EP2922936A1 - Laundry compositions - Google Patents

Laundry compositions

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Publication number
EP2922936A1
EP2922936A1 EP13771155.2A EP13771155A EP2922936A1 EP 2922936 A1 EP2922936 A1 EP 2922936A1 EP 13771155 A EP13771155 A EP 13771155A EP 2922936 A1 EP2922936 A1 EP 2922936A1
Authority
EP
European Patent Office
Prior art keywords
silicone
polymer
cationic
composition according
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP13771155.2A
Other languages
German (de)
French (fr)
Other versions
EP2922936B1 (en
Inventor
Andrew Anthony Howard Barnes
Neil Stephen Burnham
Martin Charles Crossman
Belinda Fay DAWSON
Paula Rose Bernadette GILFOYLE
Jane Catherine JONES
Atsuko KAWABATA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever Global IP Ltd
Unilever IP Holdings BV
Original Assignee
Unilever PLC
Unilever NV
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Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to EP13771155.2A priority Critical patent/EP2922936B1/en
Publication of EP2922936A1 publication Critical patent/EP2922936A1/en
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/008Polymeric surface-active agents
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/001Softening compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/222Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/227Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones

Definitions

  • This invention relates to a laundry composition. More particularly, the invention is directed to a softening in the wash laundry composition.
  • Fabric softening cationic polymers, and fabric softening silicones have been used to provide softness to fabrics from a laundry detergent composition.
  • WO 2005/087907 discloses liquid detergent compositions comprising surfactants, polydimethylsiloxane (a softening silicone) and polyquaternium 7 (a polymeric quaternary salt consisting of acrylamide and dimethyl diallyl ammonium chloride monomers).
  • the invention is directed to a laundry detergent composition
  • a laundry detergent composition comprising:-
  • weight ratio of the silicone to cationic polysaccharide polymer is from 4.5:1 to 1 .5:1 .
  • the detergent composition is a liquid detergent composition.
  • the liquid detergent composition has a pH of from 6 to 10, more preferably from pH 6.5 to 9, for example from pH 6.5 to 8.5.
  • a preferred level of the cationic polymer is from 0.1 to 2 wt.%, more preferably from 0.1 to 1 wt.%.
  • Preferred cationic polysaccharide polymers are cationic guar and cationic cellulose polymers. Particularly preferred is hydroxy ether cellulose that is modified by incorporation of cationic groups (i.e. quaternised hydroxy ethyl cellulose).
  • the silicone is in the form of an emulsion.
  • the silicone is a polydimethylsiloxane.
  • the silicone is an aminosilicone.
  • the silicone is an anionic silicone.
  • the weight ratio of the silicone to the cationic polymer is from 4:1 to 2:1 .
  • the composition further comprises an ingredient selected from, shading dye, enzyme, an antiredeposition polymer, a dye transfer inhibiting polymer, builder, sequestrant, sunscreen and/or soil release polymer.
  • the invention provides the use of a composition according to the first aspect of the invention to soften fabrics. DETAILED DESCRIPTION OF THE INVENTION
  • the term “comprising” means including, made up of, composed of, consisting and/or consisting essentially of.
  • the invention is directed to laundry compositions containing surfactant, a cationic polymer, and a fabric softening silicone, wherein the weight ratio of silicone to cationic polymer is from 4.5:1 to 1 .5:1 .
  • the composition displays improved fabric softening.
  • the invention can take any of a number of forms that are laundry compositions. Examples include powders, granules, bars, gels and liquids. Preferably the composition is in the form of a liquid laundry product. Preferably they are main wash products. It can take the form of a laundry composition for the main wash, which may be dilutable or non-dilutable.
  • the laundry composition may for example be an isotropic liquid, or a surfactant-structured liquid.
  • Particularly preferred forms of this invention include combination detergent/softener products to provide "softening in the wash".
  • the detergent composition has a pH of from 6 to 10, more preferably from pH 6.5 to 9, for example from pH 6.5 to 8.5.
  • the detergent composition comprises surfactant.
  • the surfactant comprises nonionic surfactant, and anionic surfactant.
  • the nonionic surfactant if present, preferably comprises alcohol ethoxylate.
  • the alcohol ethoxylates are formed from the reaction of primary or secondary alcohols with ethylene oxide.
  • ethylene oxide is reacted with ethylene oxide in the required molar amount to produce the alcohol ethoxylate.
  • Preferred alcohol ethoxylates have from 2 to 40, preferably from 3 to 30, more preferably from 5 to 20 ethylene oxide units attached to the aliphatic chain.
  • the surfactants may be chosen from the surfactants described in "Surface Active Agents” Vol. 1 , by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, in the current edition of "McCutcheon's Emulsifiers and Detergents” published by Manufacturing Confectioners Company or in "Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981 .
  • the surfactants used are saturated.
  • Suitable nonionic detergent compounds which may be used include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide.
  • Specific nonionic detergent compounds are C 6 to C 2 2 alkyl phenol- ethylene oxide condensates, generally 5 to 25 EO, i.e. 5 to 25 units of ethylene oxide per molecule, and the condensation products of aliphatic Cs to C-is primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 40 EO.
  • Suitable anionic detergent compounds which may be used can be water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals con- taining from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals.
  • suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher Cs to Cie alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl Cg to C20 benzene sulphonates, particularly sodium linear secondary alkyl C-m to C15 benzene sulphonates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum.
  • the anionic surfactant may also include soaps of C6-C22 fatty acids.
  • the preferred anionic detergent compounds are sodium Cn to C-I5 alkyl benzene sulphonates and sodium C12 to Ci 8 alkyl sulphates. Salts of sulphonates included as hydrotrobes can additionally be considered as anionic surfactants as defined herein. Also applicable are surfactants such as those described in EP-A-328 177 (Unilever), which show resistance to salting-out, the alkyl polyglycoside surfactants described in EP-A-070 074, and alkyl
  • the total amount of surfactant present in the composition is from 1 to 80 wt.%.
  • the surfactant level is preferably at least 6 wt.%, more preferably at least 10 wt.%, More preferably the total amount of surfactant is from 15 to 65 wt.%, preferably from 10 to 50 wt.%.
  • the nonionic detergent is preferably present in amounts of from 2 to 40 wt.%, preferably from 5 to 35 wt.%, more preferably from 6 to 20 wt.%.
  • the anionic surfactant is preferably present in amounts of from 4 to 40 wt.%, preferably from 5 to 35 wt.%, more preferably from 6 to 20 wt.%.
  • surfactants such as amphoteric, zwitterionic and cationic surfactants may also be present in addition to the aforementioned nonionic and anionic
  • the composition comprises fabric softening silicone at a level of from 0.1 to 10 wt.%, preferably from 0.2 to 5 wt.%, more preferably from 0.5 to 3 wt.%.
