EP1859016B1 - Compositions d entretien pour tissus - Google Patents

Compositions d entretien pour tissus Download PDF

Info

Publication number
EP1859016B1
EP1859016B1 EP06723210A EP06723210A EP1859016B1 EP 1859016 B1 EP1859016 B1 EP 1859016B1 EP 06723210 A EP06723210 A EP 06723210A EP 06723210 A EP06723210 A EP 06723210A EP 1859016 B1 EP1859016 B1 EP 1859016B1
Authority
EP
European Patent Office
Prior art keywords
composition
fabric
fabric softening
silica
weight
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.)
Not-in-force
Application number
EP06723210A
Other languages
German (de)
English (en)
Other versions
EP1859016A1 (fr
Inventor
Teodora A. Unilever R & D Port Sunlight DONEVA
Llyr G. Unilever R & D Port Sunlight GRIFFITHS
Mansur S. Unilever R & D Port Sunlight Mohammadi
Kevin A. Unilever R & D Port Sunlight ORMANDY
H.M. Unilever R & D Port Sunlight SOUTHEY-DAVIS
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 PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to PL06723210T priority Critical patent/PL1859016T3/pl
Publication of EP1859016A1 publication Critical patent/EP1859016A1/fr
Application granted granted Critical
Publication of EP1859016B1 publication Critical patent/EP1859016B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C11D3/3742—Nitrogen containing silicones
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • C11D3/0015—Softening compositions liquid
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/221—Mono, di- or trisaccharides or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones

