners

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EP2486118B1 true EP2486118B1 (de) 2014-12-31

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WO2013107583A1 (en) * 2012-01-19 2013-07-25 Unilever Plc Fabric treatment method and composition
CN111684072A (zh) * 2018-02-13 2020-09-18 伊士曼化工公司 制备可用作酯季铵化合物前体的中间体的酶促方法
EP3957710A1 (de) * 2020-08-21 2022-02-23 Anna Twaróg SIMPLYQ Bakteriostatisches konzentrat und weichspüler und verwendung des konzentrats und weichspülers

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Publication number Priority date Publication date Assignee Title
GB1567947A (en) 1976-07-02 1980-05-21 Unilever Ltd Esters of quaternised amino-alcohols for treating fabrics
DE3027611A1 (de) 1980-07-21 1982-02-18 Bayer Ag, 5090 Leverkusen Di- und oligo-1,2,4-triazolidin-3,5-dione und verfahren zu ihrer herstellung
US4828825A (en) * 1986-09-15 1989-05-09 University Of Miami Infrared reflecting composition for topical application to the skin
EP0311154B1 (de) 1987-04-10 1994-01-19 The Procter & Gamble Company Feste unverdauliche fettähnliche Verbindungen
LU87030A1 (fr) * 1987-10-28 1989-05-08 Oreal Utilisation en cosmetique de nouvelles substances a titre de reflecteurs du rayonnement infrarouge,compositions cosmetiques les contenant et leur utilisation pour la protection de l'epiderme humain contre le rayonnement infrarouge
WO1995034624A1 (en) * 1994-06-15 1995-12-21 The Center For Innovative Technology Porous metal oxide particles and compositions containing same
US5578563A (en) 1994-08-12 1996-11-26 The Procter & Gamble Company Composition for reducing malodor impression on inanimate surfaces
JP3834948B2 (ja) 1997-08-07 2006-10-18 Ｊｓｒ株式会社 繊維
GB9917103D0 (en) * 1999-07-22 1999-09-22 Secr Defence Barrier cream
GB9930435D0 (en) 1999-12-22 2000-02-16 Unilever Plc Fabric softening compositions
DE10105143A1 (de) * 2001-02-06 2002-08-08 Basf Ag Verfahren zur UV-Schutzausrüstung von textilem Material
DE10159000B4 (de) 2001-11-30 2006-05-04 Henkel Kgaa Konditioniermittel mit verbesserter Wiederbenetzbarkeit
DE102004020015A1 (de) 2004-04-21 2005-11-10 Henkel Kgaa Textilpflegemittel
PL1792001T3 (pl) 2004-08-30 2013-06-28 Basf Se Proces podbarwiania
US7686892B2 (en) 2004-11-19 2010-03-30 The Procter & Gamble Company Whiteness perception compositions
GB0505619D0 (en) * 2005-03-18 2005-04-27 Unilever Plc Fabric care compositions
GB0623004D0 (en) 2006-11-17 2006-12-27 Unilever Plc Fabric treatment method and composition to impart differential hydrophobocity

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ZA201202104B (en) 2013-05-29
EP2486118A1 (de) 2012-08-15
ES2531835T3 (es) 2015-03-20
AR078523A1 (es) 2011-11-16
CN102712876B (zh) 2014-03-12
WO2011042275A1 (en) 2011-04-14
BR112012007756A2 (pt) 2017-07-25

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