  • the fabric softening silicone may be but are not limited to 1 ) non-functionalized silicones such as polydimethylsiloxane (PDMS) or alkyl (or alkoxy) functional silicones 2) functionalized silicones or copolymers with one or more different types of functional groups such as amino, phenyl, polyether, acrylate, siliconhydride, carboxylic acid, quaternized nitrogen, etc.
  • the particle size is in the range from about 1 nm to 100 microns and preferably from about 10 nm to about 10 microns including microemulsions ( ⁇ 150 nm), standard emulsions (about 200 nm to about 500 nm) and macroemulsions (about 1 micron to about 20 microns).
  • Preferred silicones are selected from polydialkylsiloxanes, especially
  • polydimethylsiloxane polydimethylsiloxane; amino functionalised silicones; and anionic silicones, especially carboxyl functionalised silicone
  • the fabric softening silicone is a polydimethylsiloxane.
  • the composition comprises a cationic polysaccharide polymer at a level of from 0.05 to 2.5 wt.%, preferably from 0.1 to 2 wt.%, more preferably from 0.2 to 1 wt.%.
  • This term refers to polymers having an overall positive charge.
  • the cationic polysaccharide polymer is a cationic guar or cationic cellulose polymer. Most preferably the cationic polymer is a cationic cellulose polymer, for example, quaternised hydroxy ethyl cellulose. Cationic Polysaccharide Polymer
  • cationic polysaccharide polymer refers to polymers having a
  • Polysaccharide backbone and an overall positive charge Polysaccharides are polymers made up from monosaccharide monomers joined together by glycosidic bonds.
  • the cationic polysaccharide-based polymers present in the compositions of the invention have a modified polysaccharide backbone, modified in that additional chemical groups have been reacted with some of the free hydroxyl groups of the polysaccharide backbone to give an overall positive charge to the modified cellulosic monomer unit.
  • a preferred class of cationic polysaccharide polymers suitable for this invention are those that have a polysaccharide backbone modified to incorporate a quaternary ammonium salt.
  • the quaternary ammonium salt is linked to the polysaccharide backbone by a hydroxyethyl or hydroxypropyl group.
  • the charged nitrogen of the quaternary ammonium salt has one or more alkyl group substituents.
  • Preferred cationic polysaccharide-based polymers have a guar based, or cellulosic based backbone. Cellulose based cationic polymers are most preferred. Guar is a galactomannan having a ⁇ -1 ,4 linked mannose backbone with
  • Suitable cationic guar gum derivatives such as guar hydroxypropyltrimonium chloride, specific examples of which include the Jaguar series commercially available from Rhone-Poulenc Incorporated and the N-Hance series commercially available from Aqualon Division of Hercules, Inc.
  • An example of a preferred guar based cationic polymer is guar 2-hydroxy-3- (trimethylammonium) propyl ether salt.
  • Cellulose is a polysaccharide with glucose as its monomer, specifically it is a straight chain polymer of D-glucopyranose units linked via ⁇ -1 ,4 glycosidic bonds and is a linear, non-branched polymer.
  • Example cationic cellulose polymers are salts of hydroxyethyl cellulose reacted with trimethyl ammonium substituted epoxide, referred to in the field under the International Nomenclature for Cosmetic Ingredients as Polyquatemium 10 and is commercially available from the Amerchol Corporation, a subsidiary of The Dow Chemical Company, marketed as the Polymer LR, JR, and KG series of polymers.
  • Other suitable types of cationic celluloses include the polymeric quaternary ammonium salts of hydroxyethyl cellulose reacted with lauryl dimethyl ammonium- substituted epoxide referred to in the field under the International Nomenclature for Cosmetic Ingredients as Polyquatemium 24. These materials are available from Amerchol Corporation marketed as Polymer LM-200.
  • Typical examples of preferred cationic cellulosic polymers include
  • the cationic cellulosic polymer is a quaternised hydroxy ether cellulose cationic polymer. These are commonly known as polyquaternium-10. Suitable commercial cationic cellulosic polymer products for use according to the present invention are marketed by the Amerchol Corporation under the trade name UCARE.
  • the counterion of the cationic polymer is freely chosen from the halides: chloride, bromide, and iodide; or from hydroxide, phosphate, sulphate, hydrosulphate, ethyl sulphate, methyl sulphate, formate, and acetate.
  • the aforementioned cationic polymers can be synthesised in, and are commercially available in, a number of different molecular weights.
  • the molecular weight of the cationic polymer is from 10,000 to 2,000,000 Daltons, more preferably from 10,000 to 1 ,000,000 Daltons, even more preferably from 100,000 to 1 ,000,000 Daltons.
  • the detergent composition may optionally comprise one or more of the following optional ingredients, shading dye, enzyme, antiredeposition polymer, dye transfer inhibiting polymer, builder, sequestrant, sunscreen and/or soil release polymer.
  • the detergent compositions may also optionally contain relatively low levels of organic detergent builder or sequestrant material.
  • organic detergent builder or sequestrant material examples include the alkali metal, citrates, succinates, malonates, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetyl carboxylates.
  • specific examples include sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene
  • polycarboxylic acids ethylene diamine tetra-acetic acid, diethylenetriamine- pentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic acid, and citric acid.
  • DEQUESTTM organic phosphonate type sequestering agents sold by Thermophos and alkanehydroxy phosphonates.
  • suitable organic builders include the higher molecular weight polymers and copolymers known to have builder properties.
  • such materials include appropriate polyacrylic acid, polymaleic acid, and polyacrylic/polymaleic acid copolymers and their salts, such as those sold by BASF under the name SOKALANTM.
  • Another suitable builder is sodium carbonate.
  • the builder materials may comprise from about 0.5% to 20 wt%, preferably from 1 wt% to 10 wt%, of the composition. The preferred builder level is less than 10 wt% and preferably less than 5 wt% of the composition.
  • the laundry detergent formulation is a non-phosphate built laundry detergent formulation, i.e., contains less than 1 wt.% of phosphate.
  • Shading dyes deposit to fabric during the wash or rinse step of the washing process providing a visible hue to the fabric. Shading of white garments may be done with any colour depending on consumer preference. Blue and Violet are particularly preferred shades and consequently preferred dyes or mixtures of dyes are ones that give a blue or violet shade on white fabrics. The shading dyes used are preferably blue or violet.
  • the shading dye chromophore is preferably selected from the group comprising: mono-azo, bis-azo, triphenylmethane, triphenodioxazine, phthalocyanin, naptholactam, azine and anthraquinone. Most preferably mono-azo, bis-azo, azine and anthraquinone.
  • the dye bears at least one sulfonate group.
  • Preferred shading dyes are selected from direct dyes, acid dyes, hydrophobic dyes, cationic dyes and reactive dyes.
  • the shading dye is present is present in the composition in range from 0.0001 to 0.01 wt %.
  • the composition preferably comprises a fluorescent agent (optical brightener).
  • fluorescent agents are well known and many such fluorescent agents are available commercially. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts.
  • the total amount of the fluorescent agent or agents used in the composition is generally from 0.005 to 2 wt.%, more preferably 0.01 to 0.1 wt.%.
  • Preferred classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine stilbene di-sulphonic acid compounds, e.g.