Definitions

  • the present invention relates to fabric care compositions. More specifically, the invention relates to rinse cycle fabric care compositions which reduce the wrinkling of fabrics and in particular the dry or in-wear wrinkling giving fabrics an all-day-ironed look.
  • the lubricants used in the prior art include silicones eg PDMS, aminosilicones, modified silicones, silicone copolymers, softeners (e.g. quaternary ammonium compounds) and other lubricants such as clays, waxes, polyolefins, synthetic and natural oils.
  • WO 2004/018762A1 discloses on wrinkle benefit using fusible elastomer film formers with cross-linked particles to improve recovery from wrinkle in spray or iron cartridge applications
  • WO 2004/048677 discloses film formers for recovery in spray or iron cartridge applications including fusible elastomers + polycation salt for x-linking of elastomer.
  • WO 2001/25381-5 disclose compositions with (A) a fabric softener, (B) an additive and (C) selected polyorganosilicones to endow fabrics in domestic applications with anti-pilling, elasticity, hydrophilicity, drape, and wrinkle recovery respectively. These properties are endowed by the organosilicone.
  • the additives polysilicic acid is mentioned.
  • WO 2002/088293 and US-A1-2002/019236 both disclose fabric care compositions comprising coated particles comprising a solid core with a D 3,2 average particle size of between 10 to 700 nm in diameter and a coating of silicone polymer covalently bonded to the solid core.
  • Silica is mentioned in a list of suitable solid core materials.
  • EP 1201817 (A1 ) (Procter & Gamble) discloses aminosilicones with sterically hindered functional groups for in-wear wrinkle resistance, which are preferably delivered from a spray during domestic ironing process.
  • EP 1096060 (A1 ) (Procter & Gamble) discloses water-soluble silicone lubricants in combination with various polymeric compounds (film formers) which are said to provide fabrics with a wrinkle recovery angle of at least +15 units over and above water.
  • EP 953675 (A2,A3) (Dow Corning) a textile fabric coated with an elastomeric silicone-based compound with a reinforcing filler preferably a silica + a second laminar filler preferably talc and mica.
  • the coated fabrics amongst other benefit have less friction and are used for car seat belts. No teaching exists on the wrinkle benefit of the mixed silicone + particulate fillers.
  • GB 842027 (Monsanto Chemicals) discloses textile friction enhancing compositions based on silica nanoparticles dispersed inside an oil emulsion droplets.
  • the oil can be any of the known textile oils including mineral or vegetable oils.
  • the oil to silica ratio exceeds 6 and deposition levels of 3-7% oil and 0.1-0.5% of silica per weight of fabric are preferred.
  • US 2635056 discloses treating textiles and fabrics with an aquasol of silica plus a polyhydic alcohol such as glycerol.
  • the blends are termed alco-aquasols and provide exceptional slip resistance to textiles and surprisingly good handle and fabric feel attributed to the presence of glycerol.
  • the silica to glycerol ratio used in the example is 1.4. It is stated that polyhydric alcohol level should not exceed twice that of silica.
  • WO-2001/083875 discloses the application of silica and a softener with a cationic acrylic binder followed by application of a treatment solution containing arginine to nylon tights so as to provide skin care benefits when the tights are worn.
  • EP 1024119 (A2,A3) (Relats) discloses textile articles made of SiO 2 -containing fibres and procedure for improving their thermal stability.
  • JP 04255767 discloses coating compositions for textiles comprising a synthetic emulsion (acrylic), colloidal or microparticle metal oxide silica gel and a zeolite to provide textile coatings with good antibacterial, deodorising, drying and heat retention properties.
  • NL 8900473 (Hesco Fashion Netherlands) discloses the manufacture of viscose rayon-polyester coated with a mixture of a nonionic fatty acid condensates fabric softener and a blocking agent (blocking free movement of warp and weft - friction enhancer) acidic silica dispersion.
  • the ratio of the softener to silica is 1:1 and the level applied 1% of silica and 1% of softener.
  • EP 0474207 , US 2881146 , US 3077460 and US 5102930 all disclose fabric treatment compositions comprising silica, an organopolysiloxane and a catalyst/curing agent to cause a polymer film to form on the fabrics.
  • compositions for use in the rinse which provides effective elimination or reduction of wrinkles in dry fabric in wear in addition to the benefits of good softness and perfume normally expected from rinse added products.
  • the in-wear wrinkle resistance is provided by the composition after the first wash cycle in which it is used.
  • the present invention seeks to address one or more of the above-mentioned problems.
  • a fabric treatment composition for use in the rinse cycle of a washing machine for reducing in-wear wrinkle in fabrics, the composition comprising:
  • compositions of the invention are used in the rinse cycle of a laundry process and impart in-wear crease resistance to the treated fabrics.
  • the compositions comprise a blend of nanoparticles, which act as a friction element, and a lubricant phase.