  • Preferred fluorescers are: sodium 2-(4-styryl-3-sulfophenyl)-2H-napthol[1 ,2- d]trazole, disodium 4,4'-bis ⁇ [(4-anilino-6-(N methyl-N-2 hydroxyethyl) amino 1 ,3,5- triazin-2-yl)]amino ⁇ stilbene-2-2' disulfonate, disodium 4,4'-bis ⁇ [(4-anilino-6- morpholino-1 ,3,5-triazin-2-yl)]amino ⁇ stilbene-2-2' disulfonate, and disodium 4,4'- bis(2-sulfoslyryl)biphenyl.
  • the composition comprises a perfume.
  • the perfume is preferably in the range from 0.001 to 3 wt.%, most preferably 0.1 to 1 wt.%.
  • CTFA Cosmetic, Toiletry and
  • 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.
  • top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1955]).
  • Preferred top-notes are selected from citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol.
  • the laundry treatment composition does not contain a peroxygen bleach, e.g., sodium percarbonate, sodium perborate, and peracid.
  • a peroxygen bleach e.g., sodium percarbonate, sodium perborate, and peracid.
  • the composition may comprise one or more polymers.
  • Polymers can assist in the cleaning process by helping to retail soil in solution or suspension and/or preventing the transfer of dyes. Polymers can also assist in the soil removal process. Dye transfer, anti-redeposition and soil-release polymers are described in further detail below.
  • the composition may comprise one or more polymers. Examples are:
  • carboxymethylcellulose hydroxyethyl cellulose, hydroxpropyl cellulose, poly(ethylene glycol), polyvinyl alcohol), ethoxylated polyamines,
  • polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.
  • Modern detergent compositions typically employ polymers as so-called 'dye- transfer inhibitors'. These prevent migration of dyes, especially during long soak times.
  • dye-transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N- vinylimidazole, manganese pthalocyanine, peroxidases, and mixtures thereof, and are usually present at a level of from 0.01 to 10 wt.% based on total amount in the laundry composition.
  • Anti-redeposition polymers are designed to suspend or disperse soil.
  • antiredeposition polymers are ethoxylated and or propoxylated polyethylene imine or polycarboxylate materials, for example, Acrylic acid based homo or copolymers available under the trade mark ACUSOL from Dow Chemical, Alcosperse from Akzonobel or Sokolan from BASF. Soil Release Polymers
  • suitable soil release polymers include graft copolymers of polyvinyl ester), e.g., Ci -C 6 vinyl esters, preferably polyvinyl acetate) grafted onto polyalkylene oxide backbones.
  • Commercially available soil release agents of this kind include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (Germany).
  • Further suitable soil release polymers of a different type include the commercially available material ZELCON 5126 (from DuPont) and MILEASE T (from ICI). If present, the soil release polymer may be included at a level of from from 0.01 to 10 wt.% based on total amount in the laundry
  • soil release polymers are terephthalic acid / glycol copolymers sold under the tradenames Texcare, Repel-o-tex, Gerol, Marloquest, Cirrasol.
  • the liquid detergent composition may optionally include a hydrotrope, which can prevent liquid crystal formation.
  • a hydrotrope which can prevent liquid crystal formation.
  • the addition of the hydrotrope thus aids the clarity/transparency of the composition.
  • Suitable hydrotropes include but are not limited to propylene glycol, ethanol, glycerol, urea, salts of benzene sulphonate, toluene sulphonate, xylene sulphonate or cumene sulphonate.
  • Suitable salts include but are not limited to sodium, potassium, ammonium, monoethanolamine, triethanolamine. Salts of sulphonates can also be considered as anionic surfactants as defined herein.
  • the hydrotropes include but are not limited to propylene glycol, ethanol, glycerol, urea, salts of benzene sulphonate, toluene sulphonate, xylene sulphonate or cumene
  • hydrotrope is selected from the group consisting of propylene glycol, xylene sulfonate, ethanol, and urea to provide optimum performance.
  • the amount of the hydrotrope is generally in the range of from 0 to 30%, preferably from 0.5 to 30%, more preferably from 0.5 to 30%, most preferably from 1 to 15%.
  • Enzymes can also be present in the formulation.
  • Preferred enzymes include protease, lipase, pectate lyase, amylase, cutinase, cellulase, mannanase. If present the enzymes may be stabilized with a known enzyme stabilizer for example boric acid.
  • Silicone was a carboxylic functional silicone supplied by Wacker Chemie, added as an emulsion.
  • LR400 is a cationic hydroxyether cellulose polymer (known as polyquaternium 10) available from Dow Chemical
  • Silicone was a carboxylic functional silicone supplied by Wacker Chemie
  • 2 LR400 is a cationic hydroxyether cellulose polymer (known as polyquaternium 10) available from Dow Chemical
  • the softness was measured using a Stable Micro Systems Texture Analyser (TA) XT plus with the optional friction module attached.
  • the TA is a commercial instrument incorporating a drive mechanism and a 5 kg load cell.
  • the treated fabric was laid on the horizontal test platform of the instrument and a neoprene rubber cylindrical probe which is attached to the load cell was placed on the fabric surface.
  • the texture analyser is programmed to move the probe over a distance of 40 mm forwards and backwards over the fabric at a speed of 10 mm/s. As the probe moves the software records the frictional force experienced by the probe. The average friction coefficient over the whole test is used as a measure of softness.
  • Example 2 Further softness experiments were as performed to establish whether the effect of silicone to cationic polymer ratio is consistent across other functional silicones. In this case a PDMS and an amino silicone were used, and the results are shown in tables 4 & 5.
  • Silicone 1 was PDMS 60,000 cSt supplied by Dow Corning as an emulsion
  • Silicone 2 was amino silicone Arristan 64 supplied by CHT Beitlich as an emulsion 3 LR400 is a cationic hydroxyether cellulose polymer (known as polyquaternium 10) available from Dow Chemical Table 5
  • polyquaternium 7 from WO 2005/087907
  • Silicone deposition of both cationic polymers was tested using identical formulations varying only by the cationic polymer used. The formulations were dosed to provide silicone at 0.5g/wash and cationic polymer at 0.2g/wash. The variables tested were:-
  • Control - formulation including 0.5g/wash silicone
  • Polysaccharide - formulation including 0.5g/wash silicone + 0.2g/wash cationic polysaccharide polymer (LR400)
  • Polyquat 7 - formulation including 0.5g/wash silicone + 0.2g/wash cationic polymer (polyquaternium 7)
  • the washes were carried out on 2 different substrates, terry towelling; and repeated on white knitted cotton.
  • the articles were washed 6 times, dried and then friction measured after each wash. The friction measurement results in a average friction coefficient.
  • the friction test shows how soft the articles washed were, in that the amount of silicone deposited builds-up onto the article and decreases friction.
  • the coefficient of friction was measured using a commercially available Stable Micro Systems Texture Analyser.
  • the fabric article is placed onto a platform and a rubber probe placed on the fabric and moved at 10mm/s.
  • the probe is moved 40mm forwards, followed by 40mm backwards.
  • the instrument records the frictional force which is then converted into an average friction coefficient throughout the movement in both directions.
  • the data points in the following tables show that the polysaccharide provides statistically significant improvement in reduced friction (hence increased silicone deposition) at 95% confidence levels.
  • polysaccharide polymer provides superior deposition of silicone over that prior art polyquaternium-7 disclosed in WO 2005/087907.

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Abstract

The invention is directed to laundry compositions containing (a) surfactant, (b) a cationic polysaccharide polymer, and (c) a fabric softening silicone, wherein the weight ratio of silicone to cationic polysaccharide polymer is from 4.5:1 to 1.5:1.

Description

LAUNDRY COMPOSITIONS
FIELD OF THE INVENTION
This invention relates to a laundry composition. More particularly, the invention is directed to a softening in the wash laundry composition.
BACKGROUND OF THE INVENTION
Textile fabrics, including clothes, have traditionally been cleaned with laundry detergents. After cleaning, fabrics can often feel harsh. To prevent this, especially harshness experienced after multiple wash cycles, technologies have been developed to increase the softness of fabrics, including rinse-added conditioner compositions and softening systems added to the detergent composition.
Fabric softening cationic polymers, and fabric softening silicones have been used to provide softness to fabrics from a laundry detergent composition.
WO 2005/087907 discloses liquid detergent compositions comprising surfactants, polydimethylsiloxane (a softening silicone) and polyquaternium 7 (a polymeric quaternary salt consisting of acrylamide and dimethyl diallyl ammonium chloride monomers).
However there is a need to improve the softness benefit provided. There is further a need to provide softening detergent compositions that provide improved cleaning.
SUMMARY OF THE INVENTION
In a first aspect, the invention is directed to a laundry detergent composition comprising:-
(a) from 1 to 80 wt.% of surfactant; (b) from 0.1 to 10 wt.% of fabric softening silicone; and,
(c) from 0.05 to 2.5 wt.% of cationic polysaccharide polymer,
wherein the weight ratio of the silicone to cationic polysaccharide polymer is from 4.5:1 to 1 .5:1 .
Preferably the detergent composition is a liquid detergent composition.
Preferably the liquid detergent composition has a pH of from 6 to 10, more preferably from pH 6.5 to 9, for example from pH 6.5 to 8.5.
A preferred level of the cationic polymer is from 0.1 to 2 wt.%, more preferably from 0.1 to 1 wt.%.
Preferred cationic polysaccharide polymers are cationic guar and cationic cellulose polymers. Particularly preferred is hydroxy ether cellulose that is modified by incorporation of cationic groups (i.e. quaternised hydroxy ethyl cellulose).
Preferably the silicone is in the form of an emulsion.
Preferably the silicone is a polydimethylsiloxane.
Preferably the silicone is an aminosilicone. Preferably the silicone is an anionic silicone.
Preferably the weight ratio of the silicone to the cationic polymer is from 4:1 to 2:1 .
Optionally, but preferably, the composition further comprises an ingredient selected from, shading dye, enzyme, an antiredeposition polymer, a dye transfer inhibiting polymer, builder, sequestrant, sunscreen and/or soil release polymer. In a second aspect, the invention provides the use of a composition according to the first aspect of the invention to soften fabrics. DETAILED DESCRIPTION OF THE INVENTION
As used herein, the term "comprising" means including, made up of, composed of, consisting and/or consisting essentially of.
All percentages quoted are wt.% based on total amount in the laundry composition unless otherwise stated.
The invention is directed to laundry compositions containing surfactant, a cationic polymer, and a fabric softening silicone, wherein the weight ratio of silicone to cationic polymer is from 4.5:1 to 1 .5:1 . The composition displays improved fabric softening.
Form of the Invention
The invention can take any of a number of forms that are laundry compositions. Examples include powders, granules, bars, gels and liquids. Preferably the composition is in the form of a liquid laundry product. Preferably they are main wash products. It can take the form of a laundry composition for the main wash, which may be dilutable or non-dilutable. The laundry composition may for example be an isotropic liquid, or a surfactant-structured liquid. Particularly preferred forms of this invention include combination detergent/softener products to provide "softening in the wash".
Preferably the detergent composition has a pH of from 6 to 10, more preferably from pH 6.5 to 9, for example from pH 6.5 to 8.5.
Surfactants
The detergent composition comprises surfactant. Preferably the surfactant comprises nonionic surfactant, and anionic surfactant. The nonionic surfactant if present, preferably comprises alcohol ethoxylate.
The alcohol ethoxylates are formed from the reaction of primary or secondary alcohols with ethylene oxide. Typicially an aliphatic C8 to Ci8 primary or secondary linear or branched alcohol is reacted with ethylene oxide in the required molar amount to produce the alcohol ethoxylate. Preferred alcohol ethoxylates have from 2 to 40, preferably from 3 to 30, more preferably from 5 to 20 ethylene oxide units attached to the aliphatic chain.
The surfactants may be chosen from the surfactants described in "Surface Active Agents" Vol. 1 , by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, in the current edition of "McCutcheon's Emulsifiers and Detergents" published by Manufacturing Confectioners Company or in "Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981 .
Preferably the surfactants used are saturated. Suitable nonionic detergent compounds which may be used include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide. Specific nonionic detergent compounds are C6 to C22 alkyl phenol- ethylene oxide condensates, generally 5 to 25 EO, i.e. 5 to 25 units of ethylene oxide per molecule, and the condensation products of aliphatic Cs to C-is primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 40 EO. Suitable anionic detergent compounds which may be used can be water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals con- taining from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals. Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher Cs to Cie alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl Cg to C20 benzene sulphonates, particularly sodium linear secondary alkyl C-m to C15 benzene sulphonates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum. The anionic surfactant may also include soaps of C6-C22 fatty acids. The preferred anionic detergent compounds are sodium Cn to C-I5 alkyl benzene sulphonates and sodium C12 to Ci8 alkyl sulphates. Salts of sulphonates included as hydrotrobes can additionally be considered as anionic surfactants as defined herein. Also applicable are surfactants such as those described in EP-A-328 177 (Unilever), which show resistance to salting-out, the alkyl polyglycoside surfactants described in EP-A-070 074, and alkyl
monoglycosides.
The total amount of surfactant present in the composition is from 1 to 80 wt.%. The surfactant level is preferably at least 6 wt.%, more preferably at least 10 wt.%, More preferably the total amount of surfactant is from 15 to 65 wt.%, preferably from 10 to 50 wt.%.
The nonionic detergent is preferably present in amounts of from 2 to 40 wt.%, preferably from 5 to 35 wt.%, more preferably from 6 to 20 wt.%.
The anionic surfactant is preferably present in amounts of from 4 to 40 wt.%, preferably from 5 to 35 wt.%, more preferably from 6 to 20 wt.%.
Other surfactants such as amphoteric, zwitterionic and cationic surfactants may also be present in addition to the aforementioned nonionic and anionic
surfactants. Fabric Softening Silicone
The composition comprises fabric softening silicone at a level of from 0.1 to 10 wt.%, preferably from 0.2 to 5 wt.%, more preferably from 0.5 to 3 wt.%. The fabric softening silicone may be but are not limited to 1 ) non-functionalized silicones such as polydimethylsiloxane (PDMS) or alkyl (or alkoxy) functional silicones 2) functionalized silicones or copolymers with one or more different types of functional groups such as amino, phenyl, polyether, acrylate, siliconhydride, carboxylic acid, quaternized nitrogen, etc. When the silicone is in the form of a silicone emulsion, then preferably the particle size is in the range from about 1 nm to 100 microns and preferably from about 10 nm to about 10 microns including microemulsions ( < 150 nm), standard emulsions (about 200 nm to about 500 nm) and macroemulsions (about 1 micron to about 20 microns). Preferred silicones are selected from polydialkylsiloxanes, especially
polydimethylsiloxane; amino functionalised silicones; and anionic silicones, especially carboxyl functionalised silicone
Preferably the fabric softening silicone is a polydimethylsiloxane.
Cationic Polymer
The composition comprises a cationic polysaccharide polymer at a level of from 0.05 to 2.5 wt.%, preferably from 0.1 to 2 wt.%, more preferably from 0.2 to 1 wt.%.
This term refers to polymers having an overall positive charge.
More preferably the cationic polysaccharide polymer is a cationic guar or cationic cellulose polymer. Most preferably the cationic polymer is a cationic cellulose polymer, for example, quaternised hydroxy ethyl cellulose. Cationic Polysaccharide Polymer
The term "cationic polysaccharide polymer" refers to polymers having a