  • the balance of the nanoparticles and lubricant phase provides the desired properties by virtue of their physical properties.
  • the compositions of the invention are free from catalysts and curing agents and do not react to form a film when deposited on the fabric.
  • compositions of the present invention are typically for use as part of a fabric care composition which is delivered to the rinse cycle of an automatic washing machine.
  • compositions of the present invention comprise a nanoparticle dispersion which act as a frictional element when deposited on the fabrics.
  • the particles are inorganic.
  • Suitable inorganic nano-particles include silicas, SiO 2 .
  • the widely commercial and preferred inorganic nanoparticle are amorphous silicas available in the sol or colloidal form as defined on page 330 of The Chemistry of Silica, by R K Iler, Wiley-Interscience, New York, 1979 .
  • Silica nanoparticles could also be of non-siliceous core as long as the surface of the nanoparticle is coated with silica as described on page 330 of Iler's book.
  • the core can be of organic polymeric nature.
  • nanoparticle denotes particles having an average particle size ranging from 5 to 500 nm. Larger particle size silica also aid crease resistance but apparently they are not as effective as those between 15-100 nm. Preferably all of the particles have a particle size below 500 nm, more preferably below 100 nm.
  • Dispersions having an average particle size in the range 10 to 50 nm are particularly useful.
  • the amount to deposit between 0.25 to 2% and preferably between 0.25 to 0.5 wt% owf (0.0025 to 0.005 g/g of fabric).
  • Nanoparticles depending on their structure can provide additional benefits - aid odour absorption during the wear, increase longer lasting freshness, reduced glare and shine on ironing items, resistance to staining, and ease of stain removal in following washes can be achieved.
  • Preferred nanoparticles for use in the invention are colloidal silica.
  • the term 'colloidal silica' here refers to dispersions or sols of discrete particles of amorphous silica, which are preferably stable. Reacted silica is the hydrophobic fumed silica as used in anti-foaming emulsions mentioned above.
  • colloidal silica is available containing up to 50% silica with particle diameter between 10-21 nm under the trade name Ludox (ex Grace Davison) and Snowtex (ex Nissan). Particular examples include Ludox Cl (a cationic silica) and Ludox HS50 (an anionic silica), both having a particle size of 20 nm. The quoted size represents the linear diameter of the particle.
  • silica particles can be easily modified to endow them with additional benefits.
  • modification with aluminates allows surface charge modification (positive charge).
  • Silicas can be modified organically (organosols as described on page 412 of the above reference).
  • the preferred silicas have suitable modification for surface charge and/or other textile functional benefits including antimicrobial, dermal and transdermal, controlled release of fragrance and repellent agents, improved abrasion stability, water and oil, dirt repellency, and UV protection as described in Journal of Sol-Gel Science and Technology 27, 43-52, 2003 by B Mahltig and H Bottcher; Modified Silica Sol coatings for Water-Repellent Textiles .
  • compositions of the present invention comprise a fibre lubricant selected from silicone oils, sucrose polyester oils or oily sugar derivatives and quaternary ammonium fabric softening materials.
  • the lubricant phase of interest include silicone oils and oily sugar derivatives.
  • the silicone lubricants of interest include the classical three classes of non-reactive silicone polymers (PDMS), reactive silicone polymers (silanol terminated PDMS) and modified silicone polymers (amino/amide functional siloxanes, non-ionic modified siloxanes or polyether modified siloxanes).
  • Preferred silicones are PDMS types in emulsion or microemulsion format, which are commercially available, for example, Dow Corning 1716 (cationic) microemulsion, etc.
  • Another class of preferred silicones are those ex Wacker including Wetsoft CTA (amino glycol PDMS), Finish CT 34E (amino PDMS emulsion), Finish CT 208E (amino OH PDMS emulsion), Finish CT 96 E (amino PDMS emulsion), and their Fluid L range, Fluid L 652 for example (amino PDMS).
  • silicone oils are preferred to improve the fabric handle and softness non-silicone lubricants such as sucrose polyester oils can provide the lubrication needed for fabric recovery from wrinkle.
  • WO2002/019236A1 (Unilever) provides a fuller list of silicone polymers of interest and EP1205538 (Unilever) the class of drying oils.
  • a preferred class of commercial materials in which the particulate phase and a lubricant phase are combined include but not limited to Dow Corning's silicone + reacted silica blends marketed as anti-foaming agents including DOW CORNING® Antifoam B, DOW CORNING@ 544, DOW CORNING@ Q2-3302 ANTIFOAM COMPOUND, DOW CORNING@ 1581 WATER REPELLENT, DOW CORNING@ 2-1912 FLUID.
  • Another preferred class of materials in which the particulate phase and the lubricant phase are combined include but not limited to Dow Corning MQ silicone resin range which contains a PDMS silicone oil and a silicone resin nano-particulate phase.
  • Suitable sucrose polyester oils are the reaction products of fatty acid methyl ester (FAME) of natural oils and sucrose. Suitable oils and their preparation are described in EP323670B1 , EP 383404B1 , WO 2001/46210 , WO 98/16538 , WO 01/46359A1 and British Patent Application No. 0501006.1 .
  • oils are derived from natural oils predominantly comprising C 16 and C 18 hydrocarbon chains e.g. palm kernel oil, soy bean oil.
  • the quaternary ammonium fabric softening material is generally one that is able to form a lamellar phase dispersion in water, in particular a dispersion of liposomes.
  • the quaternary ammonium compound "QAC” is preferably one having two C 12-28 groups, that may independently be alkyl or alkenyl groups, connected to the nitrogen head group, preferably being connected to the nitrogen head group by at least one ester link, and more preferably by two ester links.
  • the average chain length of the alkyl and/or alkenyl groups is preferably at least C 14 and more preferably at least C 16 . It is particularly preferred that at least half of the groups have a chain length of C 18 . In general, the alkyl and/or alkenyl groups are predominantly linear.
  • TEA ester quats di-esters of triethanolammonium methylsulphate, otherwise referred to as "TEA ester quats".
  • Commercial examples include Prapagen TQL, ex Clariant, and Tetranyl AHT-1, ex Kao, (both di-[hardened tallow ester] of triethanolammonium methylsulphate), AT-1 (di-[tallow ester] of triethanolammonium methylsulphate), and L5/90 (di-[palm ester] of triethanolammonium methylsulphate), both ex Kao, and Rewoquat 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.
  • the second group of QACs suitable for use in the composition 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 composition 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.
  • a fourth group of QACs suitable for use in the composition is represented by formula (IV): (R 1 ) 2 -N + -(R 2 ) 2 X - (IV) 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 X - is as defined above.
  • Preferred materials of this fourth group include di(hardened tallow)dimethylammonium chloride.
  • the iodine value of the softening agent is preferably from 0 to 20, more preferably from 0 to 4, and most preferably from 0 to 2.
  • Essentially saturated material i.e. having an iodine value of from 0 to 1, is used in especially high performing compositions. At low iodine values, the softening performance is excellent and the composition has improved resistance to oxidation and associated odour problems upon storage.
  • Iodine value is defined as the number of grams of iodine absorbed per 100 g of test material. NMR spectroscopy is a suitable technique for determining the iodine value of the softening agents of the present invention, using the method described in Anal. Chem., 34, 1136 (1962) by Johnson and Shoolery and in EP 593,542 (Unilever, 1993).
  • the softening agent is usually present in the compositions of the invention at a level of 5% or greater by weight of the total composition.
  • references to levels of cationic softening agent in this specification are to the total level of cationic softening agent, including all cationic components of a complex raw material that could enter aqueous lamellar phase together.
  • a di-ester softening agent it includes any associated mono-ester or tri-ester that may be present.
  • the amount of softening agent is generally 50% or less, particularly 40% or less, and especially 30% or less by weight of the total composition. Generally the softening agent is present in an amount of from 3 to 20% by weight of the composition.
  • composition of 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.
  • Preferred fatty acids include hardened tallow fatty acid (available under the tradename Pristerene, ex Uniqema).
  • Preferred fatty alcohols include hardened tallow alcohol (available under the tradenames Stenol and Hydrenol, ex Cognis and Laurex CS, ex Albright and Wilson) and behenyl alcohol, a C22 chain alcohol, available as Lanette 22 (ex Henkel).
  • the fatty complexing agent is present in an amount of from 0.1% to 15% by weight based on the total weight of the composition. More preferably, the fatty component is present in an amount of from 0.2 to 10%, most preferably from 0.25 to 5%, e.g. 0.3 to 4% by weight.
  • compositions further comprise a nonionic surfactant. Typically these can be included for the purpose of stabilising the compositions.
  • Suitable nonionic surfactants include addition products of ethylene oxide and/or propylene oxide with fatty alcohols, fatty acids and fatty amines.
  • Suitable surfactants are substantially water soluble surfactants of the general formula: R-Y-(C 2 H 4 O) z - C 2 H 4 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.
  • nonionic surfactants examples follow.
  • the integer defines the number of ethoxy (EO) groups in the molecule.
  • deca-, undeca-, dodeca-, tetradeca-, and pentadeca-ethoxylates of n-hexadecanol, and n-octadecanol having an HLB within the range recited herein are useful viscosity/ dispersibility modifiers in the context of this invention.