polysaccharide backbone and an overall positive charge. Polysaccharides are polymers made up from monosaccharide monomers joined together by glycosidic bonds.
The cationic polysaccharide-based polymers present in the compositions of the invention have a modified polysaccharide backbone, modified in that additional chemical groups have been reacted with some of the free hydroxyl groups of the polysaccharide backbone to give an overall positive charge to the modified cellulosic monomer unit.
A preferred class of cationic polysaccharide polymers suitable for this invention are those that have a polysaccharide backbone modified to incorporate a quaternary ammonium salt. Preferably the quaternary ammonium salt is linked to the polysaccharide backbone by a hydroxyethyl or hydroxypropyl group.
Preferably the charged nitrogen of the quaternary ammonium salt has one or more alkyl group substituents. Preferred cationic polysaccharide-based polymers have a guar based, or cellulosic based backbone. Cellulose based cationic polymers are most preferred. Guar is a galactomannan having a β-1 ,4 linked mannose backbone with
branchpoints to a-1 ,6 linked galactose units. Suitable cationic guar gum derivatives, such as guar hydroxypropyltrimonium chloride, specific examples of which include the Jaguar series commercially available from Rhone-Poulenc Incorporated and the N-Hance series commercially available from Aqualon Division of Hercules, Inc. An example of a preferred guar based cationic polymer is guar 2-hydroxy-3- (trimethylammonium) propyl ether salt. Cellulose is a polysaccharide with glucose as its monomer, specifically it is a straight chain polymer of D-glucopyranose units linked via β-1 ,4 glycosidic bonds and is a linear, non-branched polymer.
Example cationic cellulose polymers are salts of hydroxyethyl cellulose reacted with trimethyl ammonium substituted epoxide, referred to in the field under the International Nomenclature for Cosmetic Ingredients as Polyquatemium 10 and is commercially available from the Amerchol Corporation, a subsidiary of The Dow Chemical Company, marketed as the Polymer LR, JR, and KG series of polymers. Other suitable types of cationic celluloses include the polymeric quaternary ammonium salts of hydroxyethyl cellulose reacted with lauryl dimethyl ammonium- substituted epoxide referred to in the field under the International Nomenclature for Cosmetic Ingredients as Polyquatemium 24. These materials are available from Amerchol Corporation marketed as Polymer LM-200.
Typical examples of preferred cationic cellulosic polymers include
cocodimethylammonium hydroxypropyl oxyethyl cellulose,
lauryldimethylammonium hydroxypropyl oxyethyl cellulose,
stearyldimethylammonium hydroxypropyl oxyethyl cellulose, and
stearyldimethylammonium hydroxyethyl cellulose; cellulose 2-hydroxyethyl 2- hydroxy 3-(trimethyl ammonio) propyl ether salt, polyquaternium-4,
polyquaternium-10, polyquaternium-24 and polyquaternium-67 or mixtures thereof.
More preferably the cationic cellulosic polymer is a quaternised hydroxy ether cellulose cationic polymer. These are commonly known as polyquaternium-10. Suitable commercial cationic cellulosic polymer products for use according to the present invention are marketed by the Amerchol Corporation under the trade name UCARE. The counterion of the cationic polymer is freely chosen from the halides: chloride, bromide, and iodide; or from hydroxide, phosphate, sulphate, hydrosulphate, ethyl sulphate, methyl sulphate, formate, and acetate. Many of the aforementioned cationic polymers can be synthesised in, and are commercially available in, a number of different molecular weights. Preferably the molecular weight of the cationic polymer is from 10,000 to 2,000,000 Daltons, more preferably from 10,000 to 1 ,000,000 Daltons, even more preferably from 100,000 to 1 ,000,000 Daltons.
Optional Ingredients
The detergent composition may optionally comprise one or more of the following optional ingredients, shading dye, enzyme, antiredeposition polymer, dye transfer inhibiting polymer, builder, sequestrant, sunscreen and/or soil release polymer.
Builders and sequestrants
The detergent compositions may also optionally contain relatively low levels of organic detergent builder or sequestrant material. Examples include the alkali metal, citrates, succinates, malonates, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetyl carboxylates. Specific examples include sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene
polycarboxylic acids, ethylene diamine tetra-acetic acid, diethylenetriamine- pentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic acid, and citric acid. Other examples are DEQUEST™, organic phosphonate type sequestering agents sold by Thermophos and alkanehydroxy phosphonates.
Other suitable organic builders include the higher molecular weight polymers and copolymers known to have builder properties. For example, such materials include appropriate polyacrylic acid, polymaleic acid, and polyacrylic/polymaleic acid copolymers and their salts, such as those sold by BASF under the name SOKALAN™. Another suitable builder is sodium carbonate. If utilized, the builder materials may comprise from about 0.5% to 20 wt%, preferably from 1 wt% to 10 wt%, of the composition. The preferred builder level is less than 10 wt% and preferably less than 5 wt% of the composition.
Preferably the laundry detergent formulation is a non-phosphate built laundry detergent formulation, i.e., contains less than 1 wt.% of phosphate.
Shading Dye
Shading dyes deposit to fabric during the wash or rinse step of the washing process providing a visible hue to the fabric. Shading of white garments may be done with any colour depending on consumer preference. Blue and Violet are particularly preferred shades and consequently preferred dyes or mixtures of dyes are ones that give a blue or violet shade on white fabrics. The shading dyes used are preferably blue or violet.
The shading dye chromophore is preferably selected from the group comprising: mono-azo, bis-azo, triphenylmethane, triphenodioxazine, phthalocyanin, naptholactam, azine and anthraquinone. Most preferably mono-azo, bis-azo, azine and anthraquinone.
Most preferably the dye bears at least one sulfonate group.
Preferred shading dyes are selected from direct dyes, acid dyes, hydrophobic dyes, cationic dyes and reactive dyes.
If included, the shading dye is present is present in the composition in range from 0.0001 to 0.01 wt %.
Fluorescent Agent The composition preferably comprises a fluorescent agent (optical brightener). Fluorescent agents are well known and many such fluorescent agents are available commercially. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts. The total amount of the fluorescent agent or agents used in the composition is generally from 0.005 to 2 wt.%, more preferably 0.01 to 0.1 wt.%. Preferred classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine stilbene di-sulphonic acid compounds, e.g. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH, and Pyrazoline compounds, e.g. Blankophor SN. Preferred fluorescers are: sodium 2-(4-styryl-3-sulfophenyl)-2H-napthol[1 ,2- d]trazole, disodium 4,4'-bis{[(4-anilino-6-(N methyl-N-2 hydroxyethyl) amino 1 ,3,5- triazin-2-yl)]amino}stilbene-2-2' disulfonate, disodium 4,4'-bis{[(4-anilino-6- morpholino-1 ,3,5-triazin-2-yl)]amino} stilbene-2-2' disulfonate, and disodium 4,4'- bis(2-sulfoslyryl)biphenyl.
Perfume
Preferably the composition comprises a perfume. The perfume is preferably in the range from 0.001 to 3 wt.%, most preferably 0.1 to 1 wt.%. Many suitable examples of perfumes are provided in the CTFA (Cosmetic, Toiletry and
Fragrance Association) 1992 International Buyers Guide, published by CFTA Publications and OPD 1993 Chemicals Buyers Directory 80th Annual Edition, published by Schnell Publishing Co.
It is commonplace for a plurality of perfume components to be present in a formulation. In the 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.
In perfume mixtures preferably 15 to 25 wt.% are top notes. Top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1955]). Preferred top-notes are selected from citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol.
It is preferred that the laundry treatment composition does not contain a peroxygen bleach, e.g., sodium percarbonate, sodium perborate, and peracid.
Polymers
The composition may comprise one or more polymers. Polymers can assist in the cleaning process by helping to retail soil in solution or suspension and/or preventing the transfer of dyes. Polymers can also assist in the soil removal process. Dye transfer, anti-redeposition and soil-release polymers are described in further detail below.
The composition may comprise one or more polymers. Examples are
carboxymethylcellulose, hydroxyethyl cellulose, hydroxpropyl cellulose, poly(ethylene glycol), polyvinyl alcohol), ethoxylated polyamines,
polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers. Dye transfer inhibitors