  • Exemplary ethoxylated primary alcohols useful herein as the viscosity/dispersibility modifiers of the compositions are C 18
  • the ethoxylates of mixed natural or synthetic alcohols in the "tallow" chain length range are also useful herein. Specific examples of such materials include tallow alcohol-EO(11), tallow alcohol-EO(18), and tallow alcohol-EO (25), coco alcohol-EO(10), coco alcohol-EO(15), coco alcohol-EO(20) and coco alcohol-EO(25).
  • deca-, undeca-, dodeca-, tetradeca-, pentadeca-, octadeca-, and nonadeca-ethoxylates of 3-hexadecanol, 2-octadecanol, 4-eicosanol, and 5-eicosanol having an HLB within the range recited herein are useful viscosity and/or dispersibility modifiers in the context of this invention.
  • Exemplary ethoxylated secondary alcohols useful herein as the viscosity and/or dispersibility modifiers of the compositions are: C 16 EO(11); C 20 EO(11); and C 16 EO(14).
  • Branched chain primary and secondary alcohols which are available from the well-known "OXO" process can be ethoxylated and employed as the viscosity and/or dispersibility modifiers of compositions herein.
  • Suitable polyol based surfactants include sucrose esters such sucrose monooleates, alkyl polyglucosides such as stearyl monoglucosides and stearyl triglucoside and alkyl polyglycerols.
  • the nonionic surfactant is preferably present in an amount from 0.01 to 10%, more preferably 0.1 to 5%, most preferably 0.35 to 3.5%, e.g. 0.5 to 2% by weight, based on the total weight of the composition.
  • co-active softeners may also be incorporated in an amount from 0.01 to 20% by weight, more preferably 0.05 to 10%, based on the total weight of the composition.
  • Preferred co-active softeners include fatty esters, and fatty N-oxides.
  • Preferred fatty esters include fatty monoesters, such as glycerol monostearate. If GMS is present, then it is preferred that the level of GMS in the composition, is from 0.01 to 10 wt%, based on the total weight of the composition.
  • the co-active softener may also comprise an oily sugar derivative.
  • oily sugar derivatives Suitable oily sugar derivatives, their methods of manufacture and their preferred amounts are described in WO-A1-01/46361 on page 5 line 16 to page 11 line 20, the disclosure of which is incorporated herein.
  • compositions comprise one or more polymeric viscosity control agents.
  • Suitable polymeric viscosity control agents include nonionic and cationic polymers, such as hydrophobically modified cellulose ethers (e.g. Natrosol Plus, ex Hercules), cationically modified starches (e.g. Softgel BDA and Softgel BD, both ex Avebe).
  • a particularly preferred viscosity control agent is a copolymer of methacrylate and cationic acrylamide available under the tradename Flosoft 200 (ex SNF Floerger).
  • Nonionic and/or cationic polymers are preferably present in an amount of 0.01 to 5wt%, more preferably 0.02 to 4wt%, based on the total weight of the composition.
  • compositions may also contain one or more optional ingredients conventionally included in liquid rinse fabric conditioning compositions such as pH buffering agents, perfume carriers, fluorescers, colourants, hydrotropes, antifoaming agents, antiredeposition agents, polyelectrolytes, enzymes, optical brightening agents, anti-shrinking agents, anti-spotting agents, antioxidants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents, ironing aids and dyes.
  • optional ingredients conventionally included in liquid rinse fabric conditioning compositions such as pH buffering agents, perfume carriers, fluorescers, colourants, hydrotropes, antifoaming agents, antiredeposition agents, polyelectrolytes, enzymes, optical brightening agents, anti-shrinking agents, anti-spotting agents, antioxidants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents, ironing aids and dyes.
  • the lubricant and the particulate phases in the compositions of the invention can be in a fully dispersed state, partially flocculated or associated in the form of a Pickering emulsion where the particles stud the surface of the emulsion or liposome droplets to form a nanoparticle-droplet composite - studded particles.
  • the composition may be prepared according to any suitable method.
  • the nanoparticle dispersion plus the lubricant emulsion or microemulsion if needed can be post dosed into the fabric softening base after it is manufactured with minimum agitation to prevent flocculation.
  • the nanoparticle phase at the required level can be post-dosed into an off-the-shelf ready fabric conditioner.
  • the product preferably comprises a liquid, preferably an aqueous liquid.
  • the composition can be a rinse cycle fabric care composition for use in a conventional automatic washing machine.
  • the AATCC 128 Wrinkle Recovery Test is that most widely used to determine the wrinkle recovery of garments and is referenced widely in the external literature.
  • a test fabric is wrinkled under standard conditions of load, time and environmental conditions using a standard Wrinkle Recovery Tester model 155 device supplied by James H Heal & Co Ltd ( Figure 1 ).
  • Figure 2 shows this 3D AATCC 128 wrinkle scale.
  • the existing AATCC 128 3D standards cannot allow a panellist to distinguish fine differences in intensity of wrinkling. For example in in-wear wrinkling the range of wrinkle falls around 2.5 to 3.5 but the 128 scale covers the broad brush scale of 1 to 5 missing details in the 2.5-3.5 range of interest.