Modern detergent compositions typically employ polymers as so-called 'dye- transfer inhibitors'. These prevent migration of dyes, especially during long soak times. Generally, such dye-transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N- vinylimidazole, manganese pthalocyanine, peroxidases, and mixtures thereof, and are usually present at a level of from 0.01 to 10 wt.% based on total amount in the laundry composition.
Anti-redeposition polymers
Anti-redeposition polymers are designed to suspend or disperse soil. Typically antiredeposition polymers are ethoxylated and or propoxylated polyethylene imine or polycarboxylate materials, for example, Acrylic acid based homo or copolymers available under the trade mark ACUSOL from Dow Chemical, Alcosperse from Akzonobel or Sokolan from BASF. Soil Release Polymers
Examples of suitable soil release polymers include graft copolymers of polyvinyl ester), e.g., Ci -C6 vinyl esters, preferably polyvinyl acetate) grafted onto polyalkylene oxide backbones. Commercially available soil release agents of this kind include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (Germany). Further suitable soil release polymers of a different type include the commercially available material ZELCON 5126 (from DuPont) and MILEASE T (from ICI). If present, the soil release polymer may be included at a level of from from 0.01 to 10 wt.% based on total amount in the laundry
composition. Further examples of soil release polymers are terephthalic acid / glycol copolymers sold under the tradenames Texcare, Repel-o-tex, Gerol, Marloquest, Cirrasol.
Hydrotrope
If in the form of a liquid, then the liquid detergent composition may optionally include a hydrotrope, which can prevent liquid crystal formation. The addition of the hydrotrope thus aids the clarity/transparency of the composition. Suitable hydrotropes include but are not limited to propylene glycol, ethanol, glycerol, urea, salts of benzene sulphonate, toluene sulphonate, xylene sulphonate or cumene sulphonate. Suitable salts include but are not limited to sodium, potassium, ammonium, monoethanolamine, triethanolamine. Salts of sulphonates can also be considered as anionic surfactants as defined herein. Preferably, the
hydrotrope is selected from the group consisting of propylene glycol, xylene sulfonate, ethanol, and urea to provide optimum performance. The amount of the hydrotrope is generally in the range of from 0 to 30%, preferably from 0.5 to 30%, more preferably from 0.5 to 30%, most preferably from 1 to 15%. Enzymes
Enzymes can also be present in the formulation. Preferred enzymes include protease, lipase, pectate lyase, amylase, cutinase, cellulase, mannanase. If present the enzymes may be stabilized with a known enzyme stabilizer for example boric acid.
Examples
Two control formulations 'A' and 'B' that did not include the cationic polymer or a silicone were tested against formulations 'C, ', Έ' and formulations 1 and 2, all with and without silicone (e.g. 1 & 1 (Sil)). The formulations are listed in tables 1 and 2.
Method of Production of formulation
Water and hydrotropes are mixed together at ambient temperature (approximately 22°C) for 2-3 minutes at a shear rate of 150 rpm using a Janke & Kunkel IKA
RW20 overhead mixer. Salts and alkalis are added and mixed for 5 minutes prior to addition of surfactants and fatty acid. The mixture will exhibit a slight exotherm at this point. After allowing to cool to <30°C, the LR400 solution, and any remaining components such as perfume, preservatives, and dyes are added.
Softness experiment
12 pieces of 20cm x 20cm terry towel along with 1 .8kg of polycotton ballast fabric was added to a front loading automatic washing machine. 75ml of formulation was dosed into a dosing ball, followed by the required amount of silicone emulsion. The mixture was stirred for 2 minutes. The dosing ball containing the formulation and silicone was then added to the drum of the washing machine. The fabrics were then washed using the cotton short cycle at 40°C of a Miele automatic washing machine. After the cycle the fabrics were line dried. This process was repeated 5 times. Table 1
Silicone was a carboxylic functional silicone supplied by Wacker Chemie, added as an emulsion.
LR400 is a cationic hydroxyether cellulose polymer (known as polyquaternium 10) available from Dow Chemical
Table 2
1 Silicone was a carboxylic functional silicone supplied by Wacker Chemie
2 LR400 is a cationic hydroxyether cellulose polymer (known as polyquaternium 10) available from Dow Chemical
The formulations were tested for softness, with the results shown in table 3.
The softness was measured using a Stable Micro Systems Texture Analyser (TA) XT plus with the optional friction module attached. The TA is a commercial instrument incorporating a drive mechanism and a 5 kg load cell. The treated fabric was laid on the horizontal test platform of the instrument and a neoprene rubber cylindrical probe which is attached to the load cell was placed on the fabric surface. The texture analyser is programmed to move the probe over a distance of 40 mm forwards and backwards over the fabric at a speed of 10 mm/s. As the probe moves the software records the frictional force experienced by the probe. The average friction coefficient over the whole test is used as a measure of softness. For formulations C, D, E, 1 and 2, the formulation without silicone (but with cationic polymer), i.e. 'C was measured against the formulation including silicone, i.e. C(Sil) in pairs. The results for each pair were assessed to see if there was a statistically significant (at 95% confidence level) improvement for the silicone & cationic polymer formulation.
Table 3
As can be seen from the results in table 3, only when the ratio of silicone to cationic polymer is from 4.5:1 to 1 .5:1 does the inclusion of a fabric softening silicone provide a statistical significant benefit over just inclusion of the cationic polymer alone.
Example 2 Further softness experiments were as performed to establish whether the effect of silicone to cationic polymer ratio is consistent across other functional silicones. In this case a PDMS and an amino silicone were used, and the results are shown in tables 4 & 5.
Table 4
1 Silicone 1 was PDMS 60,000 cSt supplied by Dow Corning as an emulsion
2 Silicone 2 was amino silicone Arristan 64 supplied by CHT Beitlich as an emulsion 3 LR400 is a cationic hydroxyether cellulose polymer (known as polyquaternium 10) available from Dow Chemical Table 5
The results in table 5 show that a statistically significant softening benefit (in comparison to the controls) can be achieved only when the ratio of silicone to cationic polymer is from 4.5:1 to 1 .5:1 .
Example 3
Cleaning experiments were carried out that showed that when the ratio of silicone to cationic polymer is from 4.5:1 to 1 .5:1 the cleaning is improved compared to a ratio of silicone to cationic polymer lower than 1 .5:1 (i.e. 1 :1 and 1 :2).
Example 4
Comparative Example of a cationic polysaccharide polymer versus
polyquaternium 7 from WO 2005/087907
Silicone deposition of both cationic polymers was tested using identical formulations varying only by the cationic polymer used. The formulations were dosed to provide silicone at 0.5g/wash and cationic polymer at 0.2g/wash. The variables tested were:-
Control - formulation including 0.5g/wash silicone
Polysaccharide - formulation including 0.5g/wash silicone + 0.2g/wash cationic polysaccharide polymer (LR400) Polyquat 7 - formulation including 0.5g/wash silicone + 0.2g/wash cationic polymer (polyquaternium 7)
The washes were carried out on 2 different substrates, terry towelling; and repeated on white knitted cotton. The articles were washed 6 times, dried and then friction measured after each wash. The friction measurement results in a average friction coefficient. The friction test shows how soft the articles washed were, in that the amount of silicone deposited builds-up onto the article and decreases friction.
Friction test details
The coefficient of friction was measured using a commercially available Stable Micro Systems Texture Analyser. The fabric article is placed onto a platform and a rubber probe placed on the fabric and moved at 10mm/s. The probe is moved 40mm forwards, followed by 40mm backwards. The instrument records the frictional force which is then converted into an average friction coefficient throughout the movement in both directions. The data points in the following tables show that the polysaccharide provides statistically significant improvement in reduced friction (hence increased silicone deposition) at 95% confidence levels.
Table 6 - Silicone build-up on terry towelling
Wash No. Control Polyquat 7 Polysaccharide
(comparative)
0 1 .465 (± 0.010) - -
1 1 .425 (± 0.017) 1.328 (± 0.01 1 ) 1 .432 (± 0.013)
2 1 .502 (± 0.010) 1.319 (± 0.010) 1 .142 (± 0.01 1 )
3 1 .390 (± 0.030) 1.317 (± 0.013) 1 .072 (± 0.014)
4 1 .424 (± 0.028) 1.293 (± 0.010) 1 .050 (± 0.014)
5 1 .469 (± 0.012) 1.344 (± 0.010) 1 .035 (± 0.020)
6 1 .407 (± 0.013) 1.280 (± 0.014) 1 .027 (± 0.010) Table 7 - Silicone build-up on white knitted cotton
Thus it can be seen from the results in tables 6 & 7 that the cationic
polysaccharide polymer provides superior deposition of silicone over that prior art polyquaternium-7 disclosed in WO 2005/087907.