  • test solution is prepared with the desired strength or the desired % owf and stabilised overnight on a roller bank.
  • the monitor is then weighed (W1), soaked in the test solution and compressed between the rollers of the Werner Mathis AG padder so that it weighs double its original weight.
  • the monitor is left to dry at controlled temperature and RH (20°C/65%RH) for 24 hours and then re-weighed (W2).
  • the weight of additive on the monitor is (W2 - W1) from which the %owf can be calculated.
  • the dry monitor is ironed flat using the Philips Azur 4000 iron on the hottest setting and with highest steam setting and left to condition for a further 24 hours at controlled T and RH (20°C/65%RH).
  • control monitors for comparison with the composition treated monitors.
  • These control monitors are treated with demineralised water instead of the compositions and prepared in the same way.
  • the monitors are loaded onto a Wrinkle Recovery Tester model 155 so that the warp direction is vertical.
  • the fabric is then compressed (wrinkled) using no additional weight for 8 minutes.
  • a digital photograph image is taken of each monitor using a Nokia Digital Camera under identical lighting conditions.
  • the standard lighting conditions are achieved using a Verivide Crease Imaging Cabinet.
  • the images are then loaded into a panelling programme and each image is presented to the panellist to score against_images of the scale being used - either AATCC128 or U Scale.
  • the formulations in the following Table 1 were prepared by co-melting the quaternary ammonium fabric softening material, tallow alcohol, and nonionic, heating water and adding the co-melt to the water under stirring to form a homogeneous mixture, allowing the mixture to cool and then adding the dye/perfume and preservative at 40°C. The mixture was allowed to cool further and then the silica dispersion was post-dosed with stirring.
  • Example 1 Example 2
  • Example A Tetranyl AHT-1 (1) 14.94 6.035 14.94 Genapol C200 (2) 0.38 0.10 0.38 Hydronol D(3) 1.00 0.20 1.00 silica(4) 10.96 4.43 - polymer (5) - 0.030 - Dye/perfume/pr eservative minor minor minor water to 100 to 100 to 100
  • Tetranyl AHT-1 is a fully hardened tallow triethanolamine quaternary fabric softener supplied by KAO at 85% active level
  • Genapol C200 is a coco (C9-C11) 20EO nonionic (Clariant)
  • Hydrenol D (Cognis) is a fully hardened vegetable derived C16-C18 fatty alcohol.
  • C820 is a 11% silica dispersion in water (Ciba) with 22 nm size silica particles.
  • the quantities in the table show the amount of silica.
  • Natrasol 331 a hydrophobically modified hydroxy ethyl cellulose.
  • Example A silica (C820) Water Quat : silica ratio 1:0 1.3:1 0:1 Control Score 2.86 3.39 3.53 3.17
  • Table 3 characterises the fabric handle obtained using the formulations.
  • a lower 2HG5 score means that there is a more elastic response when a shearing force is applied to the treated fabric.
  • a lower G score means that a lower level of stiffness is experienced when a shearing force is applied.
  • Table 3 Kawabata shear hysteresis (2HG5)and shear rigidity (G) data. % owf Example A Example 1 Silica (C820) water control 0.3% (2HG5) 10.60 6.30 12.36 10.807 0.3% (G) 1.98 1.68 2.49 2.00
  • the formulations reported in the following Table 4 were prepared by mixing a silica dispersion with off-the-shelf fabric conditioning compositions.
  • the silica dispersions was Ludox SP532-10519 a 40% silicon dispersion with 50 nm particle size ex Grace Davison.
  • the fabric conditioning compositions were:
  • Another class of lubricant-particle blends belong to the MQ silicone resin class from Dow Corning shown in Tables 5 and 6.
  • the intensity of wrinkling is reduced compared to untreated after 1 hr and 24hrs at the preferred deposition levels.
  • Table 5 U scale wrinkle scores after 1 hr and 24hrs for o/w emulsion of silicone oil/silicone resin blends using cationic emulsifier.
  • Tables 5 and 6 the composition of the internal phase of the emulsions is the same. They differ in the type of surfactant used for emulsification.
  • Table 7 shows the composition of the oil and water phases of the emulsions.
  • the PDMS/resin blends in D5 are mixed with water and emulsifier (not shown in Table 7).
  • Table 7 Composition of PDMS/resin blend in emulsions. Ingredient % in composition Water 50 D5 25 PDMS / Resin blend 25
  • Siloxane resin consisting of monovalent trisiloxy (M) groups having formula R 3 SiO 1/2 and tetravalent siloxy (Q) groups having formula SiO 4/2 and the polymer is amino functionalised PDMS with some degree of OH termination of viscosity 4000 mPa s.
  • Table 8 provides the droplet sizes of the resin blend emulsions used in Tables 8 and 9. Table 8. Emulsion droplet Size of PDMS/silicone resin polymer blends. PDMS/MQ blend ratio Surfactant Type PSD (nm) 40/60 Nonionic 139 30/70 Nonionic 129 20/80 Nonionic 161 40/60 Cationic 116 30/70 Cationic 154 20/80 Cationic 139
  • the silicon resin blend treated monitors showed better softness and handle compared to silica at equal add-on level. Their ease of ironing was also improved compared to the silica.