Claims

1 . A laundry detergent composition comprising:-
(a) from 1 to 80 wt.% of surfactant;
(b) from 0.1 to 10 wt.% of fabric softening silicone; and
(c) from 0.05 to 2.5 wt.% of cationic polysaccharide polymer,
wherein the weight ratio of silicone to cationic polysaccharide poly from 4.5:1 to 1 .5:1 .
A composition according to claim 1 , which is a liquid detergent composition.
A composition according to claim 2, wherein liquid composition has a pH of from 6 to 10, preferably from pH 6.5 to 9, most preferably from pH 6.5 to 8.
A composition according to any preceding claim, wherein the cationic polysaccharide polymer is present at a level of from 0.1 to 2 wt.%, preferably from 0.1 to 1 wt.%.
A composition according to any preceding claim, wherein the cationic polysaccharide polymer comprises cationic guar and/or cationic cellulose polymers.
6. A composition according to claim 5, wherein the cationic polysaccharide polymer is a cationic cellulose polymer, preferably quaternised hydroxy ethyl cellulose.
7. A composition according to any preceding claim, wherein the silicone is in the form of an emulsion. 8. A composition according to any preceding claim, wherein the silicone is polydimethylsiloxane.
9. A composition according to any preceding claim, wherein the silicone is an amino silicone. 10. A composition according to any preceding claim, wherein the silicone is an anionic functionalised silicone, preferably a carboxyl functionalised silicone.
1 1 . A composition according to any preceding claim, wherein the composition further comprises an ingredient selected from, shading dye, enzyme, an antiredeposition polymer, a dye transfer inhibiting polymer, builder, sequestrant, sunscreen and/or soil release polymer.
12. Use of a composition according to any one of claims 1 to 1 1 to soften
fabrics.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021194808A1 (en) * 2020-03-24 2021-09-30 Rohm And Haas Company Fabric care composition

Families Citing this family (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10604723B2 (en) 2014-11-11 2020-03-31 Rohm And Haas Company Cationic carbohydrate polymers for fabric care
TR201901003T4 (en) 2014-11-17 2019-02-21 Unilever Nv Fabric Processing Composition
EP3221440B1 (en) 2014-11-17 2020-09-23 Unilever PLC Fabric treatment composition
WO2017102874A1 (en) 2015-12-18 2017-06-22 Henkel Ag & Co. Kgaa Liquid detergent composition
WO2017211699A1 (en) 2016-06-09 2017-12-14 Unilever Plc Laundry liquid mixing apparatus
PL3580318T3 (en) 2017-02-13 2023-10-02 Unilever Ip Holdings B.V. Method of delivering a laundry composition
CN110291179B (en) * 2017-02-13 2021-11-16 联合利华知识产权控股有限公司 Laundry adjunct composition
CN110352232A (en) * 2017-02-13 2019-10-18 荷兰联合利华有限公司 Laundry composition additive
ES2932443T3 (en) 2017-02-13 2023-01-19 Unilever Ip Holdings B V washing composition
EP3676244A4 (en) 2017-08-30 2021-05-05 Ecolab Usa Inc. Molecules having one hydrophobic group and two identical hydrophilic ionic groups and compositions thereof
TR202004710U5 (en) 2017-10-05 2021-01-21 Unilever Nv Methods and apparatuses for specialized laundry.
CN216764833U (en) 2017-10-05 2022-06-17 联合利华知识产权控股有限公司 Combination of reservoirs
GB2571336A (en) 2018-02-26 2019-08-28 Unilever Plc Methods and system for monitoring and replenishing one or more laundry components
US11814607B2 (en) 2018-03-02 2023-11-14 Conopco, Inc. Laundry additive composition comprising a soil release polymer/silicone mixture
BR112020017947B1 (en) * 2018-03-02 2024-02-15 Unilever Ip Holdings B.V. METHOD FOR SOFTENING COTTON KNIT AND USE OF THE COMPOSITION FOR LAUNDRY
CA3110365C (en) 2018-08-29 2023-05-09 Ecolab Usa Inc. Use of multiple charged ionic compounds derived from polyamines for waste water clarification
US11084974B2 (en) 2018-08-29 2021-08-10 Championx Usa Inc. Use of multiple charged cationic compounds derived from polyamines for clay stabilization in oil and gas operations
AU2019332961B2 (en) 2018-08-29 2022-04-07 Ecolab Usa Inc. Multiple charged ionic compounds derived from polyamines and compositions thereof and methods of preparation thereof
EP3844112A1 (en) 2018-08-29 2021-07-07 Ecolab USA Inc. Use of multiple charged cationic compounds derived from primary amines or polyamines for microbial fouling control in a water system
CA3110854A1 (en) 2018-08-29 2020-03-05 Ecolab Usa Inc. Multiple charged ionic compounds derived from polyamines and compositions thereof and use thereof as reverse emulsion breakers in oil and gas operations
CN112805360A (en) * 2018-10-29 2021-05-14 陶氏环球技术有限责任公司 Fabric care compositions containing silicone
EP3897143A1 (en) 2019-01-29 2021-10-27 Ecolab USA Inc. Use of cationic sugar-based compounds for microbial fouling control in a water system
WO2020159955A1 (en) 2019-01-29 2020-08-06 Ecolab Usa Inc. Use of cationic sugar-based compounds as corrosion inhibitors in a water system
EP3956496A1 (en) 2019-04-16 2022-02-23 Ecolab USA Inc. Use of multiple charged cationic compounds derived from polyamines and compositions thereof for corrosion inhibition in a water system
US11910982B2 (en) 2019-11-01 2024-02-27 Conopco Inc. Recyclable auto-dosing container
US11220657B2 (en) 2019-12-31 2022-01-11 Henkel IP & Holding GmbH Solid perfume composition delivering softening
US11447722B2 (en) 2020-01-30 2022-09-20 Henkel Ag & Co. Kgaa Detergent composition for textile softening and anti-redeposition
US11499120B2 (en) 2020-01-30 2022-11-15 Henkel Ag & Co. Kgaa Three polymer blend to achieve fabric care in laundry

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0070074B2 (en) 1981-07-13 1997-06-25 THE PROCTER &amp; GAMBLE COMPANY Foaming surfactant compositions
US4820308A (en) 1984-10-12 1989-04-11 L'oreal Detergent cosmetic compositions containing a soap and cationic compound and direct dye
GB8803036D0 (en) 1988-02-10 1988-03-09 Unilever Plc Liquid detergents
GB9216758D0 (en) * 1992-08-07 1992-09-23 Unilever Plc Detergent composition
GB9216766D0 (en) * 1992-08-07 1992-09-23 Unilever Plc Detergent compositions for enhanced silicone deposition comprising silicone and cationic polymers and method for detecting such compositions
US6126954A (en) * 1999-04-05 2000-10-03 Unilever Home & Personal Care Usa, Division Of Conopco Liquid compositions comprising stable emulsion of small particle skin benefit agent
JP4147067B2 (en) 2002-08-09 2008-09-10 花王株式会社 Cleaning composition
DE60319845T2 (en) 2002-09-09 2009-03-05 The Procter & Gamble Company, Cincinnati USE OF CATIONIC CELLULOSIS TO INCREASE THE RELEASE OF TEXTILE PRODUCTS
CA2502303C (en) * 2002-11-04 2010-08-17 The Procter & Gamble Company Liquid laundry detergent
BR0315989A (en) * 2002-11-04 2005-09-20 Procter & Gamble Compositions for treating fabrics containing oppositely charged polymers, use and method comprising the same
EP1431383B1 (en) 2002-12-19 2006-03-22 The Procter & Gamble Company Single compartment unit dose fabric treatment product comprising pouched compositions with cationic fabric softener actives
GB0405414D0 (en) 2004-03-11 2004-04-21 Reckitt Benckiser Nv Improvements in or relating to liquid detergent compositions
US20060030513A1 (en) 2004-08-03 2006-02-09 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Softening laundry detergent
WO2008120176A1 (en) 2007-04-02 2008-10-09 The Procter & Gamble Company Fabric care composition
WO2008152602A1 (en) * 2007-06-15 2008-12-18 Ecolab Inc. Liquid fabric conditioner composition and method of use

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2014079621A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021194808A1 (en) * 2020-03-24 2021-09-30 Rohm And Haas Company Fabric care composition

Also Published As

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EP2922936B1 (en) 2019-08-14
BR112015008917B1 (en) 2022-02-01
ZA201502942B (en) 2016-09-28
CN104781381B (en) 2018-02-23
AR093522A1 (en) 2015-06-10
WO2014079621A1 (en) 2014-05-30
CN104781381A (en) 2015-07-15
BR112015008917A2 (en) 2017-07-04
CL2015001055A1 (en) 2015-08-28

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