Landscapes

  • 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)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

L’invention a pour objet une composition de traitement du tissu destinée à être utilisée pendant le cycle de rinçage d’un lave-linge afin de réduire les faux plis que forment les tissus lorsqu’ils sont portés et comprenant : a) une dispersion de nanoparticules dont la grandeur particulaire moyenne varie de 5 à 500 nm, b) une phase lubrifiante sélectionnée parmi un assouplissant cationique, une huile de silicone, une huile de polyester de saccharose et des mélanges de ces composants et c) de l’eau dans laquelle le rapport massique de a) : b) varie de 3 : 1 à 1 : 3.

Claims (19)

  1. Composition de traitement du tissu destinée à une utilisation dans le cycle de rinçage d'une machine à laver pour réduire le froissement du tissu lorsqu'il est porté, la composition comprenant :
    a) une dispersion de nanoparticules comprenant des particules ayant une taille moyenne de particules dans la plage de 5 à 500 nm,
    b) une phase lubrifiante choisie parmi un adoucissant cationique du tissu, une huile de silicone, une huile de polyester de saccharose et les mélanges de ceux-ci, et
    c) de l'eau,
    dans laquelle le rapport en poids de a) : b) est dans la plage de 3:1 à 1:3, et dans laquelle la dispersion de nanoparticules est une dispersion colloïdale cationique ou neutre de silice.
  2. Composition de traitement du tissu selon la revendication 1, dans laquelle le rapport en poids de a) : b) est dans la plage de 2:1 à 1,5:1.
  3. Composition de traitement du tissu selon la revendication 1 ou la revendication 2, dans laquelle toutes les particules de la dispersion de nanoparticules ont une taille de particules inférieure à 500 nm.
  4. Composition de traitement du tissu selon l'une quelconque des revendications précédentes, dans laquelle toutes les particules de la dispersion de nanoparticules ont une taille de particules inférieure à 100 nm.
  5. Composition de traitement du tissu selon l'une quelconque des revendications précédentes, dans laquelle les particules de la dispersion de nanoparticules ont une taille moyenne de particules dans la plage de 10 à 50 nm.
  6. Composition de traitement du tissu selon l'une quelconque des revendications précédentes, dans laquelle l'huile de silicone comprend du polydiméthylsiloxane.
  7. Composition aqueuse d'assouplissement du tissu selon l'une quelconque des revendications précédentes, dans laquelle le composé d'assouplissement du tissu est un composé d'ammonium quaternaire.
  8. Composition aqueuse d'assouplissement du tissu selon la revendication 7, dans laquelle le composé d'assouplissement du tissu comprend un composé d'ammonium quaternaire ayant des liaisons ester.
  9. Composition aqueuse d'assouplissement du tissu selon la revendication 8, dans laquelle le composé d'assouplissement du tissu comprend un composé de triéthanolamine-ammonium à base de suif.
  10. Composition aqueuse d'assouplissement du tissu selon l'une quelconque des revendications précédentes, dans laquelle le polyester de saccharose est dérivé de l'huile de palmiste ou de l'huile de soja.
  11. Composition aqueuse d'assouplissement du tissu selon l'une quelconque des revendications précédentes, dans laquelle la phase lubrifiante b) est présente dans une proportion de 0,5 à 20 % en poids de la composition.
  12. Composition aqueuse d'assouplissement du tissu selon l'une quelconque des revendications précédentes, qui comprend de plus un alcool gras ou un acide gras contenant de 8 à 22 atomes de carbone.
  13. Composition aqueuse d'assouplissement du tissu selon la revendication 12, qui comprend de 0,3 à 2 % en poids d'un alcool gras en C16-C18.
  14. Composition aqueuse d'assouplissement du tissu selon l'une quelconque des revendications précédentes, qui comprend de plus de 0,01 à 10 % en poids d'un tensioactif non ionique.
  15. Composition aqueuse d'assouplissement du tissu selon la revendication 14, dans laquelle le tensioactif non ionique est un produit d'addition d'oxyde d'éthylène et/ou d'oxyde de propylène avec un alcool gras, un acide gras ou une amine grasse.
  16. Procédé de traitement d'un tissu, qui comprend l'application d'une composition selon l'une quelconque des revendications précédentes dans une quantité permettant de déposer de 0,2 à 4 pour cent en poids du total de la phase particulaire et de la phase lubrifiante et, par la suite, le séchage du tissu.
  17. Procédé selon la revendication 16, dans lequel la composition est appliquée dans une quantité permettant de déposer de 0,5 à 2 pour cent en poids du total de la phase particulaire et de la phase lubrifiante.
  18. Procédé selon la revendication 16 ou la revendication 17, dans lequel la composition est appliquée pendant le cycle de rinçage d'une machine à laver.
  19. Procédé selon l'une quelconque des revendications 16 à 18, comprenant l'étape supplémentaire de repassage du tissu.
EP06723210A 2005-03-18 2006-02-28 Compositions d entretien pour tissus Not-in-force EP1859016B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL06723210T PL1859016T3 (pl) 2005-03-18 2006-02-28 Kompozycje przeznaczone do pielęgnacji tkanin

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB0505619.7A GB0505619D0 (en) 2005-03-18 2005-03-18 Fabric care compositions
PCT/EP2006/001971 WO2006097207A1 (fr) 2005-03-18 2006-02-28 Compositions d’entretien pour tissus

Publications (2)

Publication Number Publication Date
EP1859016A1 EP1859016A1 (fr) 2007-11-28
EP1859016B1 true EP1859016B1 (fr) 2012-05-16

Family

ID=34531500

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06723210A Not-in-force EP1859016B1 (fr) 2005-03-18 2006-02-28 Compositions d entretien pour tissus

Country Status (9)

Country Link
EP (1) EP1859016B1 (fr)
CN (1) CN101142306B (fr)
AR (1) AR053178A1 (fr)
CA (1) CA2595362A1 (fr)
ES (1) ES2388072T3 (fr)
GB (1) GB0505619D0 (fr)
PL (1) PL1859016T3 (fr)
WO (1) WO2006097207A1 (fr)
ZA (1) ZA200705505B (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070130694A1 (en) * 2005-12-12 2007-06-14 Michaels Emily W Textile surface modification composition
CA2646543A1 (fr) * 2006-03-21 2007-09-27 The Procter & Gamble Company Nanofluides en tant que compositions de nettoyage pour le nettoyage de surfaces tachees, procede de formulation et utilisation
CN102124092B (zh) * 2008-08-15 2014-06-18 宝洁公司 包含聚甘油酯的有益组合物
CN102712876B (zh) * 2009-10-07 2014-03-12 荷兰联合利华有限公司 织物调理剂
JP2013543543A (ja) 2010-09-20 2013-12-05 ザ プロクター アンド ギャンブル カンパニー 非フルオロポリマー表面保護組成物
EP2431402B1 (fr) 2010-09-20 2013-09-18 Wacker Chemie AG Mélanges comprenant des polyorganosiloxanes à base d'aminoalkyle et résines de silicone
WO2012040171A1 (fr) 2010-09-20 2012-03-29 The Procter & Gamble Company Composition de protection des surfaces exempte de polymère fluoré
EP2431421B1 (fr) 2010-09-20 2013-11-06 Wacker Chemie AG Mélanges aqueux comprenant des polyorganosiloxanes à base d'aminoalkyle et résines de silicone
WO2013107583A1 (fr) * 2012-01-19 2013-07-25 Unilever Plc Procédé et composition de traitement de tissu
GB2507750A (en) * 2012-11-07 2014-05-14 Intelligent Fabric Technologies Plc Fabric softener with colloidal silica for imparting stain resistant properties

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5174912A (en) * 1990-07-23 1992-12-29 The Procter & Gamble Company Microemulsified silicones in liquid fabric care compositions containing dye
DE19961939A1 (de) * 1999-12-22 2001-06-28 Cognis Deutschland Gmbh Verwendung von nanoskaligen kationischen Verbindungen
FR2813313B1 (fr) * 2000-08-25 2007-06-15 Rhodia Chimie Sa Composition a base de nanoparticules ou de nanolatex de polymeres pour le soin du linge
EP1371718A1 (fr) * 2002-06-14 2003-12-17 Rohm And Haas Company Compositions de nanoparticules polymériques et leur emploi comme additifs d'entretien de tissus
DE10248583A1 (de) * 2002-10-17 2004-04-29 Nanogate Technologies Gmbh Textilbehandlungsmittel
US20040152616A1 (en) * 2003-02-03 2004-08-05 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Laundry cleansing and conditioning compositions

Also Published As

Publication number Publication date
EP1859016A1 (fr) 2007-11-28
CN101142306A (zh) 2008-03-12
CA2595362A1 (fr) 2006-09-21
GB0505619D0 (en) 2005-04-27
AR053178A1 (es) 2007-04-25
CN101142306B (zh) 2012-08-01
ES2388072T3 (es) 2012-10-08
PL1859016T3 (pl) 2012-10-31
WO2006097207A1 (fr) 2006-09-21
ZA200705505B (en) 2008-10-29

Similar Documents

Publication Publication Date Title
EP1859016B1 (fr) Compositions d entretien pour tissus
US20090050838A1 (en) Fabric Care Compositions
CA2745628C (fr) Ameliorations se rapportant a des agents de traitement de tissus
US20100184634A1 (en) Process For Preparing Fabric Softener Compositions
MXPA01011893A (es) Composiciones suavizantes de telas.
EP3172299A1 (fr) Compositions de traitement pour le linge et l'entretien ménager
US7060666B2 (en) Fabric conditioning composition
AU769162B2 (en) Siloxane emulsions
CA2435931C (fr) Composes de conditionnement de tissus comportant de l'ammoniaque quaternaire a liaison ether et un agent complexant gras
JP4982487B2 (ja) 折り目形成を低減するためのシロキサン含有調製物
JP4101751B2 (ja) 布帛に防しわ効果を提供する布帛ケア系
EP1646707B1 (fr) Utilisation d'un tensioactif non ionique dans une composition de traitement du linge
KR102133808B1 (ko) 카르바메이트 작용화된 오르가노폴리실록산 및 양이온성 계면활성제를 포함하는 조성물
MXPA04002239A (es) Composiciones acondicionadoras de telas.
GB2429979A (en) Reducing leakage in encapsulated perfumes
ZA200109568B (en) Fabric softening compositions.
EP1746153A1 (fr) Perfectionnements au lavage du linge
WO2003052035A1 (fr) Utilisation de compositions de conditionnement pour tissus contenant un compose d'ammonium quaternaire
GB2230787A (en) Aqueous polysiloxane compositions and process for the treatment of textiles

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20070605

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: UNILEVER PLC

Owner name: UNILEVER N.V.

DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: UNILEVER PLC

Owner name: UNILEVER N.V.

17Q First examination report despatched

Effective date: 20090525

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 558102

Country of ref document: AT

Kind code of ref document: T

Effective date: 20120615

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602006029452

Country of ref document: DE

Effective date: 20120719

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20120516

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2388072

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20121008

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

Effective date: 20120516

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120516

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120516

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120516

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120916

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120516

REG Reference to a national code

Ref country code: PL

Ref legal event code: T3

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 558102

Country of ref document: AT

Kind code of ref document: T

Effective date: 20120516

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120817

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120917

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120516

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120516

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120516

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120516

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120516

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120516

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120516

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120516

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120516

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120516

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20130219

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602006029452

Country of ref document: DE

Effective date: 20130219

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120816

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130228

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130228

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130228

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130228

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PL

Payment date: 20140203

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20060228

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130228

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 11

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150228

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20170217

Year of fee payment: 12

Ref country code: DE

Payment date: 20170217

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20170216

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20170213

Year of fee payment: 12

Ref country code: IT

Payment date: 20170221

Year of fee payment: 12

Ref country code: TR

Payment date: 20170214

Year of fee payment: 12

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602006029452

Country of ref document: DE

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20180228

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20181031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180901

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180228

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180228

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180228

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20190801

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180301

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